1. A preparation method of a polymer array structure film is characterized by comprising the following steps:

step 1: spin-coating photoresist on a silicon wafer, forming a target pattern mask after exposure and development by using a photoetching machine, and then etching the silicon wafer without a photoresist pattern area to obtain a silicon template;

step 2: and spin-coating polydimethylsiloxane solution on the surface of the silicon template, and curing and demolding to obtain the polymer array structure film.

2. The method of claim 1, wherein the silicon template has a micro-scale array of pore structures.

3. The method according to claim 1, wherein the polydimethylsiloxane solution is prepared by a method comprising the steps of:

mixing the prepolymer with a curing agent, and then putting the mixture into a vacuum box to remove bubbles;

the vacuum degree of the vacuum box is 133Pa, and the vacuum time is 30 min.

4. The production method according to claim 3, wherein the mass ratio of the prepolymer to the curing agent is 8: 1-16: 1.

5. the method according to claim 1, wherein before the curing in step 2, the method further comprises: placing the silicon template spin-coated with the polydimethylsiloxane solution in a vacuum box;

the vacuum degree of the vacuum box is 133Pa, and the vacuum time is 30 min.

6. The method of claim 1, wherein the curing is photo-curing;

the curing temperature is 100 ℃ and the curing time is 45 min.

7. The method according to claim 1, wherein after obtaining the silicon template in step 1, the method further comprises: c4Fs was sputtered onto the silicon template surface.

8. The method according to claim 1, wherein the exposure time in step 1 is 7 s;

the development time was 45 s;

the etching rate is 2 μm/min.

9. Use of the polymer array structure film prepared by the preparation method of any one of claims 1 to 8 in a stimuli-responsive material.

10. A composite membrane, comprising: the polymer array structure membrane prepared by the preparation method of any one of claims 1 to 8, and polydiacetylene micelle gel disposed on the surface of the polymer array structure membrane.

Background

The polymer micro-nano array structure is a structure system formed by combining organic synthesis and material science and selecting corresponding micro-nano structure units such as micro-nano holes and the like on a certain substrate according to a certain rule, is an important component of a micro-nano material system, and is also one of important leading-edge subjects in the fields of modern organic chemistry and material chemistry. The polymer micro-nano array structure not only has inherent properties of micro-nano structure unit materials, but also has performance characteristics which some isolated units do not have. The biomimetic principle is utilized to guide the organic synthesis of special materials, namely, the preparation of polymer micro-nano arrays and the performance of the polymer micro-nano arrays are simulated or utilized to research the structure, the function and the biochemical process of organisms and the application to material design are inspired by the special structure and the function of the natural organism, so as to obtain new materials which are close to or exceed the superiority of the biological materials, or a natural biosynthesis method is utilized to obtain required materials. The polymer micro-nano array structure has wide application prospects in the aspects of gecko-foot-imitated high-adhesiveness materials, lotus leaf-imitated self-cleaning super-hydrophobic materials, organic catalysis, information science, biotechnology and the like.

However, the existing preparation of the polymer array structure film has the problems of complicated preparation steps, high preparation difficulty, difficulty in one-step forming and small production capacity.

Disclosure of Invention

In view of the above, the present invention provides a method for preparing a polymer array structure film and applications thereof, wherein the method can be designed according to array structure arrangement requirements to obtain a desired polymer array structure film.

The specific technical scheme is as follows:

the invention provides a preparation method of a polymer array structure film, which comprises the following steps:

step 1: spin-coating photoresist on a silicon wafer, forming a target pattern mask after exposure and development by using a photoetching machine, and then etching the silicon wafer without a photoresist pattern area to obtain a silicon template;

step 2: and spin-coating polydimethylsiloxane solution on the surface of the silicon template, and curing and demolding to obtain the polymer array structure film.

The invention takes polydimethylsiloxane as a preparation raw material and adopts a template method to prepare the polymer array structure membrane. The template method is a technology for synthesizing a novel polymer micro-nano array structure by a series of technologies by selecting a micro-nano structure array with a certain regular arrangement as a template. That is, an array of holes with a certain depth and diameter is made on a certain material by a proper method, and the hole array has a certain distribution rule and a certain interval. And pouring a layer of liquid or colloid polymer on the female die template, carrying out polymerization or condensation reaction curing molding, and removing the template to obtain the micro-nano array structure corresponding to the template. Generally, a micro-nano structure array in a certain regular arrangement can be formed by a self-organization method or an etching method. The template method not only utilizes the characteristics of simplicity and convenience of the self-organization method, but also utilizes the chemical etching method to easily control the form of the micro-nano array, and also overcomes the defect that the self-organization method is only suitable for specific materials and specific form systems, thereby being beneficial to the synthesis of the multiple organic polymer ordered array structure and the control of the form thereof. For example, an alumina template synthesized by a self-organization method, porous silicon synthesized by a chemical etching method and an ordered pore template synthesized by a micro-contact printing method can be used for synthesizing various polymer micro-nano array structures.

In step 1 of the invention, the exposure time is 7 s; the development time is 45 s; the etching reaction gas is SF₆(ii) a The etching rate is 2 μm/min.

The silicon template obtained in step 1 of the invention is in a micron-sized pore structure.

In order to prevent the microstructure of the PDMS film from being damaged due to excessive adhesion force in the demolding process, the invention further comprises the following steps before the step 2: octafluorocyclobutane C4Fs is sprayed onto the surface of the silicon template to reduce the adhesion between the array structure film and the silicon template, so that the array structure film is more easily peeled off from the silicon template.

In step 2 of the present invention, the preparation method of the polydimethylsiloxane solution comprises the following steps:

mixing the prepolymer with a curing agent, and then putting the mixture into a vacuum box to remove bubbles;

the mass ratio of the prepolymer to the curing agent is 8: 1-16: 1, preferably 10: 1;

the vacuum degree of the vacuum box is 133Pa, and the vacuum time is 30 min.

In step 2 of the present invention, after spin coating a polydimethylsiloxane solution on the surface of the silicon template, the method further comprises: placing the silicon template spin-coated with the polydimethylsiloxane solution in a vacuum box;

the vacuum degree of the vacuum box is 133Pa, and the vacuum time is 60 min.

In step 2 of the invention, the curing temperature is 100 ℃ and the curing time is 45 min.

In step 2 of the present invention, the stripping specifically comprises: and cooling at room temperature after the curing is finished, taking the lower support after the PDMS array structure film is cooled to the room temperature, and then slowly stripping the PDMS array structure film from the silicon plate at the edge of the PDMS array structure film by using tweezers, thereby finally obtaining the PDMS structure film with the microstructure array.

The invention also provides a polymer array structure film prepared by the preparation method.

The polymer array structure film prepared by the invention can be applied to the fields of response materials, nano displays, flexible displays and bionics.

Other functional materials can be added into the polymer array structure film provided by the invention, so that the polymer array structure film has certain functions. For example: adding a fluorescent molecule into the polymer array structure film, and displaying fluorescence under special illumination; and adding responsive molecules into the polymer array structure film to enable the polymer array structure film to have a temperature prompting function.

In the invention, the other functional materials are added into the prepared PDMS mixed solution.

The invention also provides application of the polymer array structure membrane prepared by the preparation method in a stimulus response material.

The invention also provides a composite membrane, which comprises the polymer array structure membrane prepared by the preparation method and polydiacetylene micelle gel arranged on the surface of the polymer array structure membrane.

The polydiacetylene micelle gel has poor mechanical property, the PDMS array structure film provided by the invention can provide support for the polydiacetylene micelle gel, and the PDMS array structure film is transparent and has an array structure, so that the PDMS film and the polydiacetylene micelle gel composite film can generate fluorescence under the stimulation of temperature and pH environment and have high sensitivity. According to the technical scheme, the invention has the following advantages:

the invention provides a preparation method of a polymer array structure film, which takes polydimethylsiloxane as a raw material and adopts a template method to prepare the array structure film. The array structure film is a PDMS structure film, is a flexible film, can be deformed at will and can also keep a structure. The micro-nano structure on the surface of the PDMS structural film has excellent optical property, electrochemical property, biological property and the like; the design of the micro-nano structure on the surface of the PDMS structure film not only increases the contact surface of the surface, but also increases the friction force, and is more favorable when other materials are spin-coated (for example, the polydimethylsiloxane film is designed to have an array structure on the surface, which is favorable for the attachment of polydiacetylene micelle gel and better optical property). Moreover, the flexible backbone of PDMS plus side chain groups that act as a barrier to the backbone give it a number of excellent properties: the composite material has the advantages of low surface energy, good affinity and hydrophobicity, good permeability, high chemical stability, high solvent resistance, good heat resistance and cold resistance, good adhesive property, good insulativity, good elasticity and optical property, durability, reusability and low price, and can be widely applied to the fields of micro-nano manufacturing, elastomer molds, microelectronic industry, nano imprinting, optical detection, soft lithography technology and the like. In addition, the preparation method of the polymer array structure film can be designed according to the array structure arrangement requirement, and the required polymer array structure film is obtained. The preparation method is simple and quick to operate, can be used for large-scale mass molding at one time, and is quick and simple.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.

FIG. 1 is a flow chart showing the production of a polymer array structure film in example 1 of the present invention;

FIG. 2 is a schematic diagram of a silicon template according to example 1 of the present invention;

FIG. 3 is an SEM photograph of a silicon template in example 1 of the present invention, wherein (a) is 10 μm, (b) is 2 μm, and (c) is 1 μm;

FIG. 4 is a flow chart of spin-on silicon template in example 1 of the present invention;

FIG. 5 is a schematic representation of a polymer array structured film according to example 1 of the present invention;

FIG. 6 is an SEM photograph of a polymer array structure film according to example 1 of the present invention, wherein (a) is 50 μm and (b) is 10 μm.

FIG. 7 is a flow chart of the preparation of the PDMS film and the polydiacetylene micelle gel composite film prepared in example 2 of the present invention;

FIG. 8 is a diagram of the UV-VIS absorption spectrum of the PDMS film and the polydiacetylene micelle gel composite film prepared in example 2 according to the present invention;

FIG. 9 is a fluorescence spectrum of a PDMS film and a polydiacetylene micelle gel composite film prepared in example 2 of the present invention;

FIG. 10 is a UV-VIS absorption spectrum of a polydiacetylene micelle gel quartz plate prepared in comparative example 1 of the present invention;

FIG. 11 is a fluorescence spectrum of a quartz plate of polydiacetylene micelle gel prepared in comparative example 1 of the present invention.

Detailed Description

In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the embodiment of the invention, octafluorocyclobutane is purchased from Shenzhen Jingu gas Co.

In inventive example 1, the prepolymer and curing agent were obtained from Dow Corning SYLGARD84 silicone rubber, including PDMS SYLGUARD-184A as the base and SYLGUARD-184B as the curing agent.

Example 1

This example is a preparation of a PDMS polymer array structure film (as shown in fig. 1), and the specific preparation steps are as follows:

1. fabrication of silicon template

Cleaning inorganic and organic pollutants on the surface of a silicon wafer by concentrated sulfuric acid and acetone respectively, then spin-coating photoresist on the silicon wafer, exposing in a photoetching machine, developing by a developing solution to form a target pattern mask, and then using in a deep silicon etching machineAnd etching the silicon without the photoresist pattern region by using a BOSCH process to reach a target depth, removing the photoresist by using acetone and isopropanol, and completing the preparation of the silicon template (the diameter of the silicon template is 10cm, the depth of the array hole on the surface of the silicon template is 10 microns, and the length and the width of the array hole are both 5 microns). The photoresist model: AZ 5214; the exposure time was 7 seconds and the development time was 45 seconds. Etching reaction gas: SF₆And the etching rate is as follows: 2 μm/min.

FIG. 2 is a schematic diagram of a silicon template according to the present embodiment; FIG. 3 is an electron scanning microscope photograph of the silicon template of the present embodiment. As can be seen in fig. 3, the array hole structure of the silicon template surface.

2. And sputtering octafluorocyclobutane on the surface of the silicon template for 120 s.

3. Preparing PDMS mixed solution

Mixing the prepolymer and the curing agent in a mass ratio of 10: mixing at a ratio of 1, stirring thoroughly until the two are completely mixed, and vacuumizing in a vacuum chamber with a vacuum degree of 133Pa for 30min to remove bubbles in the mixed solution.

4. Spin-coated PDMS film

As shown in fig. 4, the spin-coating of the PDMS film is divided into four process diagrams (a) in which when the PDMS colloid is just dropped into the silicon template, the PDMS colloid gradually forms droplets with specific shapes under the action of surface tension and adhesion force: the second process is an adsorption spin coating process, wherein (b) is that the silicon template is fixed on a vacuum chuck in a vacuum adsorption mode, and a spin coating experiment is started; the third stage is the spreading process of the PDMS colloid, and (c) shows that the centrifugal force applied to the PDMS colloid is larger than the adhesion force due to the rotation of the silicon template. The silicon template is radially and outwardly spread on the surface of the silicon template to form a film with uniform thickness, but the silicon template is required to be subjected to bubble removal treatment because of small holes of a microstructure array, and is placed in a vacuum box with the vacuum degree of about 133Pa for vacuumizing for 30min to remove bubbles in PDMS colloid of the silicon template, remove the bubbles, and the third stage is repeated; and (d) curing PDMS (polydimethylsiloxane), namely placing the silicon template on a heating platform, carrying out photocuring on the PDMS, setting the heating temperature to be 100 ℃, and setting the curing time to be 45 min.

5. Demoulding

And (3) after heating, trying to cool, taking the lower support after the temperature of the PDMS is reduced to room temperature, and then slowly stripping the PDMS from the silicon plate at the edge of the PDMS mold by using tweezers to finally obtain the PDMS film with the microstructure array.

FIG. 5 is a schematic diagram of a PDMS film of the microstructure array of this embodiment. As can be seen from fig. 5, the PDMS film of the microstructure array is transparent.

FIG. 6 is an electron scanning microscope image of a PDMS film of the microstructure array of this embodiment. As can be seen from fig. 6, the PDMS film has a microarray structure.

Example 2

This embodiment is a preparation of a PDMS film and a polydiacetylene micelle gel composite film, and the specific preparation steps are shown in fig. 7.

The polydiacetylene micelle gel is heated to 50 ℃ and stirred continuously until the hydrogel is dissolved into liquid. The first process is a dropping process: placing a PDMS film on a spin coater, dropwise adding two drops of polydiacetylene micelle hydrogel by a dropper, wherein (a) in the figure is polydiacetylene micelle gel which gradually forms liquid drops with a specific form under the action of surface tension and adhesion force when the polydiacetylene micelle gel is just dropped on the PDMS film prepared in the embodiment; in the figure, (b) a silicon template is fixed on a vacuum chuck in a vacuum adsorption mode, and a spin coating experiment is started; the third stage is that the rotational speed of the spin coater is adjusted in the spreading process of the polydiacetylene micelle gel (firstly, the rotational speed is 200rpm for 30s, and the high speed is 0; in the figure, (c), the centrifugal force borne by the polydiacetylene micelle gel is greater than the adhesive force, the polydiacetylene micelle gel can be spread outwards along the radial direction on the surface of the PDMS membrane to form a thin membrane with uniform thickness, but as the PDMS membrane has a microstructure array structure, the friction force is increased, and in the third stage, the fourth stage is repeated, the fourth stage is a thin membrane curing process (the thickness of the polydiacetylene micelle gel membrane is 50 mu m), and in the figure, (d), the polydiacetylene micelle gel is cooled for 24h at normal temperature, so that the PDMS membrane and the polydiacetylene micelle gel composite membrane (150 mu m) can be obtained.

Comparative example

Ultraviolet-visible light absorption and fluorescence test experiment of polydiacetylene micelle gel film on quartz plate

1. Cleaning method of quartz plate

Soaking the quartz plate in acetone solution, performing ultrasonic treatment for half an hour, washing with deionized water, and placing the quartz plate in H₂O₂: concentrated H₂SO₄1: 5 proportion of mixed solvent is heated and boiled for one hour. Washing with water, putting in ionized water, performing ultrasonic treatment for half an hour, taking out ammonia water: hydrogen peroxide: concentrated sulfuric acid is 1: 1: 5 the mixed solvent ratio is heated to boiling for one hour. Rinsing the quartz plate in ultrapure water, performing ultrasonic treatment on the quartz plate for half an hour by using deionized water for 3 times, and storing the quartz plate in the deionized water.

2. The polydiacetylene micelle gel film is compounded on a quartz plate

Heating a polydiacetylene micelle gel film in a water bath at 50 ℃, stirring continuously until the polydiacetylene micelle gel is dissolved, cleaning and debugging a spin coater, putting the spin coater on a quartz plate, dropwise adding two drops of hydrogel by using a dropper, adjusting the low-speed and high-speed rotating speed (the low speed is 200rpm and the high speed is 0), repeating the upper experiment, spin-coating a layer of thin hydrogel on the quartz plate (wherein the thickness of the quartz plate is 2mm, and the thickness of the polydiacetylene micelle gel is 50 mu m), manufacturing 8 quartz plates, placing a film on the quartz plate, taking out 6 samples, and irradiating for 10min under an ultraviolet lamp, observing that a polydiacetylene micelle gel composite film turns blue, and indicating that the polydiacetylene micelle gel has activity. And taking out two quartz plates, wherein one quartz plate is used for performing ultraviolet-visible light absorption spectrum, and the other quartz plate is used for performing fluorescence spectrum.

3. Testing of Polydiacetylene (PDA) micelle gel Membrane temperature

A beaker is filled with hot water of 100 ℃, 2 quartz plates containing gelatin gel of polydiacetylene are taken out, and the lower bottoms of the quartz plates are contacted with the hot water to form a heating process to keep the balance of the quartz plates. During heating, the gel began as a solution, changing color from blue to red. And (5) waiting for the hot water to cool to room temperature, and taking off 2 quartz plates to wait for the gel to solidify. One quartz plate is used for ultraviolet-visible light absorption spectrum, and the other quartz plate is used for fluorescence spectrum.

4. Testing of alkaline environment of polydiacetylene micelle gel composite membrane

Respectively adding 5ml of ammonia water into 2 10ml beakers, taking out quartz plates of blue polydiacetylene gelatin gel, respectively pouring the quartz plates on the beakers, slightly shaking the ammonia water in the beakers to enable white fog to appear in the beakers, observing that the hydrogel of the quartz plates turns red from blue, then taking down the quartz plates, making an ultraviolet-visible light absorption spectrum on one quartz plate, and making a fluorescence spectrum on the other quartz plate.

Test examples

Ultraviolet-visible light absorption and fluorescence test experiment

1. And taking 8 PDMS films and the polydiacetylene micelle gel composite film prepared in the example 2, taking 6 samples, and placing the samples under an ultraviolet lamp for 10min to observe that the PDMS films turn blue. And taking out the two PDMS composite films, wherein one PDMS composite film is used for making an ultraviolet-visible light absorption spectrum, and the other PDMS composite film is used for making a fluorescence spectrum.

2. Test of temperature of PDMS film and polydiacetylene micelle gel composite membrane

Adding 100 ℃ hot water into a beaker, taking 2 composite films subjected to ultraviolet irradiation in the step 1, and enabling the lower bottom of the PDMS film to contact with the hot water to form a heating process and keep balance. During heating, the polydiacetylene micelle gel dissolves. The color changes from blue to red. After the hot water is cooled to room temperature, 2 PDMS films are taken off, and the polydiacetylene micelle gel is solidified. One PDMS film and the polydiacetylene micelle gel composite film are used for ultraviolet-visible light absorption spectrum, and the other PDMS film and the polydiacetylene micelle gel composite film are used for fluorescence spectrum.

3. Test of alkaline environment of PDMS (polydimethylsiloxane) film and polydiacetylene micelle gel composite membrane

Taking 2 composite films subjected to ultraviolet irradiation in the step 1, respectively adding 5ml of ammonia water into 2 10ml beakers, enabling the PDMS film and the polydiacetylene micelle gel composite film to cover the beakers, slightly shaking the ammonia water in the beakers to enable white fog to appear in the beakers, observing that hydrogel of the PDMS film and the polydiacetylene micelle gel composite film changes from blue to red, taking out the PDMS film and the polydiacetylene micelle gel composite film, enabling one PDMS film and the polydiacetylene micelle gel composite film to be used for ultraviolet-visible light absorption spectroscopy, and enabling the other PDMS film and the polydiacetylene micelle gel composite film to be used for fluorescence spectroscopy.

Three tests of the polydiacetylene micelle gel membrane quartz plate prepared in comparative example 1 were the same as in example 2.

Fig. 8 is an ultraviolet-visible light absorption spectrum curve of the PDMS film and the polydiacetylene micelle gel composite film after experimental tests. In the figure, B is the ultraviolet-visible light absorption spectrum curve of the PDMS film and the PDA micelle gel composite film without any treatment, the curve is close to a horizontal line, and no absorption peak exists. The ultraviolet-visible light absorption spectrum of the PDMS film and the PDA micelle gel composite film has no peak value under the condition of not passing through ultraviolet illumination with the wavelength of 265 nm; the curve D in the figure is an ultraviolet-visible light absorption spectrum curve of the PDMS film and the PDA micelle gel composite film after being irradiated for 10min by 265nm ultraviolet, two wave crests are arranged in the curve, namely a 540nm large wave crest and a 640nm small wave crest, and the spectrum is mainly embodied as a 640nm wave crest. The PDMS film and the PDA micelle gel composite film are irradiated by ultraviolet light to be blue. In the figure A, an ultraviolet-visible light absorption spectrum curve of an ultraviolet irradiation PDMS film and a PDA micelle gel composite film heated to above 70 ℃ in a water area exists, and a peak exists in the curve at 540nm of an ultraviolet absorption spectrum, and the other peaks do not exist. In the figure, C is an ultraviolet-visible light absorption spectrum curve of the ultraviolet irradiated PDMS film and the PDA micelle gel composite film in an alkaline environment, and a peak exists at the position where the ultraviolet absorption spectrum is 540 nm.

Fig. 9 is a fluorescence spectrum curve of the PDMS film and the PDA micelle gel composite film after experimental tests, with an excitation wavelength of 450, in which a is a curve of the PDMS film and the PDA micelle gel composite film processed under the irradiation of ultraviolet light with a wavelength of 265nm, the curve is close to a horizontal line, and there is no fluorescence peak. The fluorescence spectra of the PDMS film and the PDA micelle gel composite film after being irradiated by 265nm ultraviolet light have no peak value, and A can be regarded as a reference group in the experiment. In the figure B, the fluorescence intensity curve of the blue PDMS membrane and the PDA micelle gel composite membrane under the stimulation of an alkaline environment is shown, two wave peaks are arranged in the curve, the wave peaks are respectively 560nm wave peaks and 640nm wave peaks, and the blue PDA micelle gel is changed from non-fluorescence to red fluorescence after the PDMS membrane and the PDA micelle gel composite membrane become alkaline. In the figure C, the fluorescence intensity curve of the blue PDA micelle gel heated to above 70 ℃ by a water area has a 560nm peak, and the temperature is further raised, so that the blue PDMS film and the PDA micelle gel composite film fluoresce from no fluorescence to red fluorescence. Through fluorescence spectrum, the blue PDMS film and the PDA micelle gel composite film can be obtained to be red after being stimulated by temperature rise and alkaline environment.

FIG. 10 is an ultraviolet-visible light absorption spectrum of a polydiacetylene micelle gel membrane quartz plate, wherein A is an ultraviolet-visible light absorption spectrum curve of a PDA micelle gel without any treatment, the line is close to a horizontal line, which shows that the PDA micelle gel has no peak value of the ultraviolet-visible light absorption spectrum under the condition of not irradiating by ultraviolet light with the wavelength of 265nm, and group A is set as a reference group. In the figure B, the ultraviolet-visible light absorption spectrum curve of the PDA micelle gel under the condition of ultraviolet irradiation with the wavelength of 265nm for 10min has two wave peaks which are respectively a 640nm large wave peak and a 600nm small wave peak. The absorption wavelength of the PDA micelle gel with the visible wavelength of 265nm ultraviolet radiation is 640 nm; and after the PDA micelle gel is irradiated by ultraviolet light, the gel is blue. In the figure C, the ultraviolet-visible light absorption spectrum curve of the PDA micelle gel is heated to more than 70 ℃ in a water area after the PDA micelle gel is irradiated by ultraviolet, and the curve has a large peak at 540nm on the ultraviolet absorption spectrum and does not have peaks at other positions. In the figure, D is the ultraviolet-visible light absorption spectrum curve of the PDA micelle gel under the stimulation of alkaline environment by ultraviolet irradiation, and the curve has two peaks of 540nm and 640nm on the ultraviolet absorption spectrum.

In the overall experimental design, a is set as a blank group, and the other sample groups are experimental groups which change under the stimulation of the environment. When the PDA micelle gel is stimulated by ultraviolet illumination, the PDA micelle gel absorbs at 640nm, and the color of the micelle gel is changed from colorless to blue. The blue PDA micelle gel is stimulated by different conditions, and the ultraviolet absorption spectrum of the blue PDA micelle gel is greatly different. At ambient temperatures above 70 ℃, the PDA stimulus-responsive activity inside the PDA micelle gel will be excited, shifting the peak on the uv-absorption spectrum to the left, and causing the PDA micelle gel to appear red. When the PDA micelle gel is stimulated in an alkaline environment, the PDA stimulus response activity in the PDA micelle gel is also stimulated, and compared with the ultraviolet-visible light absorption spectrum of the untreated blue PDA micelle gel, a new 540nm absorption peak appears on the ultraviolet-visible light absorption spectrum under the stimulation of the alkaline environment, but the 640nm peak value is reduced.

FIG. 11 is the fluorescence spectrum of the quartz plate with polydiacetylene micelle gel membrane, the excitation wavelength is 450nm, and C is the fluorescence spectrum curve after being irradiated by ultraviolet light with the wavelength of 265nm, the curve is close to a horizontal line and has no fluorescence peak. The PDA micelle gel has no peak value in the fluorescence spectrum after being irradiated by ultraviolet light with the wavelength of 265nm, and C is a reference group in the experiment. In the graph A, the fluorescence spectrum curve of the blue PDA micelle gel heated to above 70 ℃ by a water area has two peaks of 560nm and 640nm respectively, which shows that the blue PDA micelle gel generates fluorescence from no fluorescence after being heated. In the graph B, the fluorescence spectrum curve of the blue PDA micelle gel stimulated by the alkaline environment is shown, and two peaks are arranged in the curve, wherein the two peaks are respectively 560nm and 640nm, which shows that the blue PDA micelle gel can be stimulated from no fluorescence to fluorescence by using the alkaline environment. The experimental results show that temperature and alkaline environmental stimulus can cause the PDA micelle gel to appear red.

Compared with a polydiacetylene micelle gel membrane quartz plate, the PDM film and the quartz plate support and load polydiacetylene micelle gel well, have good stimulus response characteristics, can generate fluorescence under the stimulus of temperature and pH environment, and have high sensitivity. Compared to quartz plates, PDMS films have very good flexibility and microstructures on the surface can increase PDA micelle gel adsorption.

The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.