Cold atmospheric pressure plasma-assisted aerosol deposition of pedot and application thereof

Abstract

The present invention successfully utilizes room-temperature atmospheric pressure plasma-assisted aerosol deposition technology to effectively deposit poly(3,4-ethylenedioxythiophene) (PEDOT) dual-band electrochromic thin films. These films exhibit excellent visible (VIS) and near-infrared (NIR) transmittance properties, along with rapid color-switching response through efficient perclorate-ion intercalation. The dual-band electrochromic thin films fabricated via room-temperature atmospheric pressure plasma-assisted aerosol deposition demonstrate outstanding electrochromic performance, fast switching speed, high stability, and manufacturing efficiency. This technology holds significant potential in the field of smart energy-saving windows and offers high-efficiency, low-cost energy-saving solutions for the construction and automotive industries.

Description

Technical Field

[0001] A method for synthesizing and coating polydioxyethylthiophene, particularly a method for synthesizing polydioxyethylthiophene using plasma-assisted aerosol and its application. Prior Technology

[0002] Extreme climate change is becoming increasingly severe globally, including more frequent heat waves, droughts, torrential rains, and stronger hurricanes, all stemming from global warming. Global warming is primarily caused by the greenhouse effect, which is caused by emissions of greenhouse gases such as carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O). These gases act like a barrier around the Earth, preventing the effective dissipation of solar radiation and leading to rising global temperatures.

[0003] Statistics show that the building sector accounts for approximately 35% of global energy consumption and contributes about 38% of greenhouse gas emissions. Of this, about 50% of building energy loss occurs through heat conduction through glass openings, including heat loss from indoor air conditioning cooling and heating. Therefore, the development of modern glass technology aims to reduce building energy loss while improving the thermal and visual comfort of residents. Glass curtain wall systems can be adjusted according to the needs of residents and external environmental conditions to enhance the building's energy efficiency.

[0004] Traditional static glazing technologies cannot be adjusted according to environmental conditions or user needs, thus dynamic glazing technologies have gradually become a research focus. Dynamic glazing can change optical and thermal properties through passive or active control mechanisms to regulate solar energy absorption and transmittance. However, each type of active dynamic glazing technology has its limitations. In comparison, electrochromic devices (ECDs) have the longest history of use and the best durability, but improvements are still needed to increase the number of color-changing states, improve the color-changing speed, reduce costs, and provide more diverse color-changing modes so that users can choose different light transmission and heat insulation effects. Summary of the Invention

[0005] To address the limitations of existing traditional static glass technology in adapting to environmental conditions or user needs, and the need for improvements in electrochromic devices (ECDs) to increase the number of color-changing states, improve color-changing speed, reduce costs, and provide more diverse color-changing modes so that users can choose different light transmission and heat insulation effects, this invention provides a plasma-assisted aerosol method for synthesizing poly(dioxyethylthiophene), which possesses multi-colored dual-band electrochromic (EC) properties and can achieve electrochromic effects by selectively controlling the transmittance of visible light (VIS) and near-infrared light (NIR).

[0006] The first inventive concept of this invention is a method for synthesizing poly(3,4-ethylenedioxythiophene), PEDOT, using plasma-assisted aerosol, the steps of which include: Step 1: Provide a 3,4-ethylenedioxythiophene solution to an aerosol generator; Step 2: The 3,4-ethylenedioxythiophene solution is generated into a 3,4-ethylenedioxythiophene aerosol by the aerosol generator and then sprayed onto a plasma jet ejected from a plasma nozzle; and Step 3: The 3,4-ethylenedioxythiophene aerosol is synthesized into polydioxyethylthiophene by the plasma jet and then deposited on the surface of a substrate.

[0007] The substrate is a conductive substrate or more preferably indium tin oxide.

[0008] The 3,4-ethylenedioxythiophene solution contains: 3,4-Ethylenedioxythiophene is between 0.01 M and 1 M; Lithium perchlorate is between 0.01M and 1M; Propylene carbonate is between 0.01M and 1M; or Ethanol ranges from 1 vol. to 99 vol.%.

[0009] The plasma-assisted aerosol process parameters include: The injection rate of the 3,4-ethylenedioxythiophene solution was between 0.01 and 1 ml / min. The compressed air pressure for 3,4-ethylenedioxythiophene aerosol is between 0.01 and 20 bar. The nozzle height of the aerosol generator is between 0.1 and 10 cm. The nozzle angle of the aerosol generator is between 90 degrees. The nozzle distance of the aerosol generator is between 0.1 and 10 cm. The plasma jet velocity ranges from 0.01 to 50 (l / min); Plasma power ranges from 100 to 500 (Watts); Plasma frequencies range from 1 to 50 kHz. The height of the plasma nozzle is between 0.1 and 10 cm. Plasma application time is between 1 and 1000 seconds; or The substrate temperature ranges from 1 to 150 degrees Celsius.

[0010] The present invention also provides a smart window comprising a polydioxyethylthiophene film prepared by the aforementioned method for synthesizing polydioxyethylthiophene using plasma-assisted aerosol.

[0011] As can be seen from the above description, the present invention has the following beneficial effects and advantages:

[0012] 1. This invention successfully deposits a dual-band electrochromic thin film of poly(dioxyethylthiophene) (PEDOT) using atmospheric pressure plasma-assisted aerosol deposition (CAPPA-AD) technology, which has excellent visible light (VIS) and near-infrared light (NIR) transmittance and rapid color-changing response performance of perchlorate ion intercalation.

[0013] 2. The ambient temperature atmospheric pressure plasma-assisted aerosol deposition of the present invention has the advantages of low cost and high efficiency process. It does not require an expensive vacuum system. Compared with other deposition methods, such as the complex and expensive equipment required by physical / vapor deposition (PVD / CVD) processes, the equipment cost of the present invention is lower and has more potential and value for practical commercial implementation.

[0014] 3. This invention can prepare multicolor dual-band electrochromic thin films (PEDOT) through plasma-assisted aerosol at room temperature and atmospheric pressure, and has excellent color-changing performance, color-changing speed, stability and manufacturing efficiency. It has great potential in the field of smart energy-saving windows and can provide efficient and low-cost energy-saving solutions for the construction and automotive industries. Simple Explanation of the Diagram

[0015] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are merely some examples or embodiments of the present invention and are not intended to absolutely limit the technical scope of the present invention. Unless obvious from the context or otherwise stated, the same reference numerals in the drawings represent the same structures or operations. Wherein: Figures 1 and 2 are diagrams of the apparatus and flowcharts of the plasma-assisted aerosol polydioxyethylthiophene synthesis system of the present invention. Figures 3 and 4 show the changes in transmittance (T%), wavelength, and charge per unit area (q, C / cm²) of the preferred embodiment and comparative example of the present invention. Implementation

[0016] The present invention will be described in detail below with reference to several preferred embodiments. The accompanying drawings are merely some exemplary representations or embodiments of the present invention. For those skilled in the art, the present invention can be applied to other similar situations based on these drawings without any further effort.

[0017] The terms “system,” “apparatus,” “unit,” and / or “module” used in this invention are to distinguish different components, elements, parts, sections, or assemblies at different levels. However, if other terms can achieve the same purpose, they may be replaced by other expressions. As illustrated in this invention, unless the context clearly indicates otherwise, words such as “a,” “an,” “an,” and / or “the” do not specifically refer to the singular and may also include the plural. Generally, the terms “comprising” and “including” only indicate the inclusion of explicitly identified steps and elements, which do not constitute an exclusive list; the method or apparatus may also include other steps or elements.

[0018] This invention uses flowcharts to illustrate the operations performed by the system according to embodiments of the invention. It should be understood that the preceding or following operations are not necessarily performed precisely in sequence. Instead, the steps can be processed in reverse order or simultaneously. Furthermore, other operations can be added to these processes, or one or more steps can be removed from them.

[0019] < [Synthesis method of poly(dioxyethylthiophene) using plasma-assisted aerosols]

[0020] Please refer to Figures 1 and 2, which illustrate the method and system for synthesizing poly(dioxyethylthiophene) using plasma-assisted aerosols according to the present invention. The steps include:

[0021] Step S1: Provide a 3,4-ethylenedioxythiophene (EDOT) solution to an aerosol generator 10;

[0022] Step S2: The EDOT solution is formed into an EDOT aerosol 11 by the aerosol generator 10 and then sprayed onto a plasma jet 21 ejected by a plasma nozzle 20;

[0023] Step S3: The EDOT aerosol 11 is synthesized into poly(dioxyethylthiophene) (PEDOT) by the plasma jet 21 and then deposited on the surface of a substrate 30.

[0024] Please refer to Table 1 below, which is a preferred embodiment formulation of the EDOT solution. Preferably, EDOT is mixed in a specific ratio in a solution prepared from lithium perchlorate, propylene carbonate, and ethanol.

[0025] Table 1. Material Proportion EDOT 0.01M~1M Lithium perchlorate (LiClO 4) 0.01M~1M Propylene carbonate (PC) 0.1 vol.% - 50 vol.% Ethanol 1 vol. - 99 vol.%

[0026] Please refer to Table 2 below, which contains the process parameters for a preferred embodiment of the aerosol generator 10 and the plasma nozzle 20.

[0027] Table 2. aerosol end Process conditions parameter EDOT solution injection rate (sprayed towards the aerosol generator 10) 0.01~100 (ml / min) EDOT aerosol compressed air pressure (sprayed onto the plasma jet 21) 0.01~20 (bar) The aerosol generator has 10 nozzles at a height of [missing information]. 0.1~10 (cm) The nozzle angle of the aerosol generator 10 (compared to the plasma jet 21) 90 (degrees) The distance between the nozzles of the aerosol generator 10 and the plasma jet 21. 0.1~10 (cm) Plasma end Plasma gas jet rate (sprayed onto the substrate 30) 0.01~50 (l / min) Plasma power 100~500 (Watts) Plasma frequency 1~50 (kHz) The plasma nozzle has a nozzle height of 20 (compared to the substrate of 30). 0.1~10 (cm) Plasma application time 1~1000 (seconds) The substrate is at a temperature of 30°C. 1~150 (degree)

[0028] Preferably, the substrate 30 of the present invention is a conductive substrate, such as an indium tin oxide (ITO) conductive substrate.

[0029] <Validity Test>

[0030] Please refer to Tables 3 and 4 and Figures 3 and 4, which show the material formulation and process parameters of the preferred embodiment of the present invention, as well as the corresponding transmittance (T%) and wavelength variation in Figure 3, and the charge per unit area variation (q, C / cm²) in Figure 4. Table 3 is only one preferred embodiment of the present invention and is not intended to limit the scope claimed in this application; parameters and ratios in other scopes have been proven effective.

[0031] Meanwhile, Figures 3 and 4 in this case also compare the performance of the comparative example without plasma-assisted process and the simple indium tin oxide (ITO) conductive substrate.

[0032] Table 3. Material Proportion EDOT 0.1M Lithium perchlorate (LiClO 4) 0.05M Propylene carbonate (PC) 4.7 vol.% Ethanol 94.1 vol.% Substrate Indium tin oxide (ITO) conductive substrate

[0033] Table 4. aerosol end Process conditions parameter EDOT solution injection rate (sprayed towards the aerosol generator 10) 0.6 (ml / min) EDOT aerosol compressed air pressure (sprayed onto the plasma jet 21) 2 bar The aerosol generator has 10 nozzles at a height of [missing information]. 0.8 (cm) The nozzle angle of the aerosol generator 10 (compared to the plasma jet 21) 90 (degrees) The distance between the nozzles of the aerosol generator 10 and the plasma jet 21. 7 (cm) Plasma end Plasma gas jet rate (sprayed onto the substrate 30) 33.3 (l / min) Plasma power 300 (Watts) Plasma frequency 20 (kHz) The plasma nozzle has a nozzle height of 20 (compared to the substrate of 30). 2 (cm) Plasma application time 90 seconds The substrate is at a temperature of 30°C. 95 (degrees)

[0034] Figure 3 shows the changes in transmittance (T%) versus wavelength. Compared to comparative examples without plasma application and those using pure ITO substrates, this invention exhibits significant perchlorate ion intercalation (ClO₄-intercalation) effects in the visible light (400nm~700nm) and near-infrared light (700nm~1500nm) ranges. The mechanism of perchlorate ion intercalation is mainly based on an electrochemical reaction that occurs within the thin film. Because the plasma-assisted aerosol process of this invention can alter the optical and electronic properties of the polymer, a better electrochromic effect is achieved.

[0035] Figure 4 shows the change in charge per unit area (q, C / cm²). Compared with the comparative example without plasma application and the comparative example with pure ITO substrate, the q value of the present invention changes the most over time, indicating that it has the best storage capacity for perchlorate ion charge and the best color change response.

[0036] The present invention provides a method for synthesizing polydioxyethylthiophene using plasma-assisted aerosols. The synthesized polydioxyethylthiophene has been tested and found to possess... This invention features dual-band electrochromic performance, with excellent wide-spectrum color-changing range, superior color-changing speed, stability, manufacturing efficiency, and cost. It has great potential for application in the field of smart energy-saving windows, providing efficient and low-cost energy-saving solutions for the construction and automotive industries.

[0037] This invention uses flowcharts to illustrate the operations performed by the system according to embodiments of the invention. It should be understood that the preceding or following operations are not necessarily performed precisely in sequence. Instead, the steps can be processed in reverse order or simultaneously. Furthermore, other operations can be added to these processes, or one or more steps can be removed from them.

[0038] In some embodiments, numbers describing the quantity of components and attributes are used. It should be understood that such numbers used in the description of embodiments are modified in some examples with the terms "approximately," "approximately," or "generally." Unless otherwise stated, "approximately," "approximately," or "generally" indicates that the numbers are allowed to vary by ±20%. Accordingly, in some embodiments, the numerical parameters used in the specification and claims are approximate values, which may be changed depending on the characteristics required by individual embodiments. In some embodiments, numerical parameters should take into account specified significant digits and employ a general method of digit reservation. Although the numerical ranges and parameters used to confirm their breadth of range in some embodiments of the invention are approximate values, in specific embodiments, such values ​​are set as precisely as feasible.

[0039] Finally, it should be understood that the embodiments described in this invention are merely illustrative of the principles of the invention. Other modifications may also fall within the scope of this invention. Therefore, alternative configurations of the embodiments of this invention are considered as examples and not limitations, and are regarded as consistent with the teachings of this invention. Accordingly, the embodiments of this invention are not limited to those explicitly described and illustrated herein.

[0040] 10: Aerosol Generator 11EDOT: Aerosol 20: Plasma nozzle 21: Plasma jet beam 30: Substrate S1~S3: Steps

Claims

1. A method for synthesizing poly(dioxyethylthiophene) using plasma-assisted aerosol, comprising the following steps: Step 1: providing a 3,4-ethylenedioxythiophene solution to an aerosol generator; Step 2: forming a 3,4-ethylenedioxythiophene aerosol from the 3,4-ethylenedioxythiophene solution using the aerosol generator and then spraying it onto a plasma jet stream ejected from a plasma nozzle; Step 3: heating a conductive substrate and controlling its temperature to 95°C, wherein the 3,4-ethylenedioxythiophene aerosol is synthesized into poly(dioxyethylthiophene) by the plasma jet stream and then deposited on the surface of the conductive substrate as a poly(dioxyethylthiophene) film; and the formed poly(dioxyethylthiophene) film, under electrochemical driving, exhibits a charge change (q) per unit area of ​​at least 0.0015 C / cm² within 40 seconds.

2. The method for synthesizing polydioxyethylthiophene from plasma-assisted aerosol as described in claim 1, wherein: the conductive substrate comprises indium tin oxide.

3. The method for synthesizing poly(ethylenedioxythiophene) from plasma-assisted aerosol as described in claim 1 or 2, wherein the 3,4-ethylenedioxythiophene solution comprises: 3,4-ethylenedioxythiophene in the range of 0.01 M to 1 M; lithium perchlorate in the range of 0.001 M to 1 M; propylene carbonate in the range of 0.1 vol.% to 50 vol.%; or ethanol in the range of 1 vol.% to 99 vol.%.

4. A method for synthesizing poly(ethylenedioxythiophene) using plasma-assisted aerosol as described in claim 1 or 2, wherein: the injection rate of the 3,4-ethylenedioxythiophene solution is between 0.01 and 100 ml / min; the compressed air pressure of the 3,4-ethylenedioxythiophene aerosol is between 0.01 and 20 bar; the nozzle height of the aerosol generator is between 0.1 and 10 cm; the nozzle angle of the aerosol generator is between 90 degrees; the nozzle distance of the aerosol generator is between 0.1 and 10 cm; the plasma gas injection rate is between 0.01 and 50 l / min; the plasma power is between 100 and 500 Watts; the plasma frequency is between 1 and 50 kHz; the nozzle height of the plasma is between 0.1 and 10 cm; or the plasma application time is between 1 and 1000 seconds.

5. A smart window comprising a polydioxyethylthiophene film prepared by the polydioxyethylthiophene synthesis method using plasma-assisted aerosol as described in any one of claims 1 to 4.

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