Bionic functional organic electronic device comprising bionic functional sealed packaging layer and preparation method thereof

Abstract

The invention discloses a bionic functional organic electronic device comprising a bionic functional sealing packaging layer and a preparation method thereof, the organic biological electronic device uses a layer-by-layer deposition method, and functionalization of the sealing packaging layer is realized under the condition that the sealing packaging layer and electric leakage performance of the organic biological electronic device are not damaged; the organic bioelectronic device comprises a flexible substrate, a connecting line and a bionic functional sealing packaging layer, the bionic functional sealing packaging layer is of a double-layer structure, the bottom layer is unmodified poly-p-xylene, and the upper layer is zwitterionic group modified poly-p-xylene. According to the invention, zwitterionic group-containing functionalized poly-p-xylylene is introduced into the bionic functionalized sealing packaging layer, so that the sealing performance of the material is maintained, and the conformality in a non-specific adhesion and wet state is maximally resisted. The bionic functional sealing packaging layer can be matched with a photoetching technology, and can be applied to the preparation process of various high-resolution thin film electronic devices.

Description

Technical Field

[0001] The present invention relates to a bionic functional organic electronic device including a bionic functional sealing encapsulation layer and a preparation method thereof. The bionic functional sealing encapsulation layer can be integrated into the insulating material part of an electrode or a transistor in combination with photolithography printing technology, significantly improving the flexibility and adhesion of the device and effectively inhibiting nonspecific adhesion interference under complex biological environmental conditions. Background Art

[0002] Flexible thin-film bioelectronics have emerged as a new biomedical tool for life science research and novel therapeutic approaches. However, establishing controllable electrical coupling between these flexible devices and biological systems is extremely challenging. To achieve high spatial resolution monitoring and stable integration with biological systems, thin-film electronics are being developed towards high density, adaptable deformation, and biocompatibility.

[0003] However, one of the main obstacles to achieving the above goals is the mismatch in mechanical properties between hard planar electronics and soft biological systems, which makes it difficult for electronic devices to fit complex three-dimensional tissue surfaces and easily leads to interfacial stress. In order to minimize the negative effects of this mechanical mismatch, researchers have used flexible elastomeric substrates with a Young's modulus as low as 10kPa to manufacture bioelectronic devices. Due to the mechanical compliance of such materials, these thin-film electronics promote close integration with biological systems and have a wide range of applications in wearable electronics, medical diagnostics, and neurophysiology research. However, the permeability and long-term sealing properties of such materials have not been verified, which poses a challenge to their practical application. In addition, these organic elastomers are generally solution-processed and are easily damaged by organic solvents and ultraviolet radiation, which makes them incompatible with standard photolithography processes. Therefore, it is difficult to prepare high-density device arrays using such elastic materials. In addition to using flexible elastomeric materials, reducing the thickness of the film can reduce the bending stiffness of the film and improve the mechanical compliance of the film to complex surfaces. However, ultra-thin geometries can compromise the support and manipulability of the film in manufacturing and applications. In addition, reducing the film thickness may also increase the Young's modulus of the polymer film, which can lead to mechanical stress at the biointerface and promote the activation of immune cells. Therefore, the development of a novel hermetic encapsulation system that is both compatible and has a soft surface modulus is necessary for compatible integration with biological systems.

[0004] In addition, thin-film electronic devices are mainly covered by sealed packaging materials and usually work in complex biological fluids, and biological molecules or cells will non-specifically adsorb on the devices. Non-specific protein adsorption of biomaterials has been proven to be one of the main factors that trigger inflammation and mediate bacterial adhesion and proliferation. For devices that detect rare biological components, since the packaging material occupies most of the area, the rare biological components will adhere to the packaging material more, resulting in distorted results.

[0005] To address these complex challenges, the present invention has developed a zwitterionic and lithography-compatible sealed packaging system to prepare conformable bioelectronic devices with controllable biointeractions. Zwitterionic polymers are grafted on the surface of poly(p-xylene) films, giving them excellent anti-fouling properties and ultra-high softness. In addition, due to deformation and capillary adhesion caused by surface stress, these zwitterionic poly(p-xylene) films have excellent mechanical compatibility after wetting. In order to highlight its versatility, this functional sealed packaging system is used to manufacture flexible sensor devices. All devices have good complex surface compatibility, good control of interactions with proteins / cells, and can effectively reduce inflammatory responses when used in vivo. The zwitterionic sealed packaging system developed by the present invention is expected to provide an attractive option for the manufacture of flexible bioelectronics with controllable biointeractions and low immune responses, providing these devices with compatible biological interfaces or more accurate signal detection. Summary of the invention

[0006] In order to solve the problems of the prior art, the purpose of the present invention is to overcome the shortcomings of existing materials and technologies, and to provide a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer and a method for preparing the same. The manufacturing platform manufactures a zwitterion-modified sealing encapsulation layer based on photolithography technology without affecting its sealing encapsulation. The zwitterion-modified sealing encapsulation layer was found to have interesting wetting-driven mechanical compliance and tissue-like surface modulus, which gives the thin-film organic electronic device array good compliance and potentially better biocompatibility. The sealing encapsulation layer can be applied to devices such as microelectrode arrays and transistors based on polyparaxylene insulating materials, significantly improving the long-term stability of their sensing and signal recording. The preparation method of the biomimetic functionalized sealing encapsulation layer of the present invention is highly operable, simple and easy to implement, and suitable for actual production.

[0007] An object of the present invention is to solve at least the above problems and / or disadvantages and to provide at least the advantages which will be described hereinafter.

[0008] The invention provides a bionic functional organic electronic device comprising a bionic functional sealing packaging layer, comprising a flexible substrate, a connecting circuit and a bionic functional sealing packaging layer, wherein the bionic functional sealing packaging layer has a double-layer structure, a bottom layer is unmodified polyparaxylene, and an upper layer is polyparaxylene modified by zwitterionic groups.

[0009] Preferably, the biomimetic functional sealing packaging layer is a biomimetic functional insulating polymer film, the main chain of the polymer film is polyparaxylene, and the polyparaxylene surface has zwitterionic groups, which can repel nonspecific adhesion of cells, viruses, fungi, bacteria and biological molecules.

[0010] Preferably, the biomimetic functionalized organic electronic device sealing and encapsulation layer has an adhesion force greater than 100 nN and a surface elastic modulus less than 1000 kPa in a wet state.

[0011] Preferably, the zwitterionic group-modified polyparaxylene comprises monomer units of formula (I):

[0012]

[0013] In formula (I):

[0014] m, n, k are positive integers, and 10≤m≤5000, 10≤n≤5000, 20≤k≤5000.

[0015] Preferably, -L 1 -for-(CH 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH 2 ) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -or-O-(CH 2 )x -O-(CH 2 -CH 2 -O) y -, wherein x, y are integers, and 0≤x≤20, 0≤y≤20;

[0016] -L 2 -for Any one or more of the following;

[0017] -L 3 -for-(CH 2 ) m -、-(CH 2 ) m -O-(CH 2 ) n -、-(CH 2 ) m -O-CO-(CH 2 ) n -、-(CH 2 ) m -(CH 2 -CH 2 -O) n -、-(CH 2 ) m -O-(CH 2 -CH 2 -O) n -、-O-(CH 2 ) m -(CH 2 -CH 2 -O) n -or-O-(CH 2 ) m -O-(CH 2 -CH 2 -O) n -, wherein m, y are integers, and 0≤m≤20, 0≤n≤20;

[0018] -L 4 -for-(CH 2 ) p -、-O-(CH 2 ) p -、-C(O)-O-(CH 2 ) p -、-C(O)-NH-(CH 2 ) p -、-C(CH 3 ) 2 -C(O)-O-(CH 2 ) p-、-CH(CH 3 )-O-(CH 2 ) p -、-S-CH 2 -CH 2 -O-(CH 2 ) p -、-S-CH 2 -CH(CH 3 )-C(O)-O-(CH 2 ) p -Any one or more of, where p is an integer and 0≤p≤20;

[0019] -R 1 -H, (CH 2 ) d CH 3 Any one of , where d is a positive integer and 0≤d≤8;

[0020] -R 2 for Any one of, wherein M is any one of K, Na, Li, Mg, Al, Fe, and X is any one of F, Cl, Br, I;

[0021] -R 3 -Br, -Cl, -I, Any one of .

[0022] Preferably, the method for preparing the biomimetic functionalized organic electronic device comprises the following steps:

[0023] Step 1: Spin-coating a water-soluble soap layer on a substrate and then depositing a flexible substrate;

[0024] Step 2: Photolithography is performed on the flexible substrate to form a sensing interface and connection circuits;

[0025] Step 3: Deposit adhesive on the flexible substrate on which the sensing interface and connection lines are deposited, and sequentially deposit polyparaxylene layer and Layer to achieve encapsulation of connection lines;

[0026] Step 4: coating a water-soluble soap layer on the electrode obtained in step 3, drying it, and then depositing a polyparaxylene sacrificial layer;

[0027] Step 5: After performing photolithography patterning and plasma dry etching on the electrode obtained in step 4, the sensing interface and connecting wire pins are exposed;

[0028] Step 6: Peel the device prepared in step 5 off the substrate and deposit a layer of layer, or no deposition layer;

[0029] Step 7: Mix the device prepared in step 6 and the water-soluble olefin monomer The polymerization reaction is carried out under the conditions of the presence of a ligand and a catalyst, or under the conditions of the presence of a free radical initiator. After a certain reaction time, a product having Organic electronic devices encapsulated by structural bionic functionalized sealing encapsulation layers.

[0030] Preferably, in the step 1, the speed of coating a layer of water-soluble soap is 0 to 9000 rpm, the time is 0 to 1200 s, the anti-sticking layer is a 0 to 10 wt % water-soluble soap solution, and the drying temperature is 30 to 300° C.;

[0031] In the step 1, the flexible substrate material is any one of polyparaxylene, polydimethylsiloxane, polyurethane, styrene-butadiene-styrene block copolymer, polyvinyl alcohol, polyethylene terephthalate, polyimide, polyethylene naphthalate, paper and textile material.

[0032] Preferably, in the step 2, the process of photolithography patterning is: spin coating the photoresist on the flexible substrate of the substrate, baking, and then exposing the substrate to ultraviolet light through a photomask; immersing the exposed substrate in a developer for treatment, then washing with ultrapure water, drying with nitrogen, and developing the photoresist; the spin coating speed is 0 to 9000 rpm, and the spin coating time is 0 to 180 s; the baking temperature is 50 to 200° C., and the time is 0 to 1200 s; the exposure time is 0 to 120 s; the immersion temperature in the developer is 0 to 90° C., and the treatment time is 0 to 1200 s; the plasma dry etching process is: using low temperature O 2 Plasma treatment instrument, treating photolithography patterned substrates at 0-1000W for 0-600min;

[0033] In the step 2, the material of the sensing interface and the connecting circuit is any one of gold, platinum, graphene, carbon nanotubes, metal nanowires and conductive polymers.

[0034] Preferably, in the step 3, the process of depositing the adhesive on the flexible substrate on which the sensing interface and the connecting circuit are deposited is to immerse the flexible substrate on which the sensing interface and the connecting circuit are deposited in the adhesive for 0 to 120 minutes, and then wash and dry it; the adhesive comprises the following components in weight percentage: silane A-1740 to 50%, ultrapure water 0 to 100%, and isopropanol 0 to 100%; the drying temperature is 0 to 200° C., and the drying time is 0 to 120 minutes;

[0035] In the step 3, the process of depositing the polyparaxylene layer is as follows: adding two polyparaxylenes to the sublimation zone of the chemical vapor deposition reactor, and depositing them by chemical vapor deposition method; the chemical vapor deposition method is as follows: under the condition of vacuum pressure of 0 to 100 Pa, first sublimating the two polyparaxylenes at 70 to 300° C., then cracking them at 400 to 1000° C., and finally depositing them at 0 to 50° C. to obtain the polyparaxylene layer;

[0036] In the step 3, the deposition The specific process is as follows: The monomer is added to the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 0-100Pa, first The monomer sublimates at 70-300°C, then cracks at 400-1000°C, and finally deposits at 0-50°C. layer.

[0037] Preferably, in step 4, the process of coating a layer of water-soluble soap is the same as the process of coating a layer of water-soluble soap in step 4.

[0038] In the step 4, the process of depositing the polyparaxylene sacrificial layer is the same as the process of depositing the polyparaxylene in the step 3.

[0039] Preferably, in the step 5, the photolithography patterning process is the same as the photolithography patterning process in the step 2;

[0040] In step 5, the plasma dry etching process is: using low temperature O 2 The plasma processor processes the photolithographically patterned thin film at 0 to 2000 W for 0 to 6 h;

[0041] Preferably,

[0042] In step 6, a layer of The process of layer deposition in step 2 The process is the same for layers;

[0043] Preferably, in step seven, the The process of forming the biomimetic functional sealing encapsulation layer of the structure adopts any one of atom transfer radical polymerization or reversible addition-fragmentation chain transfer polymerization;

[0044] In the step 7, the The process of the bionic functional sealing encapsulation layer of the structure adopts atom transfer radical polymerization, and the specific process is as follows:

[0045] Add the device prepared in step 6 to the reaction solution; weigh 0.1 mmol to 200 mmol of ligand and 0.1 mmol to 100 mmol of catalyst into the above solution, and then weigh 1 mmol to 3000 mmol of water-soluble olefin monomer. Add to the above solution, shake and oscillate, heat to 10℃~100℃, and react for 0h~24h; after the reaction, rinse with water and blow dry with nitrogen to obtain An organic electronic device encapsulated by a structural bionic functional sealing encapsulation layer; the solution is any one or more of methanol, ethanol, water, and dimethyl sulfoxide; the ligand is any one of tris[2-(dimethylamino)ethyl]amine, tris(2-pyridylmethyl)amine, 1,1,4,7,10,10-hexamethyltriethylenetetramine or pentamethyldiethylenetriamine; the catalyst is Cu, CuBr, CuBr 2 , CuCl or CuCl 2 Any one or more of .

[0046] Preferably, in step seven, in step seven, a The process of the bionic functional sealing encapsulation layer of the structure adopts reversible addition-fragmentation chain transfer polymerization, and the specific process is as follows:

[0047] Add the device prepared in step 6 to the reaction solution; weigh 0.1 mmol to 100 mmol of free radical initiator, and then weigh 1 mmol to 3000 mmol of water-soluble olefin monomer. Add to the above solution, shake and oscillate, heat to 40℃~200℃, and react for 0h~24h; after the reaction, rinse with water and blow dry with nitrogen to obtain An organic electronic device encapsulated by a structural bionic functional sealing encapsulation layer; the solution is any one or more of methanol, ethanol, water, and dimethyl sulfoxide; the free radical initiator is any one of azobisisobutyronitrile, triethylamine, azobismethoxyisoheptanenitrile, or azobiscyanovaleric acid.

[0048] Compared with the prior art, the present invention has the following obvious outstanding substantive features and significant advantages:

[0049] (1) The present invention introduces polyparaxylene functionalized with hydrophilic groups into the biomimetic functionalized sealing encapsulation layer, thereby maintaining the sealing property of the material while achieving maximum resistance to nonspecific adhesion and mechanical compliance in a wet state.

[0050] (2) The bionic functional sealing packaging layer of the present invention can match the photolithography process technology and can be used in the preparation process of various high-resolution thin-film electronic devices.

[0051] (3) The biomimetic functional sealing packaging layer of the present invention can significantly inhibit nonspecific adhesion interference and adhesion of inflammatory factors under complex biological environmental conditions, and can further achieve specific effects on cells, viruses and biological molecules, thereby maximizing the selectivity, accuracy and long-term usability of device sensing or recording.

[0052] (4) The bionic functional sealing packaging layer of the present invention has a simple process and is suitable for industrial production.

[0053] (5) The flexible bioelectronic device of the present invention includes a biomimetic functional sealing packaging layer, has good complex surface compatibility, and can well control the interaction with proteins / cells, and can effectively reduce inflammatory response when used in vivo.

[0054] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. Description of the drawings:

[0055] Figure 1 The initiator monomer of the present invention 1H-NMR spectrum of

[0056] Figure 2 The anti-bovine serum albumin adhesion ability of the biomimetic functional sealing encapsulation layer prepared in Example 9 of the present invention and pure polyparaxylene;

[0057] Figure 3 The anti-fibrinogen adhesion ability of the biomimetic functional sealing encapsulation layer prepared in Example 9 of the present invention and pure polyparaxylene;

[0058] Figure 4 The anti-fetal bovine serum adhesion ability of the biomimetic functional sealing encapsulation layer prepared in Example 9 of the present invention and pure polyparaxylene;

[0059] Figure 5 Comparison of the 24h adhesion ability of the biomimetic functional sealing encapsulation layer prepared in Example 9 of the present invention and pure polyparaxylene against microglial cells;

[0060] Figure 6 The surface Young's modulus of the biomimetic functional sealing encapsulation layer and pure polyparaxylene prepared in Example 9 of the present invention;

[0061] Figure 7 The photograph shows the adhesion between the biomimetic functional sealing packaging layer prepared in Example 9 of the present invention and pure polyparaxylene;

[0062] Figure 8 This is a comparison diagram of the adhesion between the biomimetic functional sealing packaging layer prepared in Example 9 of the present invention and pure polyparaxylene;

[0063] Fig. 9 A schematic diagram of the electrochemical transistor including a biomimetic functionalized sealing packaging layer prepared in Example 9 of the present invention realizing controllable interaction with cells; Specific implementation method:

[0064] The present invention is further described in detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

[0065] It should be understood that terms such as “having”, “including” and “comprising” used herein do not specify the existence or addition of one or more other elements or combinations thereof.

[0066] Embodiments 1 to 16:

[0067] A biomimetic functional organic electronic device including a biomimetic functional sealing packaging layer, comprising a flexible substrate, a connecting circuit and a biomimetic functional sealing packaging layer, wherein the biomimetic functional sealing packaging layer has a double-layer structure, the bottom layer is unmodified polyparaxylene, and the upper layer is polyparaxylene modified by zwitterionic groups;

[0068] Wherein, the biomimetic functional sealing encapsulation layer is a biomimetic functional insulating polymer film, the main chain of the polymer film is polyparaxylene, and the polyparaxylene surface has zwitterionic groups, which can repel nonspecific adhesion of cells, viruses, fungi, bacteria and biological molecules;

[0069] The biomimetic functionalized organic electronic device has an adhesion force greater than 100 nN and a surface elastic modulus less than 1000 kPa in a wet state;

[0070] Embodiment 1:

[0071] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0072] (1) Spin-coating a layer of water-soluble soap on a substrate, the speed of coating a layer of water-soluble soap is 3000 rpm, the time is 15 s, the anti-sticking layer is a 2 wt % water-soluble soap solution, and the drying temperature is 50° C.; then depositing a polydimethylsiloxane flexible substrate;

[0073] (2) Spin coating S1813 photoresist on the flexible substrate at a speed of 2000 rpm for 60 seconds; bake at a temperature of 100°C for 120 seconds; then expose the substrate to ultraviolet light through a photomask for 30 seconds; immerse the exposed substrate in a developer at a temperature of 25°C for 30 seconds; then wash with ultrapure water and dry with nitrogen;2 A plasma treatment apparatus was used to treat the photolithographically patterned substrate at 300W for 60 minutes. An electron beam evaporator was used to deposit 5nm of chromium and 200nm of gold on the surface of the flexible substrate as the sensing interface and connecting lines.

[0074] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (42% silane A-17, 49% ultrapure water, 49% isopropyl alcohol) for 60 minutes, then washed, and then heat-dried at 50°C for 120 minutes; then, a polyparaxylene layer and a polyparaxylene layer functionalized with chloroisobutyrate groups are sequentially deposited on the electrode to achieve encapsulation of the connecting lines;

[0075] The steps of depositing polyparaxylene are as follows: 5g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 20Pa, the polyparaxylene is first sublimated at 100°C, then cracked at 600°C, and finally deposited at 40°C to obtain a polyparaxylene layer;

[0076] The process of depositing the poly(p-xylene) layer functionalized with chloroisobutyrate groups is as follows: 1 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 20Pa, first The monomer is sublimated at 100°C, cracked at 500°C, and finally deposited at 40°C to obtain a poly(p-xylene) layer functionalized with chloroisobutyrate groups.

[0077] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the coating speed of the layer of water-soluble soap is 3000 rpm, the time is 15 s, the anti-sticking layer is a 2 wt % water-soluble soap solution, and the drying temperature is 50° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0078] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 2000 rpm for 60 seconds; bake at a temperature of 100° C. for 400 seconds; then expose the substrate to ultraviolet light through a photomask for 30 seconds; immerse the exposed substrate in a developer at a temperature of 25° C. for 400 seconds; then rinse with ultrapure water and dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 2 h at 400 W for pattern etching;

[0079] (6) peeling the device prepared in step (5) from the substrate, and depositing a layer of poly(p-xylene) functionalized with chloroisobutyrate groups on the back side of the device in the same manner as depositing the poly(p-xylene) functionalized with chloroisobutyrate groups in step (3);

[0080] (7) The device prepared in (6) was added to 20 mL of aqueous solution; 18 mmol of tris[2-(dimethylamino)ethyl]amine, 7.3 mmol of CuBr, 4.7 mmol of CuBr 2 , and then weigh 510mmol of water-soluble olefin monomer Add to the above solution, shake and oscillate, heat to 50°C, and react for 11 hours; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0081] Embodiment 2:

[0082] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0083] (1) Spin-coating a layer of water-soluble soap on a substrate, the speed of coating a layer of water-soluble soap is 2000 rpm, the time is 180 s, the anti-sticking layer is a 3 wt % water-soluble soap solution, and the drying temperature is 150° C.; then depositing a polyurethane flexible substrate;

[0084] (2) Spin coating S1810 photoresist on the flexible substrate at a speed of 3000 rpm for 180 seconds; bake at a temperature of 150°C for 300 seconds; then expose the substrate to ultraviolet light through a photomask for 5 seconds; immerse the exposed substrate in a developer at a temperature of 25°C for 60 seconds; then wash with ultrapure water and dry with nitrogen; 2 A plasma treatment apparatus was used to treat the photolithographically patterned substrate at 300W for 30 minutes. An electron beam evaporator was used to deposit 7nm of chromium and 150nm of platinum on the surface of the flexible substrate as the sensing interface and connecting lines.

[0085] (3) The flexible substrate on which the sensing interface and connecting lines are deposited is immersed in an adhesive (41% silane A-17, 49.5% ultrapure water, 49.5% isopropyl alcohol) for 60 min, then cleaned and heat-dried at 660° C. for 60 min; then, a polyparaxylene layer and a polyparaxylene functionalized with chloroisobutyrate groups are sequentially deposited on the electrode to achieve encapsulation of the connecting lines;

[0086] The steps of depositing polyparaxylene are as follows: 3g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 5Pa, the polyparaxylene is first sublimated at 150°C, then cracked at 600°C, and finally deposited at 50°C to obtain a polyparaxylene layer;

[0087] The process of depositing poly(p-xylene) functionalized with chloroisobutyrate groups is as follows: 2 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 0-100Pa, first The monomer is sublimated at 150°C, cracked at 550°C, and finally deposited at 30°C to obtain poly(p-xylene) functionalized with chloroisobutyrate groups.

[0088] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the speed of coating a layer of water-soluble soap is 2000 rpm, the time is 180 s, the anti-sticking layer is 33% water-soluble soap solution, and the drying temperature is 150° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0089] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 2000 rpm for 60 seconds; bake at a temperature of 150° C. for 1180 seconds; then expose the substrate to ultraviolet light through a photomask for 60 seconds; immerse the exposed substrate in a developer at a temperature of 25° C. for 300 seconds; then rinse with ultrapure water and blow dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 3 h at 400 W for pattern etching;

[0090] (6) peeling the device prepared in step (5) from the substrate, and depositing a layer of poly(p-xylene) functionalized with chloroisobutyrate groups on the back side of the device in the same manner as depositing the poly(p-xylene) functionalized with chloroisobutyrate groups in step (3);

[0091] (7) The device prepared in (6) was added to 15 mL of ethanol reaction solution; 15.5 mmol of tris[2-(dimethylamino)ethyl]amine was weighed, 7.1 mmol of Cu and 5.4 mmol of CuBr were weighed, and 257 mmol of water-soluble olefin monomer was weighed. Add to the above solution, shake and oscillate, heat to 60°C, and react for 1 hour; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0092] Embodiment 3:

[0093] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0094] (1) Spin-coating a layer of water-soluble soap on a substrate at a speed of 1000 rpm for 300 seconds, the anti-sticking layer is a 5 wt % water-soluble soap solution, and the drying temperature is 130° C.; then depositing a styrene-butadiene-styrene block copolymer flexible substrate;

[0095] (2) Spin coating S1813 photoresist on the flexible substrate at a speed of 2500 rpm for 180 seconds; bake at a temperature of 100°C for 120 seconds; then expose the substrate to ultraviolet light through a photomask for 120 seconds; immerse the exposed substrate in a developer at a temperature of 30°C for 200 seconds; then wash with ultrapure water and dry with nitrogen; 2 Plasma treatment equipment, treating the photolithographically patterned substrate at 500W for 4min; depositing 100nm graphene on the surface of the flexible substrate as a sensing interface and connecting circuit;

[0096] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (44% silane A-17, 48% ultrapure water, 48% isopropyl alcohol) for 120 min, then cleaned, and then heat-dried at 200° C. for 10 min; then, a polyparaxylene layer and a polyparaxylene layer functionalized with iodoisobutyrate groups are sequentially deposited on the electrode to achieve encapsulation of the connecting lines;

[0097] The steps of depositing polyparaxylene are as follows: 10 g of polyparaxylene is added to the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 110 Pa, the polyparaxylene is first sublimated at 200° C., then cracked at 700° C., and finally deposited at 20° C. to obtain a polyparaxylene layer;

[0098] The process of depositing the poly(p-xylene) layer functionalized with iodoisobutyrate groups is as follows: 2 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 30Pa, first The monomer is sublimated at 200°C, cracked at 6600°C, and finally deposited at 20°C to obtain a poly(p-xylene) layer functionalized with iodoisobutyrate groups.

[0099] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the coating speed of the layer of water-soluble soap is 100 rpm, the time is 300 s, the anti-sticking layer is a 5 wt % water-soluble soap solution, and the drying temperature is 130° C. After drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0100] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 3000 rpm for 120 seconds; bake at a temperature of 140° C. for 180 seconds; then expose the substrate to ultraviolet light through a photomask for 220 seconds; immerse the exposed substrate in a developer at a temperature of 30° C. for 180 seconds; then rinse with ultrapure water and dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, and the photolithographically patterned film is processed at 300W for 6h for pattern etching;

[0101] (6) peeling the device prepared in step (5) from the substrate, and depositing a layer of poly(p-xylene) functionalized with iodoisobutyrate groups on the back side of the device in the same manner as the process of depositing the poly(p-xylene) functionalized with iodoisobutyrate groups in step (3);

[0102] (7) Add the device prepared in (6) to 50 mL of methanol reaction solution; weigh 52 mmol mg of tris(2-pyridylmethyl)amine, 32 mmol of Cu and 50 mmol of CuCl, and 850 mmol of water-soluble olefin monomer. Add to the above solution, shake and oscillate, heat to 40°C, and react for 6 hours; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a biomimetic functional sealing encapsulation layer.

[0103] Embodiment 4:

[0104] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0105] (1) Spin-coating a layer of water-soluble soap on a substrate, the speed of coating a layer of water-soluble soap is 3000 rpm, the time is 110 s, the anti-sticking layer is a 10 wt % water-soluble soap solution, and the drying temperature is 70° C.; then depositing a polyethylene flexible substrate;

[0106] (2) Spin coating S1810 photoresist on the flexible substrate at a speed of 1000 rpm for 180 seconds; bake at a temperature of 200°C for 120 seconds; then expose the substrate to ultraviolet light through a photomask for 10 seconds; immerse the exposed substrate in a developer at a temperature of 30°C for 120 seconds; then wash with ultrapure water and dry with nitrogen; 2 A plasma treatment apparatus was used to treat the photolithographically patterned substrate at 550W for 600min to deposit 5nm carbon nanotubes on the surface of the flexible substrate as the sensing interface and connecting lines;

[0107] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (46% silane A-17, 47% ultrapure water, 47% isopropyl alcohol) for 20 minutes, then cleaned, and then heat-dried at 200°C for 120 minutes; then, a polyparaxylene layer and a polyparaxylene layer functionalized with bromoisobutyrate groups are sequentially deposited on the electrode to achieve encapsulation of the connecting lines;

[0108] The steps of depositing polyparaxylene are as follows: 5g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 8Pa, the polyparaxylene is first sublimated at 220°C, then cracked at 680°C, and finally deposited at 20°C to obtain a polyparaxylene layer;

[0109] The process of depositing the poly(p-xylene) layer functionalized with bromoisobutyrate groups is as follows: 1 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 10Pa, first The monomer is sublimated at 220°C, cracked at 600°C, and finally deposited at 30°C to obtain a poly(p-xylene) layer functionalized with bromoisobutyrate groups.

[0110] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the coating speed of the layer of water-soluble soap is 3000 rpm, the time is 110 s, the anti-sticking layer is a 10 wt % water-soluble soap solution, and the drying temperature is 70° C. After drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0111] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 3000 rpm for 120 s; bake at a temperature of 140° C. for 120 s; then expose the substrate to ultraviolet light through a photomask for 10 s; immerse the exposed substrate in a developer at a temperature of 25° C. for 120 s; then rinse with ultrapure water and dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 2 h at 500 W for pattern etching;

[0112] (6) The device prepared in (5) was added to 30 mL of dimethyl sulfoxide reaction solution; 26 mmol of tris[2-(dimethylamino)ethyl]amine was weighed, and then 13 mmol of CuCl and 9.5 mmol of CuCl were weighed. 2 , and then weigh 770mmol of water-soluble olefin monomer Add to the above solution, shake and oscillate, heat to 50°C, and react for 4 hours; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0113] Embodiment 5:

[0114] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0115] (1) Spin-coating a layer of water-soluble soap on a substrate at a speed of 1000 rpm for 1200 s, with a 6 wt % water-soluble soap solution as the anti-sticking layer, and drying at a temperature of 100° C.; then depositing a polyethylene terephthalate flexible substrate;

[0116] (2) Spin coating S1813 photoresist on the flexible substrate at a speed of 7000 rpm for 20 seconds; bake at a temperature of 200°C for 20 seconds; then expose the substrate to ultraviolet light through a photomask for 2 seconds; immerse the exposed substrate in a developer at a temperature of 30°C for 60 seconds; then wash with ultrapure water and dry with nitrogen; 2 Plasma treatment apparatus, treating the photolithographically patterned substrate at 400W for 50min; depositing 100nm metal nanowires on the surface of the flexible substrate as the sensing interface and connecting lines;

[0117] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (42% silane A-17, 49% ultrapure water, 49% isopropyl alcohol) for 20 minutes, then cleaned, and then heat-dried at 100°C for 20 minutes; then, a polyparaxylene layer and a polyparaxylene layer functionalized with iodoisobutyrate groups are sequentially deposited on the electrode to achieve encapsulation of the connecting lines;

[0118] The steps of depositing polyparaxylene are as follows: 3g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 10Pa, the polyparaxylene is first sublimated at 200°C, then cracked at 700°C, and finally deposited at 20°C to obtain a polyparaxylene layer;

[0119] The process of depositing the poly(p-xylene) layer functionalized with iodoisobutyrate groups is as follows: 2 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 100Pa, first The monomer is sublimated at 300°C, cracked at 1000°C, and finally deposited at 50°C to obtain a poly(p-xylene) layer functionalized with iodoisobutyrate groups.

[0120] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the speed of coating a layer of water-soluble soap is 1000 rpm, the time is 1200 s, the anti-sticking layer is a 6 wt % water-soluble soap solution, and the drying temperature is 100° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0121] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 3000 rpm for 180 seconds; bake at a temperature of 50° C. for 1200 seconds; then expose the substrate to ultraviolet light through a photomask for 120 seconds; immerse the exposed substrate in a developer at a temperature of 40° C. for 1200 seconds; then rinse with ultrapure water and dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, and the photolithographically patterned thin film is processed at 2000W for 6h for pattern etching;

[0122] (6) peeling the device prepared in step (5) from the substrate, and depositing a layer of poly(p-xylene) functionalized with iodoisobutyrate groups on the back side of the device in the same manner as depositing the poly(p-xylene) functionalized with iodoisobutyrate groups in step (3);

[0123] (7) The device prepared in (6) was added to a 100 mL methanol and water (volume ratio 1:1) reaction solution; 50 mmol tris(2-pyridylmethyl)amine was weighed, and then 18 mmol CuBr and 11 mmol CuBr were weighed. 2 , and then weigh 850mmol of water-soluble olefin monomer Add to the above solution, shake and oscillate, heat to 70°C, and react for 1 hour; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0124] Embodiment 6:

[0125] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0126] (1) Spin-coating a layer of water-soluble soap on a substrate at a speed of 500 rpm for 1200 s, with a 10 wt % water-soluble soap solution as the anti-sticking layer, and drying at a temperature of 300° C.; then depositing a polyimide flexible substrate;

[0127] (2) Spin coating S1810 photoresist on the flexible substrate at a speed of 1000 rpm for 180 seconds; bake at a temperature of 200°C for 1200 seconds; then expose the substrate to ultraviolet light through a photomask for 10 seconds; immerse the exposed substrate in a developer at a temperature of 30°C for 300 seconds; then wash with ultrapure water and dry with nitrogen; 2 The plasma treatment instrument treats the photolithographically patterned substrate at 300W for 5min, depositing 200nm of conductive polymer on the surface of the flexible substrate as the sensing interface and connecting circuit;

[0128] (3) The flexible substrate on which the sensing interface and the connecting lines have been deposited is immersed in an adhesive (10% silane A-174, 45% ultrapure water, 45% isopropyl alcohol) for 30 minutes, then cleaned, and then heat-dried at 60°C for 30 minutes; then, a poly(p-xylene) layer and a poly(p-xylene) layer functionalized with iodoisobutyrate groups are sequentially deposited on the electrode to achieve encapsulation of the connecting lines;

[0129] The steps of depositing polyparaxylene are as follows: 10g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 10Pa, the polyparaxylene is first sublimated at 70°C, then cracked at 1000°C, and finally deposited at 20°C to obtain a polyparaxylene layer;

[0130] The process of depositing the poly(p-xylene) layer functionalized with iodoisobutyrate groups is as follows: 110 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 20Pa, first The monomer is sublimated at 300°C, cracked at 400°C, and finally deposited at 40°C to obtain a poly(p-xylene) layer functionalized with iodoisobutyrate groups.

[0131] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the speed of coating a layer of water-soluble soap is 500 rpm, the time is 1200 s, the anti-sticking layer is a 10 wt % water-soluble soap solution, and the drying temperature is 300° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0132] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 5000 rpm for 20 seconds; bake at a temperature of 120° C. for 1000 seconds; then expose the substrate to ultraviolet light through a photomask for 20 seconds; immerse the exposed substrate in a developer at a temperature of 20° C. for 1200 seconds; then rinse with ultrapure water and dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 6 h at 0 to 2000 W for pattern etching;

[0133] (6) peeling the device prepared in step (5) from the substrate, and depositing another iodoisobutyrate group-functionalized polyparaxylene layer on the back side of the device in the same process as the process of depositing the iodoisobutyrate group-functionalized polyparaxylene layer in step (3);

[0134] (7) The device prepared in (6) was added to a reaction solution of 10 mL of ethanol and water (volume ratio 1:1); 26 mmol of tris(2-pyridylmethyl)amine, 8 mmol of Cu, and 380 mmol of a water-soluble olefin monomer were weighed. Add to the above solution, shake and oscillate, heat to 40°C, and react for 4 hours; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0135] Embodiment 7:

[0136] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0137] (1) Spin-coating a layer of water-soluble soap on a substrate at a speed of 2000 rpm for 200 seconds, the anti-sticking layer is a 4 wt % water-soluble soap solution, and the drying temperature is 120° C.; then depositing a polyethylene glycol terephthalate flexible substrate;

[0138] (2) Spin coating S1813 photoresist on the flexible substrate at a speed of 5000 rpm for 20 seconds; bake at a temperature of 100°C for 20 seconds; then expose the substrate to ultraviolet light through a photomask for 5 seconds; immerse the exposed substrate in a developer at a temperature of 25°C for 60 seconds; then wash with ultrapure water and dry with nitrogen; 2 A plasma treatment apparatus was used to treat the photolithographically patterned substrate at 100W for 30 minutes. An electron beam evaporator was used to deposit 5nm of chromium and 1100nm of gold on the surface of the flexible substrate as the sensing interface and connecting lines.

[0139] (3) The flexible substrate on which the sensing interface and connecting lines are deposited is immersed in an adhesive (46% silane A-17, 47% ultrapure water, 47% isopropyl alcohol) for 47 minutes, then cleaned and baked at 100°C for 10 minutes; then, a polyparaxylene layer and a polyparaxylene functionalized with chloroisobutyrate groups are sequentially deposited on the electrode to achieve encapsulation of the connecting lines;

[0140] The steps of depositing polyparaxylene are as follows: 8g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 10Pa, the polyparaxylene is first sublimated at 100°C, then cracked at 700°C, and finally deposited at 30°C to obtain a polyparaxylene layer;

[0141] The process of depositing the poly(p-xylene) layer functionalized with chloroisobutyrate groups is as follows: 5 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 20Pa, first The monomer is sublimated at 300°C, cracked at 1000°C, and finally deposited at 25°C to obtain a poly(p-xylene) layer functionalized with chloroisobutyrate groups.

[0142] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the speed of coating a layer of water-soluble soap is 2000 rpm, the time is 200 s, the anti-sticking layer is 4 wt % water-soluble soap solution, and the drying temperature is 120° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0143] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 2000 rpm for 60 seconds; bake at a temperature of 200° C. for 10 seconds; then expose the substrate to ultraviolet light through a photomask for 30 seconds; immerse the exposed substrate in a developer at a temperature of 30° C. for 200 seconds; then rinse with ultrapure water and dry with nitrogen; then pat dry with low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 6 h at 1000 W for pattern etching;

[0144] (6) The device prepared in (5) was added to 30 mL of methanol reaction solution; 14.5 mmol of tris(2-pyridylmethyl)amine, 88 mmol of CuBr, and 200 mmol of water-soluble olefin monomer were weighed. Add to the above solution, shake and oscillate, heat to 70°C, and react for 2 hours; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0145] Embodiment 8:

[0146] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0147] (1) Spin-coating a layer of water-soluble soap on a substrate at a speed of 300 rpm for 1200 s, a 10 wt % water-soluble soap solution for the anti-sticking layer, and a drying temperature of 130° C.; then depositing a paper sheet flexible substrate;

[0148] (2) Spin coating S1813 photoresist on the flexible substrate at a speed of 2500 rpm for 30 seconds; bake at a temperature of 150°C for 100 seconds; then expose the substrate to ultraviolet light through a photomask for 5 seconds; immerse the exposed substrate in a developer at a temperature of 30°C for 120 seconds; then wash with ultrapure water and dry with nitrogen; 2 A plasma treatment instrument was used to treat the photolithographically patterned substrate at 500W for 10 minutes. An electron beam evaporator was used to deposit 5nm of chromium and 180nm of gold on the surface of the flexible substrate as the sensing interface and connecting lines.

[0149] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (42% silane A-17, 49% ultrapure water, 49% isopropyl alcohol) for 30 minutes, then cleaned, and then heat-dried at 80°C for 100 minutes; then, a polyparaxylene layer and a polyparaxylene layer functionalized with bromoisobutyrate groups are sequentially deposited on the electrode to achieve encapsulation of the connecting lines;

[0150] The steps of depositing polyparaxylene are as follows: 10g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 10Pa, the polyparaxylene is first sublimated at 200°C, then cracked at 800°C, and finally deposited at 30°C to obtain a polyparaxylene layer;

[0151] The process of depositing the poly(p-xylene) layer functionalized with bromoisobutyrate groups is as follows: 5 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 30Pa, first The monomer is sublimated at 200°C, cracked at 600°C, and finally deposited at 30°C to obtain a poly(p-xylene) layer functionalized with bromoisobutyrate groups.

[0152] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the coating speed of the layer of water-soluble soap is 300 rpm, the time is 1200 s, the anti-sticking layer is a 10 wt % water-soluble soap solution, and the drying temperature is 130° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0153] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 2000 rpm for 180 seconds; bake at a temperature of 50° C. for 1200 seconds; then expose the substrate to ultraviolet light through a photomask for 50 seconds; immerse the exposed substrate in a developer at a temperature of 20° C. for 200 seconds; then rinse with ultrapure water and blow dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 6 h at 500 W for pattern etching;

[0154] (6) peeling the device prepared in step (5) from the substrate, and depositing a layer of poly(p-xylene) functionalized with bromoisobutyrate groups on the back side of the device in the same manner as depositing the poly(p-xylene) functionalized with bromoisobutyrate groups in step (3);

[0155] (7) Add the device prepared in (6) to 15 mL of the reaction solution; weigh 23 mmol mg of tri[2-(dimethylamino)ethyl]amine, 8 mmol of CuCl, and 1270 mmol of a water-soluble olefin monomer. Add it to the above solution, shake it, heat it to 100°C, and react it for 1 hour; after the reaction, rinse it with water and blow it dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0156] Embodiment 9:

[0157] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0158] (1) Spin-coating a layer of water-soluble soap on a substrate, the speed of coating a layer of water-soluble soap is 1500 rpm, the time is 15 s, the anti-sticking layer is a 2 wt % water-soluble soap solution, and the drying temperature is 120° C.; then depositing a polyparaxylene flexible substrate;

[0159] (2) Spin coating S1813 photoresist on the flexible substrate at a speed of 3500 rpm for 60 seconds; bake at a temperature of 115°C for 60 seconds; then expose the substrate to ultraviolet light through a photomask for 2 seconds; immerse the exposed substrate in a developer at a temperature of 25°C for 10 seconds; then wash with ultrapure water and dry with nitrogen; 2 A plasma treatment instrument was used to treat the photolithographically patterned substrate at 400W for 5 minutes. An electron beam evaporator was used to deposit 5nm of chromium and 180nm of gold on the surface of the flexible substrate as the sensing interface and connecting lines.

[0160] (3) The flexible substrate on which the sensing interface and the connection circuits are deposited is immersed in an adhesive (41% silane A-17, 49.5% ultrapure water, 49.5% isopropanol) for 30 minutes, then cleaned, and then heat-dried at 70°C for 30 minutes; then, a polyparaxylene layer and a polyparaxylene layer functionalized with bromoisobutyrate groups are sequentially deposited on the electrode to achieve encapsulation of the connection circuits;

[0161] The steps of depositing polyparaxylene are as follows: 5g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 5Pa, the polyparaxylene is first sublimated at 120°C, then cracked at 670°C, and finally deposited at 25°C to obtain a polyparaxylene layer;

[0162] The process of depositing the poly(p-xylene) layer functionalized with bromoisobutyrate groups is as follows: 1 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 10Pa, first The monomer is sublimated at 120°C, cracked at 550°C, and finally deposited at 25°C to obtain a poly(p-xylene) layer functionalized with bromoisobutyrate groups.

[0163] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the coating speed of the layer of water-soluble soap is 1500 rpm, the time is 15 s, the anti-sticking layer is a 2 wt % water-soluble soap solution, and the drying temperature is 120° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0164] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 2000 rpm for 20 seconds; bake at a temperature of 105° C. for 180 seconds; then expose the substrate to ultraviolet light through a photomask for 30 seconds; immerse the exposed substrate in a developer at a temperature of 25° C. for 420 seconds; then rinse with ultrapure water and blow dry with nitrogen; then immerse in a developer at low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 2 h at 400 W for pattern etching;

[0165] (6) peeling the device prepared in step (5) from the substrate, and depositing a layer of poly(p-xylene) functionalized with bromoisobutyrate groups on the back side of the device in the same process as depositing the poly(p-xylene) functionalized with bromoisobutyrate groups in step (3);

[0166] (7) The device prepared in (6) was added to a reaction solution of 6 mL of water and dimethyl sulfoxide (volume ratio: 1:1); 10.64 mmol of tris(2-pyridylmethyl)amine was weighed, and then 2.5 mmol of CuBr and 2.5 mmol of CuBr were weighed. 2 , and then weigh 665mmol of water-soluble olefin monomer Add to the above solution, shake and oscillate, heat to 50°C, and react for 3 hours; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0167] Embodiment 10:

[0168] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0169] (1) Spin-coating a layer of water-soluble soap on a substrate, the speed of coating a layer of water-soluble soap is 3000 rpm, the time is 15 s, the anti-sticking layer is a 2 wt % water-soluble soap solution, and the drying temperature is 50° C.; then depositing a polydimethylsiloxane flexible substrate;

[0170] (2) Spin coating S1813 photoresist on the flexible substrate at a speed of 2000 rpm for 60 seconds; bake at a temperature of 100°C for 120 seconds; then expose the substrate to ultraviolet light through a photomask for 30 seconds; immerse the exposed substrate in a developer at a temperature of 25°C for 30 seconds; then wash with ultrapure water and dry with nitrogen; 2 A plasma treatment apparatus was used to treat the photolithographically patterned substrate at 300W for 60 minutes. An electron beam evaporator was used to deposit 5nm of chromium and 200nm of gold on the surface of the flexible substrate as the sensing interface and connecting lines.

[0171] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (42% silane A-17, 49% ultrapure water, 49% isopropyl alcohol) for 60 minutes, then cleaned, and then heat-dried at 50°C for 120 minutes; then, a polyparaxylene layer and a dithioester derivative functionalized polyparaxylene layer are sequentially deposited on the electrode to achieve the encapsulation of the connecting lines;

[0172] The steps of depositing polyparaxylene are as follows: 5 g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 20 Pa, the polyparaxylene is first sublimated at 100° C., then cracked at 600° C., and finally deposited at 10° C. to obtain a polyparaxylene layer;

[0173] The process of depositing the poly(p-xylene) layer functionalized with dithioester derivatives is as follows: 1 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 20Pa, first The monomer is sublimated at 100°C, cracked at 500°C, and finally deposited at 10°C to obtain a poly(p-xylene) layer functionalized with a dithioester derivative.

[0174] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the coating speed of the layer of water-soluble soap is 3000 rpm, the time is 15 s, the anti-sticking layer is a 2 wt % water-soluble soap solution, and the drying temperature is 50° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0175] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 2000 rpm for 60 seconds; bake at a temperature of 100° C. for 400 seconds; then expose the substrate to ultraviolet light through a photomask for 30 seconds; immerse the exposed substrate in a developer at a temperature of 25° C. for 400 seconds; then rinse with ultrapure water and dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 2 h at 400 W for pattern etching;

[0176] (6) peeling the device prepared in step (5) from the substrate, and depositing a layer of dithioester derivative functionalized polyparaxylene on the back side of the device in the same process as the process of depositing the dithioester derivative functionalized polyparaxylene layer in step (3);

[0177] (7) Add the device prepared in (6) to 15 mL of the reaction solution; weigh 4.2 mmol of azobisisobutyronitrile free radical initiator, and then weigh 680 mmol of a water-soluble olefin monomer. Add it to the above solution, shake it, heat it to 200°C, and react it for 4 hours; after the reaction, rinse it with water and blow it dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0178] Embodiment 11:

[0179] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0180] (1) Spin-coating a layer of water-soluble soap on a substrate, the speed of coating a layer of water-soluble soap is 2000 rpm, the time is 180 s, the anti-sticking layer is a 3 wt % water-soluble soap solution, and the drying temperature is 150° C.; then depositing a polyurethane flexible substrate;

[0181] (2) Spin coating S1810 photoresist on the flexible substrate at a speed of 3000 rpm for 180 seconds; bake at a temperature of 150°C for 300 seconds; then expose the substrate to ultraviolet light through a photomask for 5 seconds; immerse the exposed substrate in a developer at a temperature of 25°C for 60 seconds; then wash with ultrapure water and dry with nitrogen; 2 A plasma treatment apparatus was used to treat the photolithographically patterned substrate at 300W for 30 minutes. An electron beam evaporator was used to deposit 7nm of chromium and 150nm of platinum on the surface of the flexible substrate as the sensing interface and connecting lines.

[0182] (3) The flexible substrate on which the sensing interface and the connection circuits were deposited was immersed in an adhesive (41% silane A-17, 49.5% ultrapure water, 49.5% isopropyl alcohol) for 60 min, then cleaned, and then heat-dried at 660° C. for 60 min; then, a polyparaxylene layer and a dithioester derivative functionalized polyparaxylene layer were sequentially deposited on the electrode to achieve encapsulation of the connection circuits;

[0183] The steps of depositing polyparaxylene are as follows: 3g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 5Pa, the polyparaxylene is first sublimated at 150°C, then cracked at 600°C, and finally deposited at 50°C to obtain a polyparaxylene layer;

[0184] The process of depositing the poly(p-xylene) layer functionalized with dithioester derivatives is as follows: 2 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 0-100Pa, first The monomer is sublimated at 150°C, cracked at 555°C, and finally deposited at 30°C to obtain a poly(p-xylene) layer functionalized with a dithioester derivative.

[0185] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the speed of coating a layer of water-soluble soap is 2000 rpm, the time is 180 s, the anti-sticking layer is 33% water-soluble soap solution, and the drying temperature is 150° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0186] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 2000 rpm for 60 seconds; bake at a temperature of 150° C. for 1180 seconds; then expose the substrate to ultraviolet light through a photomask for 60 seconds; immerse the exposed substrate in a developer at a temperature of 25° C. for 300 seconds; then rinse with ultrapure water and blow dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 3 h at 400 W for pattern etching;

[0187] (6) peeling the device prepared in step (5) from the substrate, and depositing a layer of dithioester derivative functionalized polyparaxylene on the back side of the device in the same process as the process of depositing the dithioester derivative functionalized polyparaxylene layer in step (3);

[0188] (7) Add the device prepared in (6) to 20 mL of ethanol reaction solution; weigh 43 mmol of triethylamine free radical initiator, and then weigh 2260 mmol of water-soluble olefin monomer. Add to the above solution, shake and oscillate, heat to 60°C, and react for 1 hour; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0189] Embodiment 12:

[0190] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0191] (1) Spin-coating a layer of water-soluble soap on a substrate at a speed of 1000 rpm for 300 seconds, the anti-sticking layer is a 5 wt % water-soluble soap solution, and the drying temperature is 130° C.; then depositing a styrene-butadiene-styrene block copolymer flexible substrate;

[0192] (2) Spin coating S1813 photoresist on the flexible substrate at a speed of 2500 rpm for 180 seconds; bake at a temperature of 100°C for 120 seconds; then expose the substrate to ultraviolet light through a photomask for 120 seconds; immerse the exposed substrate in a developer at a temperature of 30°C for 200 seconds; then wash with ultrapure water and dry with nitrogen; 2 Plasma treatment equipment, treating the photolithographically patterned substrate at 500W for 4min; depositing 100nm graphene on the surface of the flexible substrate as a sensing interface and connecting circuit;

[0193] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (44% silane A-17, 48% ultrapure water, 48% isopropyl alcohol) for 120 min, then cleaned, and then heat-dried at 200°C for 10 min; then, a polyparaxylene layer and a dithioester derivative functionalized polyparaxylene layer are sequentially deposited on the electrode to achieve the encapsulation of the connecting lines;

[0194] The steps of depositing polyparaxylene are as follows: 10 g of polyparaxylene is added to the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 110 Pa, the polyparaxylene is first sublimated at 200° C., then cracked at 700° C., and finally deposited at 10° C. to obtain a polyparaxylene layer;

[0195] The process of depositing the poly(p-xylene) layer functionalized with dithioester derivatives is as follows: 2 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 30Pa, first The monomer is sublimated at 200°C, cracked at 6600°C, and finally deposited at 20°C to obtain a poly(p-xylene) layer functionalized with a dithioester derivative.

[0196] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the coating speed of the layer of water-soluble soap is 100 rpm, the time is 300 s, the anti-sticking layer is a 5 wt % water-soluble soap solution, and the drying temperature is 130° C. After drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0197] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 3000 rpm for 120 seconds; bake at a temperature of 140° C. for 180 seconds; then expose the substrate to ultraviolet light through a photomask for 220 seconds; immerse the exposed substrate in a developer at a temperature of 30° C. for 180 seconds; then rinse with ultrapure water and dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, and the photolithographically patterned film is processed at 300W for 6h for pattern etching;

[0198] (6) Add the device prepared in (5) to 50 mL of methanol reaction solution; weigh 60 mmol of azobismethoxyisoheptanenitrile and 60 mmol of a water-soluble olefin monomer; Add to the above solution, shake and oscillate, heat to 140°C, and react for 6 hours; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0199] Embodiment 13:

[0200] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0201] (1) Spin-coating a layer of water-soluble soap on a substrate, the speed of coating a layer of water-soluble soap is 3000 rpm, the time is 110 s, the anti-sticking layer is a 10 wt % water-soluble soap solution, and the drying temperature is 70° C.; then depositing a polyethylene flexible substrate;

[0202] (2) Spin coating S1810 photoresist on the flexible substrate at a speed of 1000 rpm for 180 seconds; bake at a temperature of 200°C for 120 seconds; then expose the substrate to ultraviolet light through a photomask for 10 seconds; immerse the exposed substrate in a developer at a temperature of 30°C for 120 seconds; then wash with ultrapure water and dry with nitrogen; 2 A plasma treatment apparatus was used to treat the photolithographically patterned substrate at 550W for 600min to deposit 5nm carbon nanotubes on the surface of the flexible substrate as the sensing interface and connecting lines;

[0203] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (46% silane A-17, 47% ultrapure water, 47% isopropyl alcohol) for 20 minutes, then cleaned, and then heat-dried at 200°C for 120 minutes; then, a polyparaxylene layer and a dithioester derivative functionalized polyparaxylene layer are sequentially deposited on the electrode to achieve the encapsulation of the connecting lines;

[0204] The steps of depositing polyparaxylene are as follows: 5g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 8Pa, the polyparaxylene is first sublimated at 220°C, then cracked at 680°C, and finally deposited at 20°C to obtain a polyparaxylene layer;

[0205] The process of depositing the poly(p-xylene) layer functionalized with dithioester derivatives is as follows: 1 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 10Pa, first The monomer is sublimated at 220°C, cracked at 600°C, and finally deposited at 30°C to obtain a poly(p-xylene) layer functionalized with a dithioester derivative.

[0206] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the coating speed of the layer of water-soluble soap is 3000 rpm, the time is 110 s, the anti-sticking layer is a 10 wt % water-soluble soap solution, and the drying temperature is 70° C. After drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0207] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 3000 rpm for 120 s; bake at a temperature of 140° C. for 120 s; then expose the substrate to ultraviolet light through a photomask for 10 s; immerse the exposed substrate in a developer at a temperature of 25° C. for 120 s; then rinse with ultrapure water and dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 2 h at 500 W for pattern etching;

[0208] (6) peeling the device prepared in step (5) from the substrate, and depositing a layer of dithioester derivative functionalized polyparaxylene on the back side of the device in the same process as the process of depositing the dithioester derivative functionalized polyparaxylene layer in step (3);

[0209] (7) Add the device prepared in (6) to 30 mL of dimethyl sulfoxide reaction solution; weigh 50 mmol of azobiscyanovaleric acid and 500 mmol of a water-soluble olefin monomer; Add to the above solution, shake and oscillate, heat to 50°C, and react for 4 hours; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0210] Embodiment 14:

[0211] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0212] (1) Spin-coating a layer of water-soluble soap on a substrate at a speed of 1000 rpm for 1200 s, with a 6 wt % water-soluble soap solution as the anti-sticking layer, and drying at a temperature of 100° C.; then depositing a polyethylene terephthalate flexible substrate;

[0213] (2) Spin coating S1813 photoresist on the flexible substrate at a speed of 7000 rpm for 20 seconds; bake at a temperature of 200°C for 20 seconds; then expose the substrate to ultraviolet light through a photomask for 2 seconds; immerse the exposed substrate in a developer at a temperature of 30°C for 60 seconds; then wash with ultrapure water and dry with nitrogen; 2 Plasma treatment apparatus, treating the photolithographically patterned substrate at 400W for 50min; depositing 100nm metal nanowires on the surface of the flexible substrate as the sensing interface and connecting lines;

[0214] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (42% silane A-17, 49% ultrapure water, 49% isopropyl alcohol) for 20 minutes, then cleaned, and then heat-dried at 100°C for 20 minutes; then, a polyparaxylene layer and a dithioester derivative functionalized polyparaxylene layer are sequentially deposited on the electrode to achieve the encapsulation of the connecting lines;

[0215] The steps of depositing polyparaxylene are as follows: 3g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 10Pa, the polyparaxylene is first sublimated at 200°C, then cracked at 700°C, and finally deposited at 20°C to obtain a polyparaxylene layer;

[0216] The process of depositing the poly(p-xylene) layer functionalized with dithioester derivatives is as follows: 2 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 100Pa, first The monomer is sublimated at 300°C, cracked at 1000°C, and finally deposited at 50°C to obtain a poly(p-xylene) layer functionalized with a dithioester derivative.

[0217] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the speed of coating a layer of water-soluble soap is 1000 rpm, the time is 1200 s, the anti-sticking layer is a 6 wt % water-soluble soap solution, and the drying temperature is 100° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0218] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 3000 rpm for 180 seconds; bake at a temperature of 50° C. for 1200 seconds; then expose the substrate to ultraviolet light through a photomask for 120 seconds; immerse the exposed substrate in a developer at a temperature of 40° C. for 1200 seconds; then rinse with ultrapure water and dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, and the photolithographically patterned thin film is processed at 2000W for 6h for pattern etching;

[0219] (6) The device prepared in (5) was added to a 100 mL methanol and water (volume ratio 1:1) reaction solution; 18 mmol of azobisisobutyronitrile was weighed, and then 170 mmol of a water-soluble olefin monomer was weighed. Add to the above solution, shake and oscillate, heat to 70°C, and react for 1 hour; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0220] Embodiment 15:

[0221] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0222] (1) Spin-coating a layer of water-soluble soap on a substrate at a speed of 500 rpm for 1200 s, with a 10 wt % water-soluble soap solution as the anti-sticking layer, and drying at a temperature of 300° C.; then depositing a polyimide flexible substrate;

[0223] (2) Spin coating S1810 photoresist on the flexible substrate at a speed of 1000 rpm for 180 seconds; bake at a temperature of 200°C for 1200 seconds; then expose the substrate to ultraviolet light through a photomask for 10 seconds; immerse the exposed substrate in a developer at a temperature of 30°C for 300 seconds; then wash with ultrapure water and dry with nitrogen; 2 The plasma treatment instrument treats the photolithographically patterned substrate at 300W for 5min, depositing 200nm of conductive polymer on the surface of the flexible substrate as the sensing interface and connecting circuit;

[0224] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (10% silane A-174, 45% ultrapure water, 45% isopropyl alcohol) for 30 minutes, then washed, and then heat-dried at 60°C for 30 minutes; then, a poly(p-xylene) layer and a poly(p-xylene) dithioester derivative functionalized poly(p-xylene) layer are sequentially deposited on the electrode to achieve the encapsulation of the connecting lines;

[0225] The steps of depositing polyparaxylene are as follows: 10g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 10Pa, the polyparaxylene is first sublimated at 70°C, then cracked at 1000°C, and finally deposited at 20°C to obtain a polyparaxylene layer;

[0226] The process of depositing the poly(p-xylene) layer functionalized with dithioester derivatives is as follows: 110 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 20Pa, first The monomer is sublimated at 300°C, cracked at 400°C, and finally deposited at 40°C to obtain a poly(p-xylene) layer functionalized with a dithioester derivative.

[0227] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the speed of coating a layer of water-soluble soap is 500 rpm, the time is 1200 s, the anti-sticking layer is a 10 wt % water-soluble soap solution, and the drying temperature is 300° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0228] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 5000 rpm for 20 seconds; bake at a temperature of 120° C. for 1000 seconds; then expose the substrate to ultraviolet light through a photomask for 20 seconds; immerse the exposed substrate in a developer at a temperature of 20° C. for 1200 seconds; then rinse with ultrapure water and dry with nitrogen; then purify with low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 6 h at 0 to 2000 W for pattern etching;

[0229] (6) peeling the device prepared in step (5) from the substrate, and depositing another dithioester derivative functionalized polyparaxylene layer on the back side of the device in the same process as the process of depositing the dithioester derivative functionalized polyparaxylene layer in step (3);

[0230] (7) The device prepared in (6) was added to a reaction solution of 10 mL of ethanol and water (volume ratio 1:1); 62 mmol of azobisisobutyronitrile and 340 mmol of a water-soluble olefin monomer were weighed. Add to the above solution, shake and oscillate, heat to 40°C, and react for 4 hours; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0231] Embodiment 16:

[0232] A method for preparing a biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer comprises the following steps:

[0233] (1) Spin-coating a layer of water-soluble soap on a substrate, the speed of coating a layer of water-soluble soap is 1500 rpm, the time is 15 s, the anti-sticking layer is a 2 wt % water-soluble soap solution, and the drying temperature is 120° C.; then depositing a polyparaxylene flexible substrate;

[0234] (2) Spin coating S1813 photoresist on the flexible substrate at a speed of 3500 rpm for 60 seconds; bake at a temperature of 115°C for 60 seconds; then expose the substrate to ultraviolet light through a photomask for 2 seconds; immerse the exposed substrate in a developer at a temperature of 25°C for 10 seconds; then wash with ultrapure water and dry with nitrogen; 2 A plasma treatment instrument was used to treat the photolithographically patterned substrate at 400W for 5 minutes. An electron beam evaporator was used to deposit 5nm of chromium and 180nm of gold on the surface of the flexible substrate as the sensing interface and connecting lines.

[0235] (3) The flexible substrate on which the sensing interface and the connecting lines are deposited is immersed in an adhesive (41% silane A-17, 49.5% ultrapure water, 49.5% isopropyl alcohol) for 30 minutes, then cleaned, and then heat-dried at 70°C for 30 minutes; then, a polyparaxylene layer and a dithioester derivative functionalized polyparaxylene layer are sequentially deposited on the electrode to achieve the encapsulation of the connecting lines;

[0236] The steps of depositing polyparaxylene are as follows: 5g of polyparaxylene is added into the sublimation zone of a chemical vapor deposition reactor, and the polyparaxylene is deposited by a chemical vapor deposition method; the chemical vapor deposition method is as follows: under a vacuum pressure of 5Pa, the polyparaxylene is first sublimated at 120°C, then cracked at 670°C, and finally deposited at 25°C to obtain a polyparaxylene layer;

[0237] The process of depositing the poly(p-xylene) layer functionalized with dithioester derivatives is as follows: 1 g The monomer is added into the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 10Pa, first The monomer is sublimated at 120°C, cracked at 550°C, and finally deposited at 25°C to obtain a poly(p-xylene) layer functionalized with a dithioester derivative.

[0238] (4) coating a layer of water-soluble soap on the electrode obtained in step (3), the coating speed of the layer of water-soluble soap is 1500 rpm, the time is 15 s, the anti-sticking layer is a 2 wt % water-soluble soap solution, and the drying temperature is 120° C.; after drying, depositing a polyparaxylene sacrificial layer, the steps are the same as depositing polyparaxylene in step 3;

[0239] (5) Spin coating AZ9260 photoresist on the electrode obtained in step (4) at a speed of 2000 rpm for 20 seconds; bake at a temperature of 105° C. for 180 seconds; then expose the substrate to ultraviolet light through a photomask for 30 seconds; immerse the exposed substrate in a developer at a temperature of 25° C. for 420 seconds; then rinse with ultrapure water and blow dry with nitrogen; then immerse in a developer at low temperature O 2 The plasma processor performs pattern etching, treating the photolithographically patterned film for 2 h at 400 W for pattern etching;

[0240] (6) peeling the device prepared in step (5) from the substrate, and depositing a layer of dithioester derivative functionalized polyparaxylene on the back side of the device in the same process as the process of depositing the dithioester derivative functionalized polyparaxylene layer in step (3);

[0241] (7) The device prepared in (6) was added to a reaction solution of 6 mL of water and dimethyl sulfoxide (volume ratio: 1:1); 22.7 mmol of azobismethoxyisoheptanenitrile was weighed, and 114 mmol of a water-soluble olefin monomer was weighed. Add to the above solution, shake and oscillate, heat to 50°C, and react for 3 hours; after the reaction, rinse with water and blow dry with nitrogen to obtain an organic electronic device encapsulated by a bionic functional sealing encapsulation layer.

[0242] In order to better verify the effect of the bionic functional sealing packaging layer of the present invention, the present invention uses the bionic functional sealing packaging layer prepared in Example 9 as a sample for experimental testing and analysis. Figure 1 The initiator monomer used in the method of this embodiment is 1H-NMR spectrum of Figure 1 It can be seen that we have successfully prepared the initiator monomer Figure 2 This is the anti-bovine serum albumin adhesion curve of the biomimetic functional sealing packaging layer prepared in Example 9 and pure polyparaxylene. Figure 3 This is the anti-fibrinogen adhesion ability curve of the biomimetic functional sealing packaging layer prepared in Example 9 and pure polyparaxylene. Figure 4 This is the anti-fetal bovine serum adhesion curve of the biomimetic functional sealing encapsulation layer prepared in Example 9 and pure polyparaxylene. Figure 2-Figure 4 It can be seen that the prepared bionic insulating material has high resistance to nonspecific adhesion and can effectively prevent the adhesion of various proteins. Figure 5 This is a comparison of the 24h anti-microglial cell adhesion ability of the biomimetic functional sealing encapsulation layer film prepared in Example 9 and pure polyparaxylene. Figure 5It can be seen that the prepared bionic functional sealing packaging layer has the ability to resist the adhesion of microglia, and the prepared bionic functional sealing packaging layer has significant anti-microglial nonspecific adhesion ability. The 24h anti-microglial adhesion ability of pure polyparaxylene is weak, resulting in the weakening of the performance of the in vivo implanted device packaged with pure polyparaxylene as the insulating material. Figure 6 The Young's modulus of the biomimetic functional sealing encapsulation layer film prepared in Example 9 of the present invention and pure polyparaxylene. It can be seen from the figure that the modulus of the biomimetic functional sealing encapsulation layer is significantly reduced, which is 4 orders of magnitude lower than the Young's modulus of pure polyparaxylene;

[0243] Figure 7 The photo shows the adhesion of the biomimetic functional sealing packaging layer prepared in Example 9 of the present invention to pure polyparaxylene; it can be seen from the figure that the biomimetic functional sealing packaging layer can be perfectly adhered to various surfaces of complex shapes and has very good adhesion performance. However, pure polyparaxylene cannot be adhered to various surfaces of complex shapes and has poor adhesion performance.

[0244] Figure 8 This is a comparison of the adhesion between the biomimetic functional sealing packaging layer prepared in Example 9 of the present invention and pure polyparaxylene; it can be seen from the figure that the adhesion between the biomimetic functional sealing packaging layer and the probe is 862nN, and the adhesion between the pure polyparaxylene and the probe is 22nN. In comparison, the adhesion of the biomimetic functional sealing packaging layer is 39 times higher than that of pure polyparaxylene.

[0245] Therefore, it can be expected that the bionic functional sealing packaging layer can be used as a bionic functional sealing packaging layer for flexible bioelectronic devices, which can significantly inhibit nonspecific adhesion interference and adhesion of inflammatory factors under complex biological environmental conditions, and can further achieve specific effects with cells, viruses and biological molecules, thereby maximizing the selectivity, accuracy and long-term usability of device sensing or recording.

[0246] In summary, the present invention introduces anti-adhesion groups into the surface of poly-p-xylene to prepare a type of biomimetic poly-p-xylene insulating material with anti-nonspecific adhesion ability. In the above process, the poly-p-xylene monomer containing an initiator is first deposited by chemical vapor deposition to obtain an insulating polymer containing an initiator; and then the hydrophilic anti-adhesion group is introduced into the surface of the insulating material by atom transfer radical polymerization (ATRP) to achieve the biomimetic of the insulating material, thereby giving the prepared biomimetic insulating material excellent anti-protein and anti-cell adhesion capabilities.

[0247] Fig. 9This is a schematic diagram of the electrochemical transistor prepared in Example 9 of the present invention and comprising a biomimetic functional sealing packaging layer to achieve controllable interaction with cells; it can be seen from the figure that the electrochemical transistor with the biomimetic functional sealing packaging layer can effectively control the cells within the gate or channel region.

[0248] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes, and they can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the illustrations shown and described herein.

Claims

1. A biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer, characterized in that: It comprises a flexible substrate, a connecting line and a biomimetic functional sealing packaging layer, wherein the biomimetic functional sealing packaging layer has a double-layer structure, the bottom layer is unmodified polyparaxylene, and the upper layer is polyparaxylene modified by zwitterionic groups.

2. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 1, characterized in that: The bionic functional sealing packaging layer is a bionic functional insulating polymer film, the main chain of which is polyparaxylene. The polyparaxylene surface has zwitterionic groups, which can repel nonspecific adhesion of cells, viruses, fungi, bacteria and biological molecules.

3. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 1, characterized in that: The bionic functionalized organic electronic device sealing packaging layer has an adhesion force greater than 100 nN and a surface elastic modulus less than 1000 kPa in a wet state.

4. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 1, characterized in that: The zwitterionic group-modified polyparaxylene comprises a monomer unit of formula (I): In formula (I): m, n, k are positive integers, and 10≤m≤5000, 10≤n≤5000, 20≤k≤5000.

5. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 1, characterized in that: -L1- is -(CH2) x -、-(CH2) x -O-(CH2) y -、-(CH2) x -O-CO-(CH2) y -、-(CH2) x -(CH2-CH2-O) y -、-(CH2) x -O-(CH2-CH2-O) y -、-O-(CH2) x -(CH2-CH2-O) y -or-O-(CH2) x -O-(CH2-CH2-O) y -, wherein x, y are integers, and 0≤x≤20, 0≤y≤20; -L2- is Any one or more of the following; -L3- is -(CH2) m -、-(CH2) m -O-(CH2) n -、-(CH2) m -O-CO-(CH2) n -、-(CH2) m -(CH2-CH2-O) n -、-(CH2) m -O-(CH2-CH2-O) n -、-O-(CH2) m -(CH2-CH2-O) n -or-O-(CH2) m -O-(CH2-CH2-O) n -, wherein m, y are integers, and 0≤m≤20, 0≤n≤20; -L4- is -(CH2) p -、-O-(CH2) p -、-C(O)-O-(CH2) p -、-C(O)-NH-(CH2) p -、-C(CH3)2-C(O)-O-(CH2) p -、-CH(CH3)-O-(CH2) p -、-S-CH2-CH2-O-(CH2) p -, -S-CH2-CH(CH3)-C(O)-O-(CH2) p -Any one or more of, where p is an integer and 0≤p≤20; -R1 is -H, (CH2) d Any one of CH3, wherein d is a positive integer and 0≤d≤8; -R2 is Any one of, wherein M is any one of K, Na, Li, Mg, Al, Fe, and X is any one of F, Cl, Br, I; -R3 is -Br, -Cl, -I, Any one of .

6. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 1, characterized in that: The method for preparing the bionic functionalized organic electronic device comprises the following steps: Step 1: Spin-coating a water-soluble soap layer on a substrate and then depositing a flexible substrate; Step 2: Photolithography is performed on the flexible substrate to form a sensing interface and connection circuits; Step 3: Deposit adhesive on the flexible substrate on which the sensing interface and connection lines are deposited, and sequentially deposit polyparaxylene layer and Layer to achieve encapsulation of connection lines; Step 4: coating a water-soluble soap layer on the electrode obtained in step 3, drying it, and then depositing a polyparaxylene sacrificial layer; Step 5: After performing photolithography patterning and plasma dry etching on the electrode obtained in step 4, the sensing interface and connecting wire pins are exposed; Step 6: Peel the device prepared in step 5 off the substrate and deposit a layer of layer, or no deposition layer; Step 7: Mix the device prepared in step 6 and the water-soluble olefin monomer The polymerization reaction is carried out under the conditions of the presence of a ligand and a catalyst, or under the conditions of the presence of a free radical initiator. After a certain reaction time, a product having Organic electronic devices encapsulated by structural bionic functionalized sealing encapsulation layers.

7. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 6, characterized in that: In the step 1, the speed of coating a layer of water-soluble soap is 0-9000 rpm, the time is 0-1200 s, the anti-sticking layer is 0-10 wt % water-soluble soap solution, and the drying temperature is 30-300° C.; In the step 1, the flexible substrate material is any one of polyparaxylene, polydimethylsiloxane, polyurethane, styrene-butadiene-styrene block copolymer, polyvinyl alcohol, polyethylene terephthalate, polyimide, polyethylene naphthalate, paper and textile material.

8. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 6, characterized in that: In the step 2, the process of photolithography patterning is as follows: spin coating the photoresist on the flexible substrate of the substrate, and after baking, the substrate is exposed to ultraviolet light through a photomask; the exposed substrate is immersed in a developer for treatment, and then cleaned, dried with nitrogen, and the photoresist is developed; the spin coating speed is 0 to 9000 rpm, and the spin coating time is 0 to 180 s; the baking temperature is 50 to 200° C., and the time is 0 to 1200 s; the exposure time is 0 to 120 s; the immersion temperature in the developer is 0 to 90° C., and the treatment time is 0 to 1200 s; the plasma dry etching process is as follows: using a low-temperature O2 plasma treatment instrument to treat the photolithography patterned substrate at 0 to 1000 W for 0 to 600 min; In the step 2, the material of the sensing interface and the connecting circuit is any one of gold, platinum, graphene, carbon nanotubes, metal nanowires and conductive polymers.

9. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 6, characterized in that: In the step 3, the process of depositing the adhesive on the flexible substrate on which the sensing interface and the connecting circuit are deposited is as follows: immersing the flexible substrate on which the sensing interface and the connecting circuit are deposited in the adhesive for 0 to 120 minutes, and then washing and drying; the adhesive comprises the following components in weight percentage: 40 to 50% of silane A-17, 0 to 100% of ultrapure water, and 0 to 100% of isopropanol; the drying temperature is 0 to 200° C., and the drying time is 0 to 120 minutes; In the step 3, the process of depositing the polyparaxylene layer is as follows: adding two polyparaxylenes to the sublimation zone of the chemical vapor deposition reactor, and depositing them by chemical vapor deposition method; the chemical vapor deposition method is as follows: under the condition of vacuum pressure of 0 to 100 Pa, first sublimating the two polyparaxylenes at 70 to 300° C., then cracking them at 400 to 1000° C., and finally depositing them at 0 to 50° C. to obtain the polyparaxylene layer; In the step 3, the deposition The specific process is as follows: The monomer is added to the sublimation zone of the chemical vapor deposition reactor; the chemical vapor deposition method is: under the condition of vacuum pressure of 0-100Pa, first The monomer sublimates at 70-300°C, then cracks at 400-1000°C, and finally deposits at 0-50°C. layer.

10. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 7, characterized in that: In the step 4, the process of coating a layer of water-soluble soap is the same as the process of coating a layer of water-soluble soap in the step 4. In the step 4, the process of depositing the polyparaxylene sacrificial layer is the same as the process of depositing the polyparaxylene in the step 3.

11. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 7, characterized in that: In the step 5, the photolithography patterning is the same as the photolithography patterning process in the step 2; In the step 5, the plasma dry etching process is: using a low-temperature O2 plasma processor to treat the photolithography patterned film at 0 to 2000W for 0 to 6 hours.

12. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 7, characterized in that: In step 6, a layer of The process of layer deposition in step 3 The process is the same for all layers.

13. The biomimetic functionalized organic electronic device comprising a biomimetic functionalized sealing encapsulation layer according to claim 7, characterized in that: In the step 7, the The process of forming the biomimetic functional sealing encapsulation layer of the structure adopts any one of atom transfer radical polymerization or reversible addition-fragmentation chain transfer polymerization; In the step 7, the The process of the bionic functional sealing encapsulation layer of the structure adopts atom transfer radical polymerization, and the specific process is as follows: Add the device prepared in step 6 to the reaction solution; weigh 0.1 mmol to 200 mmol of ligand and 0.1 mmol to 100 mmol of catalyst into the above solution, and then weigh 1 mmol to 3000 mmol of water-soluble olefin monomer. Add to the above solution, shake and oscillate, heat to 10℃~100℃, and react for 0h~24h; after the reaction, rinse with water and blow dry with nitrogen to obtain An organic electronic device encapsulated by a structural bionic functional sealing encapsulation layer; the solution is any one or more of methanol, ethanol, water, and dimethyl sulfoxide; the ligand is any one of tris[2-(dimethylamino)ethyl]amine, tris(2-pyridylmethyl)amine, 1,1,4,7,10,10-hexamethyltriethylenetetramine or pentamethyldiethylenetriamine; and the catalyst is any one or more of Cu, CuBr, CuBr2, CuCl or CuCl2. In the step 7, the The process of the bionic functional sealing encapsulation layer of the structure adopts reversible addition-fragmentation chain transfer polymerization, and the specific process is as follows: Add the device prepared in step 6 to the reaction solution; weigh 0.1 mmol to 100 mmol of free radical initiator, and then weigh 1 mmol to 3000 mmol of water-soluble olefin monomer. Add to the above solution, shake and oscillate, heat to 40℃~200℃, and react for 0h~24h; after the reaction, rinse with water and blow dry with nitrogen to obtain An organic electronic device encapsulated by a structural bionic functional sealing encapsulation layer; the solution is any one or more of methanol, ethanol, water, and dimethyl sulfoxide; the free radical initiator is any one of azobisisobutyronitrile, triethylamine, azobismethoxyisoheptanenitrile, or azobiscyanovaleric acid.

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