Modified stretchable electrode and preparation method and application thereof

Abstract

The invention belongs to the technical field of organic functional materials and organic electronics, and particularly relates to a modified stretchable electrode and a preparation method and application thereof. Silver nanowire dispersion liquid is spin-coated on a substrate, an obtained silver nanowire film is patterned, the obtained patterned silver nanowire film is soaked in a modifier (a small molecule compound containing a group capable of being combined with silver and a hydrogen supply group) for modification, the upper portion of the obtained modified silver nanowire film is coated with an organic polymer solution, and after annealing, the silver nanowire film is obtained. And stripping from the substrate to obtain the modified stretchable electrode. Through the interaction between the modified and enhanced silver nanowire film and the organic polymer, the tensile property is improved, the situation that the sheet resistance of the modified stretchable electrode is increased due to breakage of the silver nanowires is avoided, and the modified stretchable electrode has high conductivity, high transparency and high fatigue resistance at the same time.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic functional materials and organic electronics, and particularly relates to a modified stretchable electrode and a preparation method and application thereof. Background Art

[0002] With the increasing demand for real-time health monitoring, human-computer interaction, and implantable biomedical devices, wearable electronic devices have attracted considerable attention in the market. In order to be able to comfortably adhere to elastic human skin, dynamically moving organs, and deformable implantable devices, wearable electronic devices must have high stretchability while maintaining high sensitivity in both relaxed and stretched states. As a core component of flexible electronic devices, stretchable electrodes have demonstrated significant advantages in multiple fields. Among them, stretchable near-infrared organic photodetectors show great application potential in flexible electronics, biomedicine, environmental monitoring, and other fields.

[0003] As a fundamental component of stretchable near-infrared organic photodetectors (OPDs), stretchable transparent electrodes play a key role in achieving highly sensitive stretchable near-infrared OPDs. Among them, silver nanowires (Ag NWs) have excellent conductivity, high transparency and flexibility, and are considered to be attractive candidates for constructing stretchable transparent electrodes when integrated with elastic substrates. However, the mechanical properties (e.g., modulus) of AgNWs-based stretchable electrodes do not match those of the elastic polymer matrix, resulting in stress concentration at the Ag NWs / elastomer interface during stretching. As a result, cracks are easily formed at the Ag NWs / elastomer interface, and Ag NWs crack after cyclic stretching at large strains. In particular, for highly transparent AgNWs composite electrodes with Ag NWs networks, the fracture of AgNWs can lead to an insufficient conductive network, resulting in a significant increase in the square resistance after cyclic stretching. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide a modified stretchable electrode and a preparation method and application thereof. The modified stretchable electrode prepared by the present invention has high stretchability and avoids the increase in square resistance due to the breakage of silver nanowires.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing a modified stretchable electrode, comprising the following steps:

[0007] spin coating a silver nanowire dispersion on a substrate to obtain a silver nanowire film;

[0008] patterning the silver nanowire film to obtain a patterned silver nanowire film;

[0009] immersing the patterned silver nanowire film in a modifier for modification to obtain a modified silver nanowire film;

[0010] The modifier includes a small molecule compound containing a group capable of binding to silver and a hydrogen-donating group;

[0011] coating a solution of an organic polymer on the surface of the modified silver nanowire film, annealing it, and then peeling it from the substrate to obtain a modified stretchable electrode;

[0012] The organic polymer includes one or more of thermoplastic polyurethane, polydimethylsiloxane and polyurethane acrylate.

[0013] Preferably, the group capable of binding to silver includes one or more of carboxyl, sulfonic acid, phosphoric acid, sulfhydryl, carbonyl, hydroxyl, primary amine, secondary amine, tertiary amine, carboxylate ion, sulfonate ion and phosphate ion.

[0014] Preferably, the hydrogen-donating group includes one or more of a hydroxyl group, a primary amine group, a secondary amine group and a tertiary amine group.

[0015] Preferably, the concentration of the small molecule compound containing the group capable of binding to silver and the hydrogen-donating group in the modifier is 10 to 50 mg / mL.

[0016] Preferably, the modification time is 30 to 50 minutes.

[0017] Preferably, the diameter of the silver nanowires is 25 to 30 nm, and the average length is 10 to 30 μm.

[0018] Preferably, the sheet resistance of the silver nanowire film is 11-13Ω / sq.

[0019] The present invention also provides a stretchable bottom electrode prepared by the preparation method described in the above technical solution, comprising an organic polymer coating and a modified silver nanowire film covered on the surface of the organic polymer coating; the organic polymer comprises one or more of thermoplastic polyurethane, polydimethylsiloxane and polyurethane acrylate; the modified silver nanowire film is obtained by modifying the patterned silver nanowire film by a modifier; the modifier comprises a small molecule compound containing a group capable of binding to silver and a hydrogen-donating group; the modified silver nanowire film is bonded to the organic polymer through hydrogen bonds.

[0020] The present invention also provides an application of the stretchable bottom electrode described in the above technical solution in a stretchable near-infrared light detector.

[0021] The present invention also provides a stretchable near-infrared light detector, comprising a stretchable bottom electrode, a conductive layer, a photoactive layer, a cathode interface layer and a stretchable top electrode stacked in sequence; the stretchable bottom electrode is the modified stretchable electrode described in the above technical solution; the modified silver nanowire film side in the modified stretchable electrode is in contact with the conductive layer.

[0022] The present invention provides a method for preparing a modified stretchable electrode, comprising the following steps: spin-coating a silver nanowire dispersion on a substrate to obtain a silver nanowire film; patterning the silver nanowire film to obtain a patterned silver nanowire film; immersing the patterned silver nanowire film in a modifier for modification to obtain a modified silver nanowire film; the modifier comprises a small molecule compound containing a group capable of binding to silver and a hydrogen-donating group; coating a solution of an organic polymer on the surface of the modified silver nanowire film, annealing, and peeling it from the substrate to obtain a modified stretchable electrode; the organic polymer comprises one or more of thermoplastic polyurethane, polydimethylsiloxane, and polyurethane acrylate. The present invention uses a small molecule compound containing both a group capable of binding to silver and a hydrogen-donating group to modify a silver nanowire film. The group capable of binding to silver combines with silver atoms and / or silver ions on the surface of the silver nanowire film through coordination or electrostatic adsorption, and introduces hydrogen-donating groups on the surface of the silver nanowires. The hydrogen-donating groups interact with groups such as ester groups and carbonyl groups in the organic polymer through hydrogen bonds. Thus, the interaction between the silver nanowire film and the organic polymer is enhanced through modification, and during the stretching process, stress concentration caused by the modulus difference between the silver nanowires and the organic polymer is reduced, so that the stress on the silver nanowires can be released into the organic polymer, thereby improving the tensile properties and avoiding an increase in square resistance due to breakage of the silver nanowires. The modified stretchable electrode has high conductivity, high transparency and high fatigue resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Ag 3dXPS spectra of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3 and the stretchable electrode (AgNWs) prepared in Comparative Example 1;

[0024] Figure 2 S2p XPS spectra of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3, the stretchable electrode (AgNWs) prepared in Comparative Example 1, and TAPSO sodium salt (HOS);

[0025] Figure 3 Na 1s XPS spectra of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3, the stretchable electrode (AgNWs) prepared in Comparative Example 1, and TAPSO sodium salt (HOS);

[0026] Figure 4UPS spectra of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3 and the stretchable electrode (AgNWs) prepared in Comparative Example 1;

[0027] Figure 5 The single stretching square resistance change function diagram of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3 and the stretchable electrode (AgNWs) prepared in Comparative Example 1;

[0028] Figure 6 Graph showing the change in square resistance as a function of cyclic stretching of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3 and the stretchable electrode (AgNWs) prepared in Comparative Example 1;

[0029] Figure 7 Graphs showing the relative detectivity of the stretchable near-infrared photodetector (AgNWs-HOS) prepared in Application Example 3, the stretchable near-infrared photodetector (AgNWs) prepared in Comparative Application Example 1, and the stretchable near-infrared photodetector (ITO) prepared in Comparative Application Example 2. DETAILED DESCRIPTION

[0030] The present invention provides a method for preparing a modified stretchable electrode, comprising the following steps:

[0031] spin coating a silver nanowire dispersion on a substrate to obtain a silver nanowire film;

[0032] patterning the silver nanowire film to obtain a patterned silver nanowire film;

[0033] immersing the patterned silver nanowire film in a modifier for modification to obtain a modified silver nanowire film;

[0034] The modifier includes a small molecule compound containing a group capable of binding to silver and a hydrogen-donating group;

[0035] A solution of an organic polymer is coated on the surface of the modified silver nanowire film, and after annealing, the film is peeled off from the substrate to obtain a modified stretchable electrode.

[0036] Unless otherwise specified, the present invention has no special requirements on the sources of the raw materials used, and commercially available products known to those skilled in the art can be used.

[0037] The invention spin-coats a silver nanowire dispersion on a substrate to obtain a silver nanowire film.

[0038] As an embodiment, the substrate is a glass substrate; the diameter of the silver nanowires is 25 to 30 nm, specifically 25 nm in a specific embodiment, and the average length is 10 to 30 μm, specifically 20 μm in a specific embodiment; the silver nanowire dispersion comprises silver nanowires, a dispersant, and a polar solvent; the dispersant is polyvinyl pyrrolidone (PVP); the polar solvent is ethanol; the mass ratio of silver nanowires to polar solvent in the silver nanowire dispersion is 2 to 5:95 to 98, specifically 2.5:97.5 in a specific embodiment.

[0039] As an embodiment, before the spin coating, the process further includes: sequentially cleaning, drying, and ultraviolet ozone treatment of the substrate; the cleaning reagents are detergent, deionized water, acetone, and isopropyl alcohol; the drying temperature is 120 to 150°C, specifically 120°C in a specific embodiment, and the drying time is 50 minutes to 2 hours, specifically 1 hour in a specific embodiment; the ultraviolet ozone treatment equipment is an ultraviolet ozone meter; the ultraviolet ozone treatment power is 50 to 60W, specifically 50W in a specific embodiment, and the time is 25 to 30 minutes, specifically 25 minutes in a specific embodiment.

[0040] The present invention uses detergent for cleaning to remove large particle contaminants such as grease, fingerprints, and dust on the surface of the substrate; uses deionized water to rinse away detergent residue and soluble impurities while avoiding ion contamination; uses acetone to dissolve non-polar or weakly polar organic contaminants; and uses isopropyl alcohol to remove residual acetone, moisture, and extremely trace organic matter, and promotes rapid drying of the surface.

[0041] The invention improves the wettability of the substrate through ultraviolet ozone treatment.

[0042] As an embodiment, the spin coating has a rotation speed of 1200-1500 rpm, specifically 1200 rpm, and a time of 30-40 s, specifically 30 s in the embodiment.

[0043] As an embodiment, the sheet resistance of the silver nanowire film is 11-13Ω / sq, and in a specific embodiment, it is 11.7Ω / sq.

[0044] After obtaining the silver nanowire film, the present invention patterns the silver nanowire film to obtain a patterned silver nanowire film.

[0045] The present invention does not specifically limit the patterning method, and methods well known in the art can be used. In an embodiment of the present invention, the patterning is to retain a rectangular area in the center of the silver nanowire film, and then remove excess silver nanowire film with a scraper to retain a complete pattern.

[0046] After obtaining the patterned silver nanowire film, the present invention immerses the patterned silver nanowire film in a modifier for modification to obtain a modified silver nanowire film; the modifier includes a small molecule compound containing a group capable of binding to silver and a hydrogen-donating group.

[0047] In one embodiment, the silver-binding groups include one or more of carboxyl, sulfonic, phosphoric, sulfhydryl, carbonyl, hydroxyl, primary, secondary, tertiary amine, carboxylate, sulfonate, and phosphate ions, with specific embodiments including one or more of sulfonic, hydroxyl, and secondary amine groups. The hydrogen-donating groups include one or more of hydroxyl, primary, secondary, and tertiary amine groups, with specific embodiments including hydroxyl and / or secondary amine groups. The silver-binding groups are groups that bind to silver atoms and / or silver ions on the surface of the patterned silver nanowire film through coordination or electrostatic adsorption, and the hydrogen-donating groups are groups that provide hydrogen bonds.

[0048] As an embodiment, the concentration of the small molecule compound containing a group capable of binding to silver and a hydrogen-donating group in the modifier is 10 to 50 mg / mL, and in specific embodiments is 10 mg / mL, 25 mg / mL or 50 mg / mL.

[0049] In an embodiment of the present invention, the small molecule compound containing a group capable of binding to silver and a hydrogen-donating group is sodium salt of N-tris(hydroxymethyl)carbamate-2-hydroxypropanesulfonic acid (TAPSO). TAPSO acts as a "tether" connecting the AgNWs and the organic polymer chains, thereby achieving higher mechanical durability in the modified stretchable electrode.

[0050] As an embodiment, the modification time is 30 to 50 minutes, and in a specific embodiment, it is 30 to 40 minutes; the modification temperature is 25 to 30°C, and in a specific embodiment, it is 25°C.

[0051] The present invention uses a modifier to enhance the interaction between the silver nanowires and the organic polymer substrate, while removing part of the dispersant to improve the conductivity.

[0052] As an embodiment, after the modification, the process further includes: sequentially cleaning and annealing the modified patterned silver nanowire film; the cleaning reagent is deionized water; the number of cleanings is 3 to 5 times, and in a specific embodiment, it is 3 times; the annealing temperature is 100 to 150° C., and in a specific embodiment, it is 100 to 120° C., and the time is 25 to 60 minutes, and in a specific embodiment, it is 30 to 40 minutes.

[0053] The present invention removes excess modifier on the surface of the modified patterned silver nanowire film by cleaning; and removes moisture by annealing.

[0054] After obtaining the modified silver nanowire film, the present invention coats a solution of an organic polymer on the surface of the modified silver nanowire film, and after annealing, peels it off from the substrate to obtain a modified stretchable electrode.

[0055] As an embodiment, the organic polymer includes one or more of thermoplastic polyurethane (TPU), polydimethylsiloxane (PDMS) and polyurethane acrylate (PUA), and in a specific embodiment, it is thermoplastic polyurethane; the thermoplastic polyurethane is TPU 685A; the solvent used for the solution of the organic polymer is N,N-dimethylformamide (DMF); the mass percentage of the organic polymer in the solution of the organic polymer is 5 to 10%, and in a specific embodiment, it is 5%.

[0056] As an embodiment, the coating is drop coating; the annealing temperature is 40 to 60° C., specifically 50 to 60° C., and the annealing time is 12 to 15 hours, specifically 12 to 14 hours.

[0057] The present invention has no particular limitation on the peeling process, and any peeling process well known in the art may be used.

[0058] The present invention also provides a modified stretchable electrode prepared by the preparation method described in the above technical solution, comprising an organic polymer coating and a modified silver nanowire film covered on the surface of the organic polymer coating; the organic polymer comprises one or more of thermoplastic polyurethane, polydimethylsiloxane and polyurethane acrylate; the modified silver nanowire film is obtained by modifying a patterned silver nanowire film by a modifier; the modifier comprises a small molecule compound containing a group capable of binding to silver and a hydrogen-donating group; the modified silver nanowire film is bonded to the organic polymer through hydrogen bonds.

[0059] The present invention also provides the use of the modified stretchable electrode described in the above technical solution in a stretchable near-infrared light detector.

[0060] The present invention also provides a stretchable near-infrared light detector, comprising a stretchable bottom electrode, a conductive layer, a photoactive layer, a cathode interface layer and a stretchable top electrode stacked in sequence; the stretchable bottom electrode is the modified stretchable electrode described in the above technical solution; the modified silver nanowire film side in the modified stretchable electrode is in contact with the conductive layer.

[0061] As an embodiment, the conductive layer is composed of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and has a thickness of 50 to 60 nm, and in a specific embodiment, 60 nm.

[0062] In one embodiment, the photoactive layer comprises an organic photoelectron polymer acceptor material and an additive. The organic photoelectron polymer acceptor material is PM6, PY-IT, and N2200. The mass ratio of PM6, PY-IT, and N2200 is 1:0.8-1.0:0.4-0.5, and in a specific embodiment, it is 1:0.8:0.4. The additive is 1-chloronaphthalene or 1,8-diiodooctane, and in a specific embodiment, it is 1-chloronaphthalene. The thickness of the photoactive layer is 120-130 nm, and in a specific embodiment, it is 120 nm. The additive can improve the phase separation scale of the photoactive layer.

[0063] In one embodiment, the cathode interface layer comprises a cathode interface layer material; the cathode interface layer material is one or more of PFN-Br, PNDIT-F3N, and PNDIT-F3N-Br, with PNDIT-F3N-Br being the preferred material in the specific embodiment. The cathode interface layer has a thickness of 10 to 20 nm, with a preferred thickness of 10 nm in the specific embodiment. All cathode interface layer materials are available from Nanjing Zhiyan Technology Co., Ltd.

[0064] As an embodiment, the stretchable top electrode is a gallium-indium alloy; the thickness of the stretchable top electrode is 1 to 3 μm, and in a specific embodiment, it is 2 μm.

[0065] As an embodiment, the method for preparing the stretchable near-infrared light detector comprises the following steps:

[0066] A solution containing components of a conductive layer is first spin-coated on the surface of the silver nanowire film in the modified stretchable electrode, followed by first annealing to form a conductive layer;

[0067] a second spin coating of a solution containing components of a photoactive layer on the surface of the conductive layer, followed by a second annealing to form a photoactive layer;

[0068] a third spin coating of a solution containing components of a cathode interface layer on the surface of the photoactive layer, and a third annealing to form a cathode interface layer;

[0069] The components of the stretchable top electrode are sprayed on the surface of the cathode interface layer to form a stretchable top electrode, thereby obtaining a stretchable near-infrared light detector.

[0070] As an embodiment, the solvent in the solution containing the conductive layer components is water and / or methanol, specifically water in a specific embodiment; the first spin coating speed is 3500-4000 rpm, specifically 4000 rpm in a specific embodiment, and the time is 30-40 seconds, specifically 40 seconds in a specific embodiment; the first annealing temperature is 100-120°C, specifically 100-110°C in a specific embodiment, and the time is 20-30 minutes, specifically 20-25 minutes in a specific embodiment. In an embodiment of the present invention, the model of the solution containing the conductive layer components is AI 4083. The present invention removes excess solution and promotes crystallization through the first annealing.

[0071] In one embodiment, the solvent in the solution containing the components of the photoactive layer is one or more of chloroform, chlorobenzene, and dichlorobenzene, specifically chloroform in a specific embodiment. The concentration of the organic photoelectron polymer acceptor material in the solution containing the components of the photoactive layer is 14.3 to 16.0 mg / mL, specifically 14.3 to 15 mg / mL in a specific embodiment. The volume fraction of the additive is 0.1 to 5% of the volume fraction of the solvent, specifically 0.4% in a specific embodiment. The second spin coating speed is 2000 to 2500 rpm, specifically 2000 rpm in a specific embodiment, and the time is 30 to 40 seconds, specifically 40 seconds in a specific embodiment. The second annealing temperature is 80 to 100°C, specifically 90 to 100°C, and the time is 10 to 20 minutes, specifically 10 minutes in a specific embodiment. The present invention promotes crystallization of the organic photoelectron polymer acceptor material and improves carrier mobility through the second annealing.

[0072] As an embodiment, the solvent in the solution containing the components of the cathode interface layer is one or more of methanol, ethanol and trifluoroethanol, and in a specific embodiment, it is methanol; the concentration of the components of the cathode interface layer in the solution containing the components of the cathode interface layer is 0.2 to 1 mg / mL, and in a specific embodiment, it is 0.5 to 1 mg / mL; the rotation speed of the third spin coating is 2000 to 3000 rpm, and in a specific embodiment, it is 2000 rpm, and the time is 30 to 40 s, and in a specific embodiment, it is 30 s; the temperature of the third annealing is 25 to 40°C, and in a specific embodiment, it is 25°C, and the time is 10 to 20 min, and in a specific embodiment, it is 10 min.

[0073] As an embodiment, the spraying air pressure is 0.1-0.2 kPa, specifically 0.15 kPa, the temperature is 25-30° C., specifically 25° C., and the time is 2-3 s, specifically 2 s.

[0074] The technical solutions of the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention, but they should not be understood as limiting the scope of protection of the present invention.

[0075] Example 1

[0076] Commercial glass substrates were cleaned with detergent, deionized water, acetone, and isopropyl alcohol in sequence, then dried at 120°C for 50 minutes. The cleaned glass substrates were treated with UV-ozone at 50W power for 25 minutes using a UV-ozone analyzer. A silver nanowire solution (a silver nanowire with a diameter of 25 nm and an average length of 20 μm and a mass ratio of 2.5:97.5 to ethanol, also containing PVP) was spin-coated on the glass substrate to obtain a silver nanowire film with a square resistance of 11.7 Ω / sq. A rectangular area was retained in the center of the silver nanowire film, and then the excess silver nanowire film was removed with a scraper to retain the complete pattern.

[0077] The patterned silver nanowire film was modified by soaking it in a 10 mg / mL N-tris(hydroxymethyl)carboxylic acid-2-hydroxypropanesulfonic acid sodium salt (TAPSO sodium salt) solution (the solvent was deionized water) at 25°C for 30 minutes, then washed three times with deionized water and annealed at 100°C for 30 minutes to remove moisture. A thermoplastic polyurethane (TPU 685A) solution (the mass percentage of thermoplastic polyurethane was 5% and the solvent was DMF) was then drop-coated on the modified silver nanowire film, annealed at 60°C for 12 hours to remove N,N-dimethylformamide (DMF), and then peeled off from the glass substrate to obtain a modified stretchable electrode.

[0078] Example 2

[0079] The difference from Example 1 is that the concentration of the TAPSO sodium salt solution is 25 mg / mL, and the rest of the contents are the same as those in Example 1.

[0080] Example 3

[0081] The difference from Example 1 is that the concentration of the TAPSO sodium salt solution is 50 mg / mL, and the rest of the contents are the same as those in Example 1.

[0082] Comparative Example 1

[0083] The difference from Example 1 is that the step of modifying the TAPSO sodium salt solution is not performed, and the thermoplastic polyurethane (TPU 685A) solution is directly drop-coated on the surface of the patterned silver nanowire film. The rest of the contents are the same as those in Example 1.

[0084] Application Example 1

[0085] A poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) solution (purchased from an external source, model number AI4083) was spin-coated at 4000 rpm for 40 seconds on the surface of the silver nanowire film in the modified stretchable electrode prepared in Example 1 as the stretchable bottom electrode, and annealed at 100° C. for 20 minutes to form a 60 nm thick conductive layer;

[0086] A 1-chloronaphthalene solution (0.4% by volume of the chloroform solution) was added to a chloroform solution containing PM6, PY-IT, and N2200 in a mass ratio of 1:0.8:0.4 (total concentration of 14.3 mg / mL). The resulting mixed solution was spin-coated on the surface of the conductive layer at 2000 rpm for 40 seconds and annealed at 100°C for 10 minutes to form a 120 nm thick photoactive layer.

[0087] PNDIT-F3N-Br purchased from Nanjing Zhiyan Technology Co., Ltd. was dissolved in methanol. The resulting solution with a concentration of 1 mg / mL was spin-coated on the surface of the photoactive layer at 2000 rpm for 30 seconds and annealed at 25°C for 10 minutes to form a cathode interface layer with a thickness of 10 nm.

[0088] Gallium-indium alloy was sprayed on the surface of the cathode interface layer at a pressure of 0.15 kPa, a temperature of 25°C, and a time of 2 s to form a stretchable top electrode with a thickness of 2 μm, thereby obtaining a stretchable near-infrared light detector.

[0089] Application Examples 2-3

[0090] The difference from Application Example 1 is that the modified stretchable electrode prepared in Example 1 is replaced by the modified stretchable electrodes of Examples 2 to 3 respectively.

[0091] Comparative Application Example 1

[0092] The difference from Application Example 1 is that the modified stretchable electrode prepared in Example 1 is replaced by the stretchable electrode of Comparative Example 1.

[0093] Comparative Application Example 2

[0094] The difference from Application Example 1 is that the modified stretchable electrode prepared in Example 1 is replaced by an indium tin oxide electrode.

[0095] Performance Testing

[0096] (1) Figure 1 Ag 3dXPS spectra of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3 and the stretchable electrode (AgNWs) prepared in Comparative Example 1, measured by X-ray photoelectron spectrometer.

[0097] from Figure 1It can be seen that the XPS peak of Ag 3d shifts, indicating that there is an interaction between TAPSO sodium salt (HOS) and AgNWs.

[0098] (2) Figure 2 S2p XPS spectra of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3, the stretchable electrode (AgNWs) prepared in Comparative Example 1, and TAPSO sodium salt (HOS), measured by X-ray photoelectron spectrometer.

[0099] from Figure 2 It can be seen that the appearance of S2p XPS indicates that HOS is successfully modified on the surface of AgNWs.

[0100] (3) Figure 3 Na 1s XPS spectra of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3, the stretchable electrode (AgNWs) prepared in Comparative Example 1, and TAPSO sodium salt (HOS), measured by X-ray photoelectron spectrometer.

[0101] from Figure 3 It can be seen that the Na 1s peak disappears, indicating that the excess HOS is removed and the interaction between HOS and AgNWs is hydrogen bonding rather than physical adsorption.

[0102] (4) Figure 4 UPS spectra of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3 and the stretchable electrode (AgNWs) prepared in Comparative Example 1, measured by ultraviolet photoelectron spectrometer.

[0103] from Figure 4 It can be seen that the XPS peak of Ag 3d shifts, indicating that there is an interaction between HOS and AgNWs.

[0104] (5) Figure 5 This is a single stretching square resistance change function diagram of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3 and the stretchable electrode (AgNWs) prepared in Comparative Example 1, and the change with the stretching ratio was measured by a four-probe tester.

[0105] from Figure 5 It can be seen that after HOS modification, the secondary electron cutoff edge shifts, indicating that HOS interacts with AgNWs.

[0106] (6) Figure 6 This is a graph showing the change in square resistance as a function of cyclic stretching of the modified stretchable electrode (AgNWs-HOS) prepared in Example 3 and the stretchable electrode (AgNWs) prepared in Comparative Example 1, as measured by a four-probe tester at 50% strain with the number of stretching times.

[0107] from Figure 6 It can be seen that the tensile properties of AgNWs improve after HOS modification.

[0108] (7) Figure 7 The relative detection rate curves of the stretchable near-infrared light detector (AgNWs-HOS) prepared in Application Example 3, the stretchable near-infrared light detector (AgNWs) prepared in Comparative Application Example 1, and the stretchable near-infrared light detector (ITO) prepared in Comparative Application Example 2 are obtained by joint testing with an external quantum efficiency tester and a semiconductor parameter meter.

[0109] from Figure 7 It can be seen that after HOS modification, the stretchable near-infrared photodetector device based on AgNWs-HOS electrode has the best performance, indicating that HOS modification has a positive effect on the stretchable near-infrared photodetector.

[0110] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention rather than all the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a modified stretchable electrode, characterized in that: The following steps are involved: spin coating a silver nanowire dispersion on a substrate to obtain a silver nanowire film; patterning the silver nanowire film to obtain a patterned silver nanowire film; immersing the patterned silver nanowire film in a modifier for modification to obtain a modified silver nanowire film; The modifier includes a small molecule compound containing a group capable of binding to silver and a hydrogen-donating group; coating a solution of an organic polymer on the surface of the modified silver nanowire film, annealing it, and then peeling it from the substrate to obtain a modified stretchable electrode; The organic polymer includes one or more of thermoplastic polyurethane, polydimethylsiloxane and polyurethane acrylate.

2. The preparation method according to claim 1, characterized in that The groups capable of combining with silver include one or more of carboxyl, sulfonic acid, phosphoric acid, sulfhydryl, carbonyl, hydroxyl, primary amine, secondary amine, tertiary amine, carboxylate ion, sulfonate ion and phosphate ion.

3. The preparation method according to claim 1, characterized in that The hydrogen-donating group includes one or more of a hydroxyl group, a primary amine group, a secondary amine group and a tertiary amine group.

4. The preparation method according to claim 1, 2 or 3, characterized in that: The concentration of the small molecule compound containing the group capable of combining with silver and the hydrogen-donating group in the modifier is 10-50 mg / mL.

5. The preparation method according to claim 1, characterized in that The modification time is 30 to 50 minutes.

6. The preparation method according to claim 1, characterized in that The diameter of the silver nanowires is 25 to 30 nm, and the average length is 10 to 30 μm.

7. The preparation method according to claim 1, characterized in that The sheet resistance of the silver nanowire film is 11-13Ω / sq.

8. The stretchable bottom electrode prepared by the preparation method according to any one of claims 1 to 7, characterized in that: The invention comprises an organic polymer coating and a modified silver nanowire film coated on the surface of the organic polymer coating; the organic polymer comprises one or more of thermoplastic polyurethane, polydimethylsiloxane and polyurethane acrylate; the modified silver nanowire film is obtained by modifying a patterned silver nanowire film with a modifier; the modifier comprises a small molecule compound containing a group capable of binding to silver and a hydrogen-donating group; the modified silver nanowire film is bonded to the organic polymer through hydrogen bonds.

9. Use of the stretchable bottom electrode according to claim 8 in a stretchable near-infrared light detector.

10. A stretchable near-infrared light detector, characterized in that: It comprises a stretchable bottom electrode, a conductive layer, a photoactive layer, a cathode interface layer and a stretchable top electrode stacked in sequence; the stretchable bottom electrode is the modified stretchable electrode according to claim 8; the modified silver nanowire film side in the modified stretchable electrode is in contact with the conductive layer.

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