Pedot:pss forming method based on plasma-aerosol composite jet and printed structure and application thereof

Abstract

The application belongs to the field of functional material additive manufacturing, and particularly relates to a PEDOT:PSS forming method based on a plasma-aerosol composite jet, a printed structure thereof and application, the forming method comprising: after PEDOT:PSS ink is atomized, an aerosol is formed; in the process of aerosol jet printing, plasma is introduced, so that the plasma and the PEDOT:PSS aerosol converge and are compounded to form a plasma-aerosol composite jet; the plasma-aerosol composite jet is deposited on a substrate to realize printing forming of a PEDOT:PSS structure. By introducing plasma and cooperatively regulating various parameters, the application overcomes problems such as low rheological property, weak formability controllability and insufficient interface adhesion in traditional aerosol printing. The prepared PEDOT:PSS microstructure still has advantages such as excellent adhesion, high conductivity, good geometric precision and use stability without sintering.

Description

Technical Field

[0001] This application belongs to the field of functional material additive manufacturing, specifically involving a PEDOT:PSS molding method based on plasma-aerosol composite jet, its printed structures and applications, and is particularly suitable for realizing the printing of high-precision two-dimensional and three-dimensional PEDOT:PSS structures. Background Technology

[0002] With the rapid development of emerging fields such as flexible electronics, wearable devices, organic optoelectronic devices, and biosensors, the demand for functional materials that combine excellent conductivity, good flexibility, and high transparency is becoming increasingly urgent. PEDOT:PSS (poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate), as a conductive polymer material with excellent conductivity, good flexibility, and high transparency, is widely regarded as one of the most promising core functional materials in these emerging fields.

[0003] In the fabrication of precision electronic devices, high-precision patterning of functional materials is a crucial step in achieving device miniaturization and integration. Aerosol printing (AJP), a non-contact direct writing molding technology, offers significant advantages such as high printing resolution, a wide range of applicable materials, and the ability to create complex three-dimensional structures, providing an ideal technical path for the high-precision patterning of conductive polymer materials like PEDOT:PSS. However, in practical applications, the material properties of PEDOT:PSS and the process characteristics of aerosol printing technology mutually restrict each other, leading to numerous technical bottlenecks in achieving high-precision patterning of PEDOT:PSS using aerosol printing technology, severely limiting its reliable application in the field of precision devices.

[0004] While improving a specific performance, existing technologies sacrifice other intrinsic properties of materials, such as reduced electrical conductivity, decreased transparency, or poorer biocompatibility. They still cannot fundamentally solve problems such as low printing accuracy, weak interlayer bonding, and insufficient process stability. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, the purpose of this application is to provide a PEDOT:PSS molding method based on plasma-aerosol composite jet, its printed structure, and its applications, thereby overcoming the shortcomings of the prior art.

[0006] The following technical solutions are used to achieve the purpose of the invention:

[0007] One aspect of this application provides a PEDOT:PSS molding method based on plasma-aerosol composite jet, comprising the following steps:

[0008] PEDOT:PSS ink is atomized to form PEDOT:PSS aerosol;

[0009] Plasma is introduced during the PEDOT:PSS aerosol jet printing process, so that the plasma and PEDOT:PSS aerosol converge and recombine to form a plasma-aerosol composite jet.

[0010] The plasma-aerosol composite jet is deposited on the substrate to achieve the printing of two-dimensional or three-dimensional structures of PEDOT:PSS.

[0011] Preferably, the PEDOT:PSS ink is a PEDOT:PSS aqueous dispersion.

[0012] Preferably, the concentration of PEDOT:PSS in the PEDOT:PSS aqueous dispersion is 1~50 mg / mL.

[0013] Preferably, PEDOT:PSS ink forms tiny droplets with an average diameter of 0.1~5μm after atomization.

[0014] Preferably, PEDOT:PSS aerosol and sheath gas converge at the converging port of the printhead to form a narrow-flow aerosol jet protected by the sheath gas layer. The narrow-flow aerosol jet and plasma converge and recombine at the nozzle of the printhead to form a plasma-aerosol composite jet.

[0015] Preferably, the printhead has a coaxial dual-channel structure, with the central channel being an aerosol delivery channel and the outer channel being a plasma working gas channel; after the plasma working gas is introduced into the outer channel, it is excited to form plasma.

[0016] Preferably, the sheath gas flow rate is in the range of 20~800 sccm;

[0017] The carrier gas flow rate ranges from 10 to 400 sccm;

[0018] The plasma working gas range is 800~5000 sccm;

[0019] The flow ratio of carrier gas to sheath gas is 1:1~3.

[0020] Preferably, the sheath gas flow rate is in the range of 350~700 sccm;

[0021] The carrier gas flow rate ranges from 150 to 400 sccm;

[0022] The plasma working gas range is 1500~2700 sccm;

[0023] The flow rate ratio of carrier gas to sheath gas is 1:1.7~2.5.

[0024] Preferably, the carrier gas and sheath gas are independently selected from one or more of nitrogen, argon, and helium, and the plasma working gas is one or more of helium, argon, and oxygen.

[0025] Preferably, the plasma is excited by an electric field at atmospheric pressure, and the electric field is generated by an AC power supply or a radio frequency power supply.

[0026] Preferably, for plasma-aerosol composite jets with a diameter of 1~10 mm, when using an AC power supply to excite the plasma, the voltage range is 5~50 V, the current range is 0.1~3 A, and the frequency range is 5~20 kHz; when using a radio frequency power supply to excite the plasma, the power range is 1~500 W, and the frequency range is 10~50 MHz.

[0027] Preferably, the plasma is a low-temperature plasma with a temperature ≤100 ℃.

[0028] Preferably, the distance between the nozzle of the print head and the substrate is 0.5~12 mm.

[0029] Preferably, the moving speed of the print head is 0.01~20 mm / s.

[0030] The second aspect of this application provides a PEDOT:PSS printed structure, which is prepared by the PEDOT:PSS molding method based on plasma-aerosol composite jet as described above.

[0031] Preferably, the aspect ratio of the PEDOT:PSS printed structure is 10~100:1, and the line width is 10~60 μm.

[0032] The third aspect of this application provides the application of the described PEDOT:PSS printed structure in bioelectronics, flexible electronic devices, microsensors, and microfluidic chips.

[0033] Compared with existing PEDOT:PSS printing technologies, the PEDOT:PSS material molding process based on plasma-aerosol composite jet technology provided in this application has the following advantages:

[0034] 1. The PEDOT:PSS molding process method based on low-temperature plasma-aerosol composite jet technology proposed in this application can achieve high-precision patterning of PEDOT:PSS without relying on chemical modification of PEDOT:PSS or adding additional additives. This avoids problems such as decreased electrical conductivity, reduced transparency or poor biocompatibility caused by material modification, and fully maintains the intrinsic properties of the material.

[0035] 2. The introduction of low-temperature plasma significantly improves the bonding force between PEDOT:PSS particles and the substrate, suppresses common printing defects, and enables high-precision printing of PEDOT:PSS two-dimensional / three-dimensional structures. Furthermore, the high-energy active particles in the low-temperature plasma jet can effectively enhance the cross-linking between PEDOT:PSS particles, strengthen the bonding strength between the deposited layers, and ensure stable deposition of the deposited layers. This can form a vertical dimensional structure with an aspect ratio of up to 100, thereby improving the overall density, electrical conductivity, mechanical strength, and reliability of the printing material.

[0036] 3. By controlling the power supply parameters, gas flow parameters, aerosol characteristic parameters, and other relevant printing parameters during the generation of the composite jet and the PEDOT:PSS deposition process, the electrohydrodynamic behavior is adjusted, and precise control of the charge state and deposition trajectory of aerosol particles is achieved. This effectively suppresses defects such as droplet diffusion, overspray, and edge burrs, significantly improving the edge clarity, forming resolution, conductivity, and deposition uniformity of the printed structure, thus meeting the requirements of high-precision manufacturing.

[0037] 4. Traditional aerosol printing requires a sintering process after printing. However, this application promotes the rapid curing of PEDOT:PSS and enhances the continuity of the conductive network during the deposition process. No additional sintering or drying is required after printing. The obtained PEDOT:PSS microstructure has the advantages of excellent adhesion, high conductivity, good geometric accuracy and stability in use. It is suitable for the fabrication of functional devices and complex micro-nano structures with extremely high requirements for precision and microscopic three-dimensional structure in bioelectronics, flexible electronic devices, micro sensors and microfluidic chips.

[0038] 5. The molding process of this application has a wide molding process window, strong parameter controllability, and is applicable to a variety of flexible and rigid substrates, with good process repeatability and applicability. Attached Figure Description

[0039] Figure 1 This is a flowchart of the electrohydrodynamic process adjustment in plasma-aerosol composite jet 3D printing in this application.

[0040] Figure 2 The graph shows the variation of plasma jet length with parameter adjustment under RF / high-frequency AC power supply.

[0041] Figure 3 This is a temperature variation distribution diagram of a stable plasma under RF power supply / high-frequency AC power supply.

[0042] Figure 4 The images show the morphology of the plasma-aerosol composite jet in Example 1 and the aerosol jet in Comparative Example 1.

[0043] Figure 5The image shows the morphology of the three-dimensional structure printed by plasma-aerosol composite jet in Example 2.

[0044] Figure 6 The images show the printed morphology of the plasma-aerosol composite jets in Examples 3-5 at different heights.

[0045] Figure 7 The image shows the morphology of the PEDOT:PSS printed in Example 6.

[0046] Figure 8 The morphology of the PEDOT:PSS printed in Example 7 is shown.

[0047] Figure 9 The morphology of the PEDOT:PSS printed in Example 8 is shown.

[0048] Figure 10 The morphology of the PEDOT:PSS printed in Example 9 is shown. Detailed Implementation

[0049] In the description of this application, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, and includes both a and b. "Multiple" includes two or more types, and can be two, three, four, five, or more.

[0050] In the following sections, embodiments of the PEDOT:PSS molding method based on plasma-aerosol composite jets according to this application will be described in detail. However, these embodiments are exemplary, and the disclosure of this application is not limited thereto. Furthermore, the accompanying drawings used herein are merely for better illustration of the disclosure of this application and do not constitute a limitation on the scope of protection.

[0051] Some embodiments of this application provide a PEDOT:PSS molding method based on plasma-aerosol composite jet, including the following steps:

[0052] PEDOT:PSS ink is atomized to form PEDOT:PSS aerosol;

[0053] Plasma is introduced during the PEDOT:PSS aerosol jet printing process, so that the plasma and PEDOT:PSS aerosol converge and recombine to form a plasma-aerosol composite jet.

[0054] The plasma-aerosol composite jet is deposited on the substrate to achieve the printing of two-dimensional or three-dimensional structures of PEDOT:PSS.

[0055] This application achieves precise regulation of electrohydrodynamic behavior by controlling multiple key parameters in the generation of the composite jet and the PEDOT:PSS deposition process, thereby improving the uniformity, clarity, forming accuracy, conductivity, and deposition efficiency of the printed structure. These key parameters include power supply parameters, gas flow rate parameters, aerosol characteristic parameters, and other relevant printing parameters.

[0056] Preferably, the PEDOT:PSS ink is a PEDOT:PSS aqueous dispersion, requiring no additional modifiers or additives. The introduction of solvents such as alcohols commonly used in the prior art alters the microstructure and phase separation behavior of PEDOT:PSS, introducing residual solvents and additional process variables, thereby affecting the stability, repeatability, and accurate characterization of the material's intrinsic properties. The molding method of this application eliminates the need for these solvents, directly processing pure PEDOT:PSS through composite jet printing, thus showcasing the material's intrinsic properties and the advantages of this molding process.

[0057] The PEDOT:PSS aqueous dispersion is formed by dispersing PEDOT:PSS in water. Preferably, the concentration of PEDOT:PSS in the PEDOT:PSS aqueous dispersion is 1~50 mg / mL, for example, it can be any one value or a range between any two values ​​of 1 mg / mL, 3 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL, 10 mg / mL, 11 mg / mL, 12 mg / mL, 13 mg / mL, 14 mg / mL, 15 mg / mL, 16 mg / mL, 17 mg / mL, 18 mg / mL, 19 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, 35 mg / mL, 40 mg / mL, 45 mg / mL, and 50 mg / mL; more preferably, the concentration of PEDOT:PSS is 5~20 mg / mL.

[0058] PEDOT: PSS ink forms tiny droplets through atomization. The atomization method is not particularly limited; any atomization method that can break the liquid into tiny droplets is applicable. Examples include ultrasonic atomization: using a piezoelectric transducer to convert electrical energy into high-frequency mechanical vibration, causing the liquid to overcome surface tension and form tiny droplets; pneumatic atomization: using a high-speed carrier gas to meet the liquid, breaking the liquid into tiny droplets through airflow shearing force; and electrofluid atomization: using high voltage to stretch the liquid into a cone shape at the nozzle tip, and when the electric field force overcomes the surface tension, it is ejected as an extremely fine charged jet, which breaks in the air to form tiny droplets.

[0059] Optionally, PEDOT:PSS ink is formed into microdroplets by ultrasonic atomization. When ultrasonic atomization is used, the preferred ultrasonic atomization parameters are: ultrasonic power of 1~300 W, operating frequency of 0.5~3.0 MHz, and atomization efficiency of 1~10 ml / min. More preferably, the ultrasonic power is 100~300 W and the operating frequency is 1.0~2.0 MHz.

[0060] Preferably, the PEDOT:PSS ink, after atomization, forms microdroplets with an average diameter of 0.1~5 μm. More preferably, the average diameter of the microdroplets is 0.5~2.0 μm.

[0061] PEDOT:PSS ink is atomized into tiny droplets, which are then continuously and stably transported to the nozzle by a carrier gas. The stable colloidal dispersion system formed by the tiny droplets of PEDOT:PSS aqueous dispersion suspended in the carrier gas is called an aerosol.

[0062] PEDOT:PSS aerosol and sheath gas converge at the nozzle of the printhead, forming a narrow-flow aerosol jet protected by a sheath gas layer. This narrow-flow aerosol jet then merges with plasma at the nozzle of the printhead, forming a plasma-aerosol composite jet. During printing, PEDOT:PSS aerosol and sheath gas are delivered to the nozzle area of ​​the printhead along preset channels, where they converge and merge. The sheath gas forms a uniform sheath gas layer around the PEDOT:PSS aerosol flow, effectively limiting the diffusion of the aerosol jet and reducing interference from the external environment. This results in a stable, highly directional narrow-flow aerosol jet, ensuring print quality.

[0063] The printhead has a coaxial dual-channel structure, with the central channel being the aerosol delivery channel and the outer channel being the plasma working gas channel. After the plasma working gas is introduced into the outer channel, it is excited to form plasma. The plasma working gas carries the formed plasma and continuously delivers it to the nozzle, where it merges and combines with the aerosol jet ejected from the central channel to form a plasma-aerosol composite jet.

[0064] The entire printing process involves three key gases: carrier gas, sheath gas, and plasma working gas. The flow rates of these three gases need precise control to improve print quality. First, the sheath gas flow rate is controlled. The sheath gas surrounds the aerosol, acting as a protector and focusing agent. An appropriate sheath gas flow rate effectively constrains jet divergence, causing the atomized droplets to deposit more concentratedly on the substrate surface, thus significantly improving line focus and resolution. When the sheath gas flow rate is insufficient, its contraction and stabilization of the droplet bundle are inadequate, leading to lateral droplet diffusion and resulting in blurred edges and increased linewidth in the deposited morphology. Conversely, when the sheath gas flow rate is too high, excessive shearing and compression can disturb the droplet trajectory, similarly affecting line integrity and structural quality. Therefore, the sheath gas flow rate range is limited to 20–800 sccm. Subsequently, the carrier gas flow rate is adjusted. The carrier gas is responsible for continuously and stably transporting the aerosol formed in the generator to the nozzle. Its flow rate directly affects the droplet transport rate and concentration uniformity. Too low a carrier gas flow rate will lead to insufficient transport efficiency and unstable aerosol bundle density; while too high a flow rate may cause uneven spraying or excessive jet disturbance. Controlling the carrier gas flow rate to 10~400 sccm and maintaining a flow ratio of approximately 1:1~3 with the sheath gas can achieve more stable particle transport and more uniform deposition. Finally, the plasma working gas flow rate is adjusted. This gas determines the stability of the plasma and the jet length. Limiting the plasma working gas flow rate to 800~5000 sccm is to maintain stable plasma discharge and control the length of the plasma jet.

[0065] Preferably, the flow rate of the sheath gas is in the range of 200~750 sccm, more preferably 350~700 sccm. It can be any one value or a range between any two values ​​from 350 sccm, 360 sccm, 370 sccm, 380 sccm, 390 sccm, 400 sccm, 410 sccm, 420 sccm, 430 sccm, 440 sccm, 450 sccm, 480 sccm, 500 sccm, 520 sccm, 550 sccm, 580 sccm, 600 sccm, 620 sccm, 650 sccm, 680 sccm, and 700 sccm.

[0066] Preferably, the carrier gas flow rate is in the range of 50~350 sccm, more preferably 150~400 sccm. It can be any one value or a range between any two values ​​from 150 sccm, 160 sccm, 170 sccm, 180 sccm, 190 sccm, 200 sccm, 210 sccm, 220 sccm, 230 sccm, 240 sccm, 250 sccm, 280 sccm, 300 sccm, 350 sccm, and 400 sccm.

[0067] Preferably, the flow ratio of carrier gas to sheath gas is 1:1.7 to 2.5. More preferably, it is 1:2.

[0068] Preferably, the flow rate of the plasma working gas is in the range of 1000~4000 sccm, more preferably 1500~2700 sccm. It can be any one value or a range between any two values ​​from 1500 sccm, 1600 sccm, 1700 sccm, 1800 sccm, 1900 sccm, 2000 sccm, 2100 sccm, 2200 sccm, 2300 sccm, 2400 sccm, 2500 sccm, and 2700 sccm.

[0069] More preferably, the flow rate of the sheath gas is in the range of 350~700 sccm, the flow rate of the carrier gas is in the range of 150~400 sccm, the flow rate of the plasma working gas is in the range of 1500~2700 sccm, and the flow rate ratio of the carrier gas to the sheath gas is 1:1.7~2.5.

[0070] Preferably, the carrier gas and sheath gas can be independently selected from one or more of nitrogen, argon, and helium, and the plasma working gas is one or more of helium, argon, and oxygen. More preferably, the carrier gas, sheath gas, and plasma working gas are argon with a purity ≥99.9%.

[0071] Preferably, the plasma is excited by an electric field at atmospheric pressure, and the electric field is generated by a power source capable of providing the excitation electric field. For example, the electric field is generated by an AC power source, a radio frequency power source, or other power source capable of generating an electric field. More preferably, the electric field is generated by an AC power source or a radio frequency power source.

[0072] Preferably, the diameter of the plasma-aerosol composite jet is 1~10 mm.

[0073] Preferably, for plasma-aerosol composite jets with a diameter of 1-10 mm, when using an AC power supply to excite the plasma, the voltage range is 5-50 V, the current range is 0.1-3 A, and the frequency range is 5-20 kHz; when using a radio frequency power supply to excite the plasma, the power range is 1-500 W, and the frequency range is 10-50 MHz. A stable and controllable plasma jet can be obtained by adjusting the power supply parameters.

[0074] like Figure 2 As shown, the left side represents a plasma jet excited by a radio frequency (RF) power source. As the RF power increases from 20 W to 30 W, the plasma jet becomes significantly longer. The right side represents a plasma jet excited by an AC power source. As the voltage increases from 20 V to 35 V and the current increases from 0.45 A to 0.62 A, the plasma jet becomes longer and brighter. Within a certain range, higher excitation energy results in greater electron density and gas ionization, thus allowing for a longer plasma jet.

[0075] Preferably, the plasma is a low-temperature plasma with a temperature ≤100 °C. More preferably, it is ≤80 °C, and can be selected as 20~70 °C. The low-temperature plasma is excited by an electric field at room temperature and normal pressure.

[0076] The temperature of cryogenic plasma is affected by the type of power supply and its voltage or power. Figure 3 The images show stable plasma temperature distribution under both RF and high-frequency AC power supplies. The temperature distribution is presented using infrared thermal imaging colors (purple-yellow-orange representing temperatures from low to high) and numerical labels. The top two images show the plasma temperature distribution under AC power supply mode. As the voltage increases from 20V / 0.67A to 29V / 0.81A, the highest plasma temperature rises from 29.5℃ to 31.9℃, and the high-temperature region (orange) expands significantly. The bottom two images show the plasma temperature distribution under RF power supply mode. As the voltage increases from 20W to 30W, the highest plasma temperature rises from 50.8℃ to 62.8℃. Regardless of whether it's AC or RF power, higher input energy results in higher plasma temperatures and a larger high-temperature region; however, the overall plasma temperature level under RF power supply mode is significantly higher than under AC power supply mode.

[0077] The temperature of the plasma-aerosol composite jet can also be adjusted within the range of 20~100℃. Its temperature is determined by the plasma temperature and is also affected by the power supply type and voltage or power, increasing with the increase of input energy.

[0078] Regarding printing process parameters, the distance between the nozzle and the substrate of the print head is preferably 0.5~12 mm to form a suitable electric field gradient and maintain jet stability, and more preferably 1~8 mm. Preferably, the moving speed of the print head is 0.01~20 mm / s, and more preferably 0.1~10 mm / s, to achieve precise control of the deposition morphology.

[0079] The PEDOT:PSS pattern can be printed on any adaptable substrate using a plasma-aerosol composite jet molding process. The printing substrate includes, but is not limited to, flexible and rigid substrates. Flexible substrates can be exemplified by substrates formed from flexible materials such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyurethane (PU), poly(p-phenylene terephthalamide), polytetrafluoroethylene, cellulose, and polyolefins. Rigid substrates can be exemplified by substrates formed from rigid materials such as glass, silicon wafers, ceramics, metal plates, quartz sheets, and indium tin oxide.

[0080] The plasma-aerosol composite jet is deposited on the substrate to obtain a two-dimensional or three-dimensional PEDOT:PSS structure. No subsequent sintering or drying treatment is required to achieve the advantages of excellent adhesion, high conductivity, good geometric accuracy and stability in use of the two-dimensional or three-dimensional PEDOT:PSS structure.

[0081] The prepared PEDOT:PSS patterns have an aspect ratio of 10~100 and can achieve high-precision microstructures with feature sizes of 10~60μm.

[0082] The working principle and process of the PEDOT:PSS molding method based on plasma-aerosol composite jet in this application are as follows:

[0083] PEDOT:PSS aqueous dispersion is atomized into tiny droplets, which are continuously and stably transported to the nozzle by a carrier gas. The stable colloidal dispersion system formed by these tiny droplets suspended in the carrier gas is the aerosol. The carrier gas carries the suspended PEDOT:PSS droplets towards the nozzle. During this process, the carrier gas must maintain a stable pressure and flow rate to ensure that the droplets in the aerosol remain suspended and do not agglomerate or settle. When the aerosol reaches the collection port inside the printhead, sheath gas is ejected from the annular channel surrounding the nozzle, forming a "sheath gas layer" that surrounds the aerosol jet. The circumferential pressure of the sheath gas physically constrains the central aerosol jet, suppressing its natural divergence after the exit point and forcing the droplets to converge towards the center of the jet, forming a narrow-flow aerosol jet. The sheath gas's focusing of the aerosol jet effectively suppresses jet divergence and improves deposition accuracy. The printhead employs a coaxial dual-channel design near the nozzle, with the central channel serving as the aerosol delivery channel and the outer channel as the plasma working gas channel. After the plasma working gas enters the outer channel, it is excited by high-energy methods such as ultraviolet radiation, X-rays, and electric fields, ionizing gas molecules to produce free electrons and ions. These high-energy particles collide with neutral gas atoms, exciting and ionizing even more gas atoms, thus forming a plasma composed of electrons, ions, atoms, and molecules. The plasma working gas continuously delivers the formed plasma to the printhead outlet (i.e., the nozzle), where it precisely merges with the aerosol jet ejected from the central channel to form a plasma-aerosol composite jet. The generated plasma jet interacts with the aerosol during its flight and as it impacts and spreads onto the substrate, thus assisting in the aerosol printing process to form the target pattern.

[0084] The technical solutions of this application will be further described and illustrated below with specific embodiments and accompanying drawings. It should be understood that the specific embodiments described herein are only for the purpose of helping to understand this application and are not intended to limit the specific scope of this application. Furthermore, the accompanying drawings used herein are merely for better illustrating the content disclosed in this application and do not limit the scope of protection. Unless otherwise specified, the raw materials used in the embodiments of this application are all commonly used in the art, and the methods used in the embodiments are all conventional methods in the art.

[0085] The PEDOT:PSS aqueous dispersion used in the following examples and comparative examples is Heraeus' Clevios™ PH 1000, which is formed by dispersing PEDOT:PSS in water. Example 1

[0086] This embodiment employs low-temperature plasma-aerosol composite jet technology to fabricate high-precision PEDOT:PSS conductive patterns on a flexible polyimide (PI) substrate. The specific steps are as follows:

[0087] Commercially available PEDOT:PSS aqueous dispersion (Clevios™ PH 1000) was used as the base material, without any modifiers or additives. The concentration of the PEDOT:PSS aqueous dispersion was controlled at 12 mg / mL, and the mixture was magnetically stirred for 30 minutes and ultrasonically treated for 20 minutes to ensure uniform dispersion and remove air bubbles, resulting in PEDOT:PSS ink suitable for aerosol printing.

[0088] An ultrasonic atomizer with an ultrasonic power of 4W and a working frequency of 1.7 MHz was used for atomization, and the average diameter of the generated aerosol droplets was controlled within the range of 0.5–5.0 micrometers. High-purity argon (99.99% by volume) was used as the carrier gas at a flow rate of 200 sccm to continuously and stably deliver the aerosol particles to the nozzle outlet. Simultaneously, sheath gas (argon) was used to focus the aerosol jet at a flow rate of 400 sccm, effectively suppressing jet divergence and improving deposition accuracy.

[0089] The printhead employs a coaxial dual-channel structure, with the inner channel for aerosol delivery and the outer channel for plasma gas. The nozzle inner diameter is 200 micrometers. The plasma working gas (argon) flow rate is set to 2000 sccm, powered by an AC power supply of 17.8 V, 0.81 A, and 7.86 kHz, forming a stable and controllable cryogenic plasma jet. The cryogenic plasma jet merges with the aerosol jet ejected from the central channel to form a plasma-aerosol composite jet with a diameter of approximately 2 mm.

[0090] The nozzle-to-substrate distance is set to 2 mm to maintain a stable electric field distribution and plasma-aerosol composite jet morphology, preventing corona discharge due to excessively small distance or jet divergence due to excessively large distance. The printing substrate is a cleaned PI flexible film, which is ultrasonically cleaned with anhydrous ethanol for 5 minutes, then air-dried, and then subjected to plasma treatment for 2 minutes to improve surface wettability.

[0091] During the printing process, the three-axis platform movement speed was set to 3.0 mm / s. By adjusting the above parameters, the electrohydrodynamics was synergistically controlled. Low-temperature plasma in-situ activated the substrate surface and promoted cross-linking, significantly enhancing the interfacial bonding force of PEDOT:PSS. Simultaneously, the charge state and deposition trajectory of aerosol particles were precisely controlled, promoting rapid curing of PEDOT:PSS. The plasma-aerosol composite jet was deposited on the substrate according to the above parameters to obtain a single-layer PEDOT:PSS conductive pattern.

[0092] By adjusting the height of the printing nozzle, subsequent materials are deposited layer by layer on the already formed single-layer structure. After 5 cycles, a multi-layer conductive pattern with vertical dimensions is finally formed.

[0093] Comparative Example 1

[0094] Comparative Example 1 uses aerosol technology to prepare PEDOT:PSS conductive patterns on a flexible polyimide (PI) substrate. The specific steps are as follows:

[0095] Commercially available PEDOT:PSS aqueous dispersion (Clevios™ PH 1000) was used as the base material, without any modifiers or additives. The concentration of the PEDOT:PSS aqueous dispersion was controlled at 12 mg / mL, and the mixture was magnetically stirred for 30 minutes and ultrasonically treated for 20 minutes to ensure uniform dispersion and remove air bubbles, resulting in PEDOT:PSS ink suitable for aerosol printing.

[0096] An ultrasonic nebulizer was used for atomization, with an ultrasonic power of 4W and a working frequency of 1.7 MHz. The average diameter of the generated aerosol droplets was controlled between 0.5 and 5.0 micrometers. High-purity argon (99.99% by volume) was used as the carrier gas at a flow rate of 200 sccm to continuously and stably deliver the aerosol particles to the nozzle outlet. Simultaneously, sheath gas (argon) was used to focus the aerosol jet at a flow rate of 400 sccm.

[0097] The printing substrate was a cleaned PI flexible film, ultrasonically cleaned with anhydrous ethanol for 5 minutes, then air-dried, and subsequently subjected to plasma treatment for 2 minutes to improve surface wettability. The nozzle-to-substrate distance was set to 2 mm, and the three-axis platform movement speed was set to 3.0 mm / s during printing. The nozzle inner diameter was 200 micrometers. Aerosol was ejected from the nozzle to form an aerosol jet, which was deposited on the substrate according to the above parameters to obtain a single-layer PEDOT:PSS conductive pattern.

[0098] By adjusting the height of the printing nozzle, subsequent materials are deposited layer by layer on the already formed single-layer structure. After 5 cycles, a multi-layer conductive pattern with vertical dimensions is finally formed.

[0099] like Figure 4 As shown, the single-layer PEDOT:PSS conductive pattern prepared by low-temperature plasma-aerosol composite jet technology in Example 1 has a linewidth of approximately 52 μm and a thickness of approximately 16 nm. The lines are continuous, uniform, and have clear edges. When multilayer superposition printing is performed using the same process, the linewidth of the resulting multilayer conductive pattern is basically the same as that of the single-layer pattern, and the lines remain continuous, uniform, and clear. In contrast, the single-layer PEDOT:PSS conductive pattern prepared by aerosol printing technology in Comparative Example 1 has a linewidth of approximately 55 μm and a thickness of approximately 17 nm. The printed lines are discontinuous and have flash. When multilayer superposition printing is performed using the same process, the linewidth of the resulting multilayer conductive pattern becomes wider, and the flash is more severe.

[0100] The single-layer printed patterns obtained in Example 1 and Comparative Example 1 were directly tested for bending performance and conductivity without subsequent sintering or drying.

[0101] The bending test procedure includes: fixing a flexible substrate with a printed conductive pattern onto the bending test device, with the conductive pattern located on the outside of the bend; setting the bending radius to a fixed value of 5 mm, performing one forward bend and returning to the starting position to complete one bending cycle; continuously cyclically bending the sample under constant bending frequency conditions, and observing the integrity of the conductive pattern and whether cracks, peeling, or detachment occur after a predetermined number of cycles, while recording the number of bends at the point of failure.

[0102] The conductivity of Example 1 is 1600 S / m, while that of Comparative Example 1 is 100 S / m. The printed pattern in Example 1 only began to peel off after 8000 bending tests, while the printed pattern in Comparative Example 1 peeled off after only 600 bending tests, indicating that the printed pattern in Example 1 has excellent adhesion to the substrate.

[0103] After obtaining the single-layer printed pattern in Comparative Example 1, it was vacuum dried at 80°C for 60 minutes, and then its bending performance and conductivity were tested again. At this time, the conductivity was 800 S / m, and the printed pattern peeled off after 1000 bending tests. Even after subsequent sintering treatment of the aerosol printed pattern, its performance was still significantly lower than that of the composite printed pattern in Example 1. Example 2

[0104] This embodiment employs low-temperature plasma-aerosol composite jet technology to fabricate high-precision PEDOT:PSS conductive patterns on a flexible polyimide (PI) substrate. The specific steps are as follows:

[0105] Commercially available PEDOT:PSS aqueous dispersion (Clevios™ PH 1000) was used as the base material, without any modifiers or additives. The concentration of the PEDOT:PSS aqueous dispersion was controlled at 5 mg / mL, and the mixture was magnetically stirred for 30 minutes and ultrasonically treated for 20 minutes to ensure uniform dispersion and remove air bubbles, resulting in PEDOT:PSS ink suitable for aerosol printing.

[0106] An ultrasonic nebulizer was used for atomization, with an ultrasonic power of 4 W and a working frequency of 1.7 MHz. The average diameter of the generated aerosol droplets was controlled between 0.5 and 5.0 micrometers. High-purity argon (99.99% by volume) was used as the carrier gas, with a flow rate set at 300 sccm. Simultaneously, sheath gas (argon) was used to focus the aerosol jet, with a flow rate set at 480 sccm.

[0107] The printhead employs a coaxial dual-channel structure, with the inner channel for aerosol delivery and the outer channel for plasma gas. The nozzle inner diameter is 200 micrometers. The plasma working gas (argon) flow rate is set to 1900 sccm, powered by an AC power supply of 26 V, 0.9 A, and 7.56 kHz, forming a stable and controllable low-temperature plasma jet.

[0108] The printing substrate was a cleaned PI flexible film, ultrasonically cleaned with anhydrous ethanol for 5 minutes, then air-dried, and subsequently subjected to plasma treatment for 2 minutes to improve surface wettability. The nozzle-to-substrate distance was set to 1 mm. During printing, the three-axis platform movement speed was set to 0.01 mm / s. The plasma-aerosol composite jet was deposited on the substrate according to the above parameters. By adjusting the height of the printing nozzle, subsequent materials were deposited layer by layer on the pre-formed single-layer structure, ultimately forming a multi-layer conductive pattern with a height of 2 mm.

[0109] Comparative Example 2

[0110] Comparative Example 2 uses aerosol technology to prepare PEDOT:PSS conductive patterns on a flexible polyimide (PI) substrate. The specific steps are as follows:

[0111] Commercially available PEDOT:PSS aqueous dispersion (Clevios™ PH 1000) was used as the base material, without any modifiers or additives. The concentration of the PEDOT:PSS aqueous dispersion was controlled at 5 mg / mL, and the mixture was magnetically stirred for 30 minutes and ultrasonically treated for 20 minutes to ensure uniform dispersion and remove air bubbles, resulting in PEDOT:PSS ink suitable for aerosol printing.

[0112] An ultrasonic nebulizer was used for atomization, with an ultrasonic power of 4W and a working frequency of 1.7 MHz. The average diameter of the generated aerosol droplets was controlled between 0.5 and 5.0 micrometers. High-purity argon (99.99% by volume) was used as the carrier gas, with a flow rate set at 300 sccm. Simultaneously, sheath gas (argon) was used to focus the aerosol jet, with a flow rate set at 480 sccm.

[0113] The printing substrate was a cleaned PI flexible film, ultrasonically cleaned with anhydrous ethanol for 5 minutes, then air-dried, and subsequently subjected to plasma treatment for 2 minutes to improve surface wettability. The nozzle-to-substrate distance was set to 1 mm. During printing, the three-axis platform movement speed was set to 0.01 mm / s. The nozzle inner diameter was 200 micrometers. The aerosol jet was deposited on the substrate according to the above parameters. By adjusting the height of the printing nozzle, subsequent materials were deposited layer by layer on the pre-formed single-layer structure, ultimately forming a multi-layer conductive pattern with a height of 0.45 mm.

[0114] like Figure 5As shown, the plasma-aerosol composite jet printing in Example 2 produced a multilayer conductive pattern with a height of 2 mm, a width of approximately 181 μm, and an aspect ratio of 11. In contrast, the aerosol ink in Comparative Example 2 collapsed due to gravity during the printing deposition process, resulting in a multilayer conductive pattern with a height of only 0.45 mm, a width of approximately 0.21 mm, and an aspect ratio of 2.14. The low-temperature plasma-aerosol composite jet technology of this application demonstrates superior performance in forming multilayered three-dimensional structures. Example 3

[0115] This embodiment employs low-temperature plasma-aerosol composite jet technology to fabricate high-precision PEDOT:PSS conductive patterns on a flexible polyimide (PI) substrate. The specific steps are as follows:

[0116] Commercially available PEDOT:PSS aqueous dispersion (Clevios™ PH 1000) was used as the base material, without any modifiers or additives. The concentration of the PEDOT:PSS aqueous dispersion was controlled at 15 mg / mL, and the mixture was magnetically stirred for 30 minutes and ultrasonically treated for 20 minutes to ensure uniform dispersion and remove air bubbles, resulting in PEDOT:PSS ink suitable for aerosol printing.

[0117] An ultrasonic nebulizer was used for atomization, with an ultrasonic power of 4W and a working frequency of 2.5 MHz. The average diameter of the generated aerosol droplets was controlled between 0.5 and 5.0 micrometers. High-purity argon (99.99% by volume) was used as the carrier gas, with a flow rate set at 250 sccm. Simultaneously, sheath gas (argon) was used to focus the aerosol jet, with a flow rate set at 500 sccm.

[0118] The printhead employs a coaxial dual-channel structure, with the inner channel for aerosol delivery and the outer channel for plasma gas. The nozzle inner diameter is 200 micrometers. The plasma working gas (argon) flow rate is set to 2200 sccm, powered by an AC power supply of 30 V, 1.2 A, and 6 kHz, forming a stable and controllable low-temperature plasma jet.

[0119] The printing substrate is a cleaned PI flexible film, ultrasonically cleaned with anhydrous ethanol for 5 minutes, then air-dried, and subsequently plasma-treated for 2 minutes to improve surface wettability. The nozzle-to-substrate distance is set to 1 mm. During printing, the three-axis platform movement speed is set to 5 mm / s. The plasma-aerosol composite jet is deposited on the substrate according to the above parameters. By adjusting the height of the printing nozzle, subsequent materials are deposited layer by layer on the already formed single-layer structure, ultimately forming a multi-layer conductive pattern with vertical dimensions after 10 passes. Example 4

[0120] The difference between Example 4 and Example 3 is that the distance between the nozzle and the substrate of the nozzle in Example 4 is set to 2 mm. The rest is the same as in Example 3. After 10 passes, a multi-layer conductive pattern with vertical dimensions is finally formed. Example 5

[0121] The difference between Example 5 and Example 3 is that the distance between the nozzle and the substrate of the nozzle in Example 5 is set to 3 mm. The rest is the same as in Example 3. After 10 passes, a multi-layer conductive pattern with vertical dimensions is finally formed.

[0122] The multilayer conductive patterns in Examples 3-5 are as follows: Figure 6 As shown, the nozzle-substrate spacing has a significant impact on the final pattern morphology: when the nozzle-substrate spacing is small, the aerosol micelles are deposited on the substrate surface before fully expanding, resulting in concentrated particle flux, which is beneficial for forming printed patterns with smaller linewidths, clearer boundaries, and denser film layers. Simultaneously, the high coupling between the plasma interaction area and the substrate surface effectively promotes solvent evaporation and particle fusion, thereby improving pattern continuity and adhesion. However, too small a spacing may lead to excessively strong plasma interaction, causing localized over-drying or airflow disturbance, resulting in uneven pattern edges or increased surface roughness. As the nozzle-substrate spacing increases, the aerosol micelles gradually disperse during transport, reducing the particle flux deposited on the substrate, leading to a significant increase in printed linewidth, blurred boundaries, and even discontinuities or uneven thickness in localized areas. Furthermore, the plasma energy density significantly decreases before reaching the substrate, weakening its promoting effect on solvent removal and film densification, thus hindering the formation of structurally complete and uniform conductive patterns. Therefore, proper control of the nozzle-substrate spacing is crucial for plasma-aerosol printing of PEDOT:PSS. A suitable spacing can ensure aerosol focusing and deposition while fully leveraging the plasma's regulatory role in the film formation process, thereby obtaining printed patterns with uniform linewidth, clear boundaries, and excellent adhesion. Example 6

[0123] This embodiment employs low-temperature plasma-aerosol composite jet technology to fabricate high-precision PEDOT:PSS conductive patterns on a flexible polyimide (PI) substrate. The specific steps are as follows:

[0124] Commercially available PEDOT:PSS aqueous dispersion (Clevios™ PH 1000) was used as the base material, without any modifiers or additives. The concentration of the PEDOT:PSS aqueous dispersion was controlled at 22 mg / mL, and the mixture was magnetically stirred for 30 minutes and ultrasonically treated for 20 minutes to ensure uniform dispersion and remove air bubbles, resulting in PEDOT:PSS ink suitable for aerosol printing.

[0125] An ultrasonic nebulizer was used for atomization, with an ultrasonic power of 6 W and a working frequency of 1.8 MHz. The average diameter of the generated aerosol droplets was controlled between 0.5 and 5.0 micrometers. High-purity argon (99.99% by volume) was used as the carrier gas, with a flow rate set to 200 sccm. Simultaneously, sheath gas (argon) was used to focus the aerosol jet, with a flow rate set to 400 sccm.

[0126] The printhead employs a coaxial dual-channel structure, with the inner channel for aerosol delivery and the outer channel for plasma gas. The nozzle inner diameter is 200 micrometers. The plasma working gas (argon) flow rate is set to 1400 sccm, powered by an AC power supply of 32 V, 1.3 A, and 1.8 kHz, forming a stable and controllable cryogenic plasma jet.

[0127] The printing substrate was a cleaned PI flexible film, ultrasonically cleaned with anhydrous ethanol for 5 minutes, then air-dried, and subsequently subjected to plasma treatment for 2 minutes to improve surface wettability. The nozzle-to-substrate distance was set to 1.2 mm. During printing, the three-axis platform movement speed was set to 15 mm / s. Plasma-aerosol composite jets were deposited on the substrate according to the above parameters, and aerosol jets were deposited on the substrate according to the above parameters to obtain a single-layer PEDOT:PSS conductive pattern.

[0128] like Figure 7 As shown, the linewidth of the single-layer PEDOT:PSS conductive pattern prepared in Example 6 is about 264 μm, the lines are continuous, but there are flashes at the edges. Example 7

[0129] This embodiment employs low-temperature plasma-aerosol composite jet technology to fabricate high-precision PEDOT:PSS conductive patterns on a flexible polyimide (PI) substrate. The specific steps are as follows:

[0130] Commercially available PEDOT:PSS aqueous dispersion (Clevios™ PH 1000) was used as the base material, without any modifiers or additives. The concentration of the PEDOT:PSS aqueous dispersion was controlled at 22 mg / mL, and the mixture was magnetically stirred for 30 minutes and ultrasonically treated for 20 minutes to ensure uniform dispersion and remove air bubbles, resulting in PEDOT:PSS ink suitable for aerosol printing.

[0131] An ultrasonic nebulizer was used for atomization, with an ultrasonic power of 6 W and a working frequency of 1.8 MHz. The average diameter of the generated aerosol droplets was controlled between 0.5 and 5.0 micrometers. High-purity argon (99.99% by volume) was used as the carrier gas, with a flow rate set at 200 sccm. Simultaneously, sheath gas (argon) was used to focus the aerosol jet, with a flow rate set at 320 sccm.

[0132] The printhead employs a coaxial dual-channel structure, with the inner channel for aerosol delivery and the outer channel for plasma gas. The nozzle inner diameter is 200 micrometers. The plasma working gas (argon) flow rate is set to 1400 sccm, powered by an AC power supply of 32 V, 1.3 A, and 8.16 kHz, forming a stable and controllable low-temperature plasma jet.

[0133] The printing substrate was a cleaned PI flexible film, ultrasonically cleaned with anhydrous ethanol for 5 minutes, then air-dried, and subsequently subjected to plasma treatment for 2 minutes to improve surface wettability. The nozzle-to-substrate distance was set to 1.2 mm. During printing, the three-axis platform movement speed was set to 15 mm / s. Plasma-aerosol composite jets were deposited on the substrate according to the above parameters, and aerosol jets were deposited on the substrate according to the above parameters to obtain a single-layer PEDOT:PSS conductive pattern.

[0134] like Figure 8 As shown, the linewidth of the single-layer PEDOT:PSS conductive pattern prepared in Example 7 is about 228 μm, the lines are continuous, but the edge flash phenomenon is aggravated. Example 8

[0135] This embodiment employs low-temperature plasma-aerosol composite jet technology to fabricate high-precision PEDOT:PSS conductive patterns on a flexible polyimide (PI) substrate. The specific steps are as follows:

[0136] Commercially available PEDOT:PSS aqueous dispersion (Clevios™ PH 1000) was used as the base material, without any modifiers or additives. The concentration of the PEDOT:PSS aqueous dispersion was controlled at 22 mg / mL, and the mixture was magnetically stirred for 30 minutes and ultrasonically treated for 20 minutes to ensure uniform dispersion and remove air bubbles, resulting in PEDOT:PSS ink suitable for aerosol printing.

[0137] An ultrasonic nebulizer was used for atomization, with an ultrasonic power of 6W and a working frequency of 1.8 MHz. The average diameter of the generated aerosol droplets was controlled between 0.5 and 5.0 micrometers. High-purity argon (99.99% by volume) was used as the carrier gas, with a flow rate set at 450 sccm. Simultaneously, sheath gas (argon) was used to focus the aerosol jet, with a flow rate set at 800 sccm.

[0138] The printhead employs a coaxial dual-channel structure, with the inner channel for aerosol delivery and the outer channel for plasma gas. The nozzle inner diameter is 200 micrometers. The plasma working gas (argon) flow rate is set to 2800 sccm, powered by an AC power supply of 32 V, 1.3 A, and 8.16 kHz, forming a stable and controllable low-temperature plasma jet.

[0139] The printing substrate was a cleaned PI flexible film, ultrasonically cleaned with anhydrous ethanol for 5 minutes, then air-dried, and subsequently subjected to plasma treatment for 2 minutes to improve surface wettability. The nozzle-to-substrate distance was set to 1.2 mm. During printing, the three-axis platform movement speed was set to 15 mm / s. Plasma-aerosol composite jets were deposited on the substrate according to the above parameters, and aerosol jets were deposited on the substrate according to the above parameters to obtain a single-layer PEDOT:PSS conductive pattern.

[0140] like Figure 9 As shown, the linewidth of the monolayer PEDOT:PSS conductive pattern prepared in Example 8 is about 178 μm, the lines are continuous, but the edge burrs are aggravated. Example 9

[0141] This embodiment uses low-temperature plasma-aerosol composite jet technology to prepare high-precision PEDOT:PSS conductive patterns on a flexible PET substrate. The specific steps are as follows:

[0142] Commercially available PEDOT:PSS aqueous dispersion (Clevios™ PH 1000) was used as the base material, without any modifiers or additives. The concentration of the PEDOT:PSS aqueous dispersion was controlled at 30 mg / mL, and the mixture was magnetically stirred for 40 minutes and ultrasonically treated for 30 minutes to ensure uniform dispersion and remove air bubbles, resulting in PEDOT:PSS ink suitable for aerosol printing.

[0143] An ultrasonic nebulizer was used for atomization, with an ultrasonic power of 10 W and a working frequency of 2.5 MHz. The average diameter of the generated aerosol droplets was controlled between 0.5 and 5.0 micrometers. High-purity argon (99.99% by volume) was used as the carrier gas, with a flow rate set at 120 sccm. Simultaneously, sheath gas (argon) was used to focus the aerosol jet, with a flow rate set at 240 sccm.

[0144] The printhead employs a coaxial dual-channel structure, with the inner channel for aerosol delivery and the outer channel for plasma gas. The nozzle inner diameter is 200 micrometers. The plasma working gas (argon) flow rate is set to 1500 sccm, powered by an RF power supply with a power of 50 W and a frequency of 27.12 MHz, forming a stable and controllable low-temperature plasma jet.

[0145] The printing substrate was a cleaned flexible PET film, ultrasonically cleaned with anhydrous ethanol for 5 minutes, then air-dried, and subsequently plasma-treated for 1 minute to improve surface wettability. The nozzle-to-substrate distance was set to 2.5 mm. During printing, the three-axis platform movement speed was set to 8 mm / s. The plasma-aerosol composite jet was deposited on the substrate according to the above parameters, resulting in a folded conductive pattern as shown. Figure 10 As shown, the printed conductive lines maintain continuity, uniformity, and clear edges along the continuously bending printing path.

[0146] All aspects, embodiments, and features of this application are to be considered illustrative in all respects and not limiting of the application; the scope of this application is defined only by the claims. Other embodiments, modifications, and uses will become apparent to those skilled in the art without departing from the spirit and scope of this application as claimed.

[0147] In the preparation method of this application, the order of the steps is not limited to the listed order. For those skilled in the art, variations in the order of the steps without inventive effort are also within the scope of protection of this application. Furthermore, two or more steps or actions can be performed simultaneously.

[0148] Finally, it should be noted that the specific embodiments described herein are merely illustrative examples and are not intended to limit the implementation of this application. Those skilled in the art to which this application pertains can make various modifications or additions to the described specific embodiments or use similar methods to replace them; it is neither necessary nor possible to provide exhaustive examples of all implementations here. However, obvious variations or modifications derived from the essential spirit of this application still fall within the protection scope of this application, and interpreting them as any additional limitation would contradict the spirit of this application.

Claims

1. A method for forming PEDOT:PSS based on a plasma-aerosol hybrid jet, characterized in that, Includes the following steps: PEDOT:PSS ink is atomized to form PEDOT:PSS aerosol; PEDOT: PSS aerosol and sheath gas converge at the converging port of the print head to form a narrow aerosol jet protected by the sheath gas layer. The narrow aerosol jet and plasma converge and recombine at the nozzle of the print head to form a plasma-aerosol composite jet. The plasma-aerosol composite jet is deposited on the substrate, and no subsequent sintering or drying process is required, thus realizing the printing of two-dimensional or three-dimensional structures of PEDOT:PSS. PEDOT:PSS ink is a PEDOT:PSS aqueous dispersion formed by dispersing PEDOT:PSS in water, without any additives; the concentration of PEDOT:PSS is 1~20 mg / mL; The printhead has a coaxial dual-channel structure, with the central channel being an aerosol delivery channel and the outer channel being a plasma working gas channel; after the plasma working gas is introduced into the outer channel, it is excited to form plasma. The sheath gas flow rate ranges from 20 to 800 sccm; The carrier gas flow rate ranges from 10 to 400 sccm; The plasma working gas flow rate ranges from 800 to 5000 sccm; The flow ratio of carrier gas to sheath gas is 1:1~3; The distance between the nozzle and the substrate of the print head is 0.5~12 mm; the moving speed of the print head is 0.01~20 mm / s.

2. The PEDOT:PSS forming method based on plasma-aerosol hybrid jet according to claim 1, wherein PEDOT:PSS ink is atomized to form tiny droplets with an average diameter of 0.1~5μm.

3. The PEDOT:PSS molding method based on plasma-aerosol composite jet according to claim 1, characterized in that, The sheath gas flow rate ranges from 350 to 700 sccm; The carrier gas flow rate ranges from 150 to 400 sccm; The plasma working gas flow rate ranges from 1500 to 2700 sccm; The flow rate ratio of carrier gas to sheath gas is 1:1.7~2.

5.

4. The PEDOT:PSS molding method based on plasma-aerosol composite jet according to claim 1, characterized in that, The carrier gas and sheath gas are independently selected from one or more of nitrogen, argon, and helium, and the plasma working gas is one or more of helium, argon, and oxygen.

5. The PEDOT:PSS molding method based on plasma-aerosol composite jet according to claim 1, characterized in that, The plasma is excited by an electric field at normal pressure, and the electric field is generated by an AC power supply or a radio frequency power supply.

6. The PEDOT:PSS molding method based on plasma-aerosol composite jet according to claim 1, characterized in that, The diameter of the plasma-aerosol composite jet is 1~10 mm.

7. The PEDOT:PSS molding method based on plasma-aerosol composite jet according to claim 1 or 6, characterized in that, For plasma-aerosol composite jets with diameters of 1 to 10 mm, when using an AC power supply to excite the plasma, the voltage range is 5 to 50 V, the current range is 0.1 to 3 A, and the frequency range is 5 to 20 kHz; when using a radio frequency power supply to excite the plasma, the power range is 1 to 500 W, and the frequency range is 10 to 50 MHz.

8. The PEDOT:PSS molding method based on plasma-aerosol composite jet according to claim 1, characterized in that, The plasma is a low-temperature plasma with a temperature ≤100 ℃.

9. The PEDOT:PSS molding method based on plasma-aerosol composite jet according to claim 8, characterized in that, The temperature of low-temperature plasma is 20~70℃.

10. The PEDOT:PSS molding method based on plasma-aerosol composite jet according to claim 8, characterized in that, Low-temperature plasma is excited by an electric field at room temperature and normal pressure.

11. The PEDOT:PSS molding method based on plasma-aerosol composite jet according to claim 1, characterized in that, The distance between the nozzle and the substrate of the print head is 1~8 mm; the moving speed of the print head is 0.1~10 mm / s.

12. A PEDOT:PSS printing structure, characterized in that, It is prepared by the PEDOT:PSS molding method based on plasma-aerosol composite jet as described in any one of claims 1 to 11. The aspect ratio of the PEDOT:PSS printed structure is 10 to 100 and the line width is 10 to 60 μm.

13. The PEDOT:PSS printed structure as described in claim 12 is used in bioelectronics, flexible electronic devices, microsensors, and microfluidic chips.

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