阅读说明：本技术 用于打印pedot：pss导电水凝胶的装置及其方法 (For printing PEDOT: device and method of PSS conductive hydrogel ) 是由 梁波 任航旭 叶学松 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种用于打印PEDOT：PSS导电水凝胶的装置及其方法,涉及印刷电子的技术领域。它包含内管、外管和可拆卸喷头,所述内管嵌套在所述外管内,所述可拆卸喷头通过螺纹固定于外管下端,其中所述内管的上端设置有内管进料口,所述外管的一侧设置有外管进料口。本发明将PEDOT:PSS从内管进料口注入,将二次掺杂剂从外管进料口注入,在适宜的浓度与比例下室温条件可以从喷头位置得到均匀的PEDOT:PSS导电水凝胶。其具有良好的导电性能,并且可以在三轴平台上绘制所需要的各种图案。本发明通过同轴打印的方式,将PEDOT:PSS与二次掺杂剂由不同的管道注入,最后于喷头位置相结合形成导电水凝胶,只要将本发明固定于任意三轴平台,皆可轻易绘制各种图形,实现电子印刷。(The invention discloses a method for printing PEDOT: a PSS conductive hydrogel device and a method thereof relate to the technical field of printed electronics. It contains inner tube, outer tube and can dismantle the shower nozzle, the inner tube nestification is in the outer tube, can dismantle the shower nozzle and pass through threaded fixation in outer tube lower extreme, wherein the upper end of inner tube is provided with the inner tube feed inlet, one side of outer tube is provided with the outer tube feed inlet. According to the invention, PEDOT/PSS is injected from the inlet of the inner tube, secondary doping agent is injected from the inlet of the outer tube, and uniform PEDOT/PSS conductive hydrogel can be obtained from the position of a spray head at room temperature under appropriate concentration and proportion. The conductive film has good conductive performance, and various patterns required by the conductive film can be drawn on a triaxial platform. According to the invention, PEDOT, PSS and secondary doping agents are injected from different pipelines in a coaxial printing mode, and finally, the PEDOT, PSS and secondary doping agents are combined at the position of a spray head to form conductive hydrogel.)

1. A method for printing PEDOT: the device for the PSS conductive hydrogel is characterized by comprising an inner pipe (1), an outer pipe (2) and a sprayer (3), wherein the inner pipe (1) is coaxially nested in the outer pipe (2), and the sprayer (3) is arranged at the bottom of the outer pipe (2); the inner tube (1) is provided with an inner tube feeding hole (11) and an inner tube discharging hole (12), and a through cavity channel is arranged between the inner tube feeding hole (11) and the inner tube discharging hole (12); the inner pipe discharge port (12) and the spray head (3) are coaxially arranged, and the spray head (3) forms an annular spray nozzle around the circumference of the inner pipe discharge port (12); an outer pipe feeding hole (22) is formed in the outer pipe (2), a gap is reserved between the inner pipe (1) and the outer pipe (2), and the outer pipe feeding hole (22) is communicated with the annular nozzle in a sealing mode.

2. The printer for printing PEDOT according to claim 1: the PSS conductive hydrogel device is characterized in that the spray head (3) is detachably fixed at the bottom of the outer tube (2) in a sealing manner.

3. The method for printing PEDOT according to claim 2: the PSS conductive hydrogel device is characterized in that the spray head (3) is connected with the outer tube (2) through threads.

4. The printer for printing PEDOT according to claim 1: the PSS conductive hydrogel device is characterized in that the caliber of the inner tube discharge hole (12) is smaller than that of the inner tube feed hole (11).

5. The printer for printing PEDOT according to claim 1: the PSS conductive hydrogel device is characterized in that the spray head (3) is in an inverted frustum shape, the bottom section of the inner tube (1) is also in an inverted frustum shape, and the cross section of a channel between the spray head and the inner tube is gradually reduced from top to bottom.

6. The printer for printing PEDOT according to claim 1: the PSS conductive hydrogel device is characterized in that the top of an outer tube (2) is sealed with an inner tube (1), and a feed inlet (22) of the outer tube is formed in the side wall of the outer tube (2).

7. The printer for printing PEDOT according to claim 1: the PSS conductive hydrogel device is characterized in that the bottom surface of the spray head (3) and the bottom surface of the inner pipe (1) are in the same horizontal plane.

8. The printer for printing PEDOT according to claim 1: the device for preparing PSS conductive hydrogel is characterized in that an inner pipe feeding port (11) is connected with a first feeding device for injecting PEDOT and PSS materials, and an outer pipe feeding port (22) is connected with a second feeding device for injecting secondary dopants.

9. The printer for printing PEDOT according to claim 1: the PSS conductive hydrogel device is characterized by further comprising a three-axis moving platform, and the device is integrally carried on the three-axis moving platform through the outer tube (2) to move.

10. Printing PEDOT using an apparatus according to any one of claims 1 to 9: a method of PSS conductive hydrogel, characterized in that the device is controlled to move on the plane of the electronic device according to a planned path; in the moving process, injecting a PEDOT (PSS) material through an inner tube feeding hole (11), injecting a secondary doping agent through an outer tube feeding hole (22), synchronously ejecting the PEDOT (PSS) and the secondary doping agent from an inner tube discharging hole (12) and an annular nozzle respectively, mixing at a target position to generate PEDOT (PSS) conductive hydrogel, and obtaining a target pattern on the surface of an electronic device after shaping; the secondary dopant is preferably dodecylbenzene sulfonic acid.

Technical Field

The invention relates to a device in the technical field of printed electronics, in particular to a device for printing PEDOT: PSS conductive hydrogel devices.

Background

Printed electronics technology has been actively studied and developed as a novel technology for manufacturing lightweight, wearable electronic products. Conductive polymers are ideal electrodes for printed electronics due to their superior mechanical properties and solution processability compared to traditional semiconductors. Wherein, the poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonate) (PEDOT: PSS) is considered to be the most promising candidate material due to its tunable electrical properties, visible light transmittance, biocompatibility, and good environmental stability.

The conductivity can be improved by adding a secondary dopant such as ionic liquid or dimethyl sulfoxide to the aqueous PEDOT: PSS solution, and it has recently been found that when an excess of secondary dopant is added, the viscosity of the PEDOT: PSS increases, forming a new material, known as a conductive hydrogel.

The most common thin film patterning method currently used is photolithography, which requires custom masks as a printed electronic method, which is time and financial consuming and has the potential for contamination due to multiple processing steps. There is therefore a need for a device for printing PEDOT: PSS conductive hydrogels that can be printed quickly and with a simple process.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a device for quickly printing PEDOT/PSS conductive hydrogel with simple process. According to the invention, the PEDOT/PSS conductive hydrogel and the secondary dopant flow out of two different pipelines to a sprayer structure through a coaxial structure, and the PEDOT/PSS conductive hydrogel and the secondary dopant are in contact and quickly cured at a discharge port, so that the purpose of quickly printing the PEDOT/PSS conductive hydrogel is realized.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a method for printing PEDOT: the PSS conductive hydrogel device is provided with an inner tube, an outer tube and a sprayer, wherein the inner tube is coaxially nested in the outer tube, and the sprayer is arranged at the bottom of the outer tube; the inner pipe is provided with an inner pipe feeding hole and an inner pipe discharging hole, and a through cavity channel is arranged between the inner pipe feeding hole and the inner pipe discharging hole; the discharge port of the inner pipe is coaxially arranged with the spray head, and the spray head forms an annular spray nozzle around the circumference of the discharge port of the inner pipe; the outer pipe is provided with an outer pipe feeding hole, and a gap is reserved between the inner pipe and the outer pipe, so that the outer pipe feeding hole is communicated with the annular nozzle in a sealing mode.

Preferably, the spray head is detachably fixed at the bottom of the outer pipe in a sealing manner.

Furthermore, the spray head is connected with the outer pipe through threads.

Preferably, the caliber of the discharge hole of the inner tube is smaller than that of the feed hole of the inner tube.

Preferably, the nozzle is in an inverted circular truncated cone shape, the bottom section of the inner pipe is also in an inverted circular truncated cone shape, and the cross section of a channel between the nozzle and the inner pipe is gradually reduced from top to bottom.

Preferably, the top of the outer tube is sealed with the inner tube, and the feed inlet of the outer tube is arranged on the side wall of the outer tube.

Preferably, the bottom surface of the spray head and the bottom surface of the inner pipe are in the same horizontal plane.

Preferably, the feeding port of the inner tube is connected with a first feeding device for injecting PEDOT and PSS materials, and the feeding port of the outer tube is connected with a second feeding device for injecting secondary dopants.

Preferably, the device further comprises a three-axis moving platform, and the device is carried on the three-axis moving platform through the whole outer pipe to move.

It is another object of the invention to provide a method of printing PEDOT: the PSS conductive hydrogel preparation method comprises the following steps: controlling the device to move on the plane of the electronic device according to the planned path; in the moving process, injecting a PEDOT (PSS) material through an inner tube feeding port, injecting a secondary doping agent through an outer tube feeding port, synchronously ejecting the PEDOT (PSS) and the secondary doping agent from an inner tube discharging port and an annular nozzle respectively, mixing the PEDOT and the secondary doping agent at a target position to generate a PEDOT (PSS) conductive hydrogel, and forming to obtain a target pattern on the surface of an electronic device; the secondary dopant is preferably dodecylbenzene sulfonic acid.

According to the invention, PEDOT, PSS and secondary doping agents are injected from different pipelines in a coaxial printing mode, and finally, the PEDOT, PSS and secondary doping agents are combined at the position of a spray head to form conductive hydrogel. The product of the invention has uniform and stable outflow, convenient use, simple process, low price and convenient cleaning, and is suitable for PEDOT: printing of PSS conductive hydrogel.

Drawings

FIG. 1 is a diagram showing the effect of the assembly of the device of the present invention.

FIG. 2 is a cross-sectional assembly view of the device of the present invention.

Fig. 3 is a cross-sectional view of the inner tube of the present invention.

Figure 4 is a cross-sectional view of the outer tube of the present invention.

Fig. 5 is a schematic view of a showerhead of the present invention.

Detailed Description

The following detailed description of the embodiments of the present invention is provided in conjunction with the accompanying drawings, which are set forth in the appended claims, and are intended to illustrate the embodiments of the present invention.

In a preferred embodiment of the invention, as shown in figures 1 and 2, there is provided a device for printing conductive hydrogel of PEDOT: PSS, the main components of which comprise an inner tube 1, an outer tube 2 and a spray head 3. Wherein, the inner tube 1 is coaxially nested in the outer tube 2, and the nozzle 3 is arranged at the bottom of the outer tube 2.

As shown in fig. 3, the inner tube 1 is a straight tube, the top of which is provided with an inner tube inlet 11, the bottom of which is provided with an inner tube outlet 12, and a through channel is arranged between the inner tube inlet 11 and the inner tube outlet 12. The fluid injected from the inner tube inlet 11 can flow along the channel to the inner tube outlet 12 to be sprayed out. In order to ensure the ejection speed during printing, the diameter of the inner tube discharge port 12 may be smaller than the diameter of the inner tube feed port 11.

In this device, the fluid injected in the inner tube 1 is PEDOT: PSS, i.e., poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonate). To improve its conductivity, a secondary dopant needs to be further added to the aqueous PEDOT: PSS solution. And when the secondary doping agent is excessive, the viscosity of PEDOT (PSS) is increased, and a conductive hydrogel with high conductivity is formed. Therefore, the secondary doping agent needs to be mixed with PEDOT: PSS in the printing process, but the viscosity is too high due to early mixing, so that smooth jetting and printing cannot be realized, and the mixing position of the two is arranged at the nozzle opening position of the nozzle 3. Specifically, the inner-pipe discharge port 12 is arranged coaxially with the shower head 3. The bottom end of the inner pipe 1 occupies the central position of the nozzle head 3, but has an outer diameter smaller than the inner diameter of the nozzle orifice of the nozzle head 3, so that the nozzle head 3 forms an annular nozzle orifice circumferentially around the discharge opening 12 of the inner pipe. As shown in fig. 4, the outer tube feed opening 22 is formed on the side wall of the outer tube 2, and the outer diameter of the inner tube 1 is smaller than the inner diameter of the outer tube 2, so that a gap is left between the inner tube 1 and the outer tube 2, and the outer tube feed opening 22 is in sealed communication with the annular nozzle at the bottom. The term "close communication" as used herein means that the communication path is closed and that the material introduced through the outer tube inlet 22 can only exit through the annular nozzle. In this embodiment, the top of the outer tube 2 has a nesting opening 21 with the same outer diameter as the inner tube 1, the inner tube 1 passes through the nesting opening 21, and the two are fixed by welding to maintain the tightness of the inner tube and the outer tube.

Similarly, in order to ensure the injection speed of the secondary doping agent, the spray head 3 is designed to be in an inverted circular truncated cone shape, the bottom section of the inner tube 1 is also in an inverted circular truncated cone shape, the two are coaxially arranged, the cross section of a channel formed by clamping the spray head and the inner tube is gradually reduced from top to bottom, and the position of an annular outlet is the minimum.

In addition, for easy cleaning and disassembly, the spray head 3 is preferably fixed on the bottom of the outer tube 2 in a detachable manner in a sealing manner. In this embodiment, the outer tube 2 is provided with an internal thread 23, the top of the nozzle 3 is provided with an external thread 31, the external thread 31 at the upper end of the detachable nozzle 3 is screwed and fixed with the internal thread 23 at the lower end of the outer tube 2, and no liquid leakage occurs between the two. When cleaning is required, the spray head 3 can be directly unscrewed.

When in use, the inner pipe 1 and the outer pipe 2 are both vertically placed, and the device can be wholly carried on a three-axis moving platform through the outer pipe 2 to move. The inner tube feed port 11 is then connected to a first feed for injecting PEDOT: PSS material and the outer tube feed port 22 is connected to a second feed for injecting secondary dopant. The two materials are synchronously sprayed out from the inner tube discharge port 12 and the annular nozzle respectively to form a mixed state and then become the conductive hydrogel. In consideration of the reliability and stability of printing, the bottom surface of the head 3 and the bottom surface of the inner pipe 1 should be at the same level in this embodiment.

In a preferred embodiment of the invention, the first and second supply devices may be replaced by medical syringes. Two pipes with adapters are previously installed on the inner pipe feed port 11 and the outer pipe feed port 22, respectively. The catheter material used is preferably polytetrafluoroethylene. Then, the other ends of the two catheters are respectively connected with a 5ml medical injector filled with medicaments, wherein the medicament used at the feed inlet 11 of the inner tube is 1.1 wt% of PEDOT: PSS, and the medicament used at the feed inlet 22 of the outer tube is 96% of dodecylbenzene sulfonic acid. The two medical injectors are fixed on different injection pumps and respectively control the speed and time of medicament perfusion.

Based on this device, can provide one kind and print PEDOT: the PSS conductive hydrogel preparation method comprises the following steps:

when the device is used, the device is fixed on a three-axis moving platform, and after a program of the platform is edited, the three-axis platform can drive the device to correspondingly move on an electronic device plane to be printed according to a planned path. In the moving process, by controlling an injection pump, 1.1 wt% of PEDOT: PSS material is injected through an inner tube feeding port 11, 96 wt% of dodecylbenzene sulfonic acid is injected through an outer tube feeding port 22, PEDOT: PSS entering from the inner tube feeding port 11 and the dodecylbenzene sulfonic acid entering from the outer tube feeding port 22 are synchronously sprayed out from an inner tube discharging port 12 and an annular nozzle respectively, the PEDOT: PSS and high-concentration dodecylbenzene sulfonic acid are mixed, and high-conductivity PEDOT: PSS conductive hydrogel is generated at a target position of a device. The device prints while moving, and various patterns and lines can be realized on the device after the conductive hydrogel is shaped at normal temperature.

After the printing operation is finished, clear water is injected from the inner pipe feeding hole 11 and the outer pipe feeding hole 22, and residual PEDOT, PSS and dodecyl benzene sulfonic acid in the inner pipe cavity and the outer pipe cavity are extruded from the discharging holes. The detachable nozzle 3 can be detached along the thread subsequently, and is further cleaned by clean water, so that the whole device is cleaned.

Therefore, the PEDOT/PSS conductive hydrogel with good conductivity can be obtained from the position of a spray head under the room temperature condition at a proper concentration and proportion by injecting the PEDOT/PSS from the feed inlet of the inner tube and injecting the secondary dopant from the feed inlet of the outer tube, and various required patterns can be drawn on a triaxial platform. However, the specific concentration, type, ratio and other parameters of the PEDOT, PSS and the secondary dopant can be selected according to the actual situation without limitation.

The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.