CN116660353A - High-performance organic electrochemical transistor based on foam structure channel prepared by template sacrifice method, and preparation method and application thereof - Google Patents
High-performance organic electrochemical transistor based on foam structure channel prepared by template sacrifice method, and preparation method and application thereof Download PDFInfo
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- -1 1-ethyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 claims description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 3
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
The invention relates to a high-performance organic chemical transistor (OECT) of a foam structure channel prepared by a template sacrificial method by taking an ionic liquid as a template. A PEDOT: PSS film of a foam structure is designed and prepared by a template sacrificial method. The domain induced by phase separation of the [ EMIM ] [ PF6] ionic liquid is used as a template for the foam structure by a template sacrificial method. Due to the presence of the foam structure, the transport of electrons and ions is improved. The PEDOT-PSS film with the foam structure is used as a channel layer to prepare the high-performance OECT. OECT with improved transconductance and reduced response time can be obtained. The present method provides a new and simple strategy for preparing high performance OECTs that can be used in a variety of wearable applications, including biological detection or health monitoring. The method has proved that the high-performance OECT of the foam structure channel prepared by taking the ionic liquid as the template can be successfully prepared.
Description
Technical Field
The invention relates to a high-performance organic electro-chemical transistor (OECT) of a foam structure channel prepared by a template sacrificial method by taking an ionic liquid as a template, which is particularly applicable to the flexible wearable field, and belongs to the technical field of composite structure design and preparation.
Background
Currently generally known: due to their high sensitivity and low operating voltage, organic electrochemical transistors (OECTs) are becoming promising devices for sensitive detection of chemical and biological analytes. A typical OECT consists of source, drain and gate electrodes, where the source and drain electrodes are connected by an organic semiconductor channel. During operation, ions in the electrolyte can effectively dope the semiconductor channels under the appropriate bias applied to the gate electrode, thereby doping or de-doping the channels. Thus, the modulation of the source-drain current by the application of the gate voltage can facilitate detection of the analyte. Many parameters are used to define the sensing capabilities of OECT. One of the key parameters is transconductance, which quantifies the ability of the gate voltage to modulate leakage current. OECTs with high transconductance typically have relatively high sensitivity in sensing applications. Another key parameter is the response time, which generally means fast chemical sensing and high sensitivity. Therefore, there is a need to develop new OECTs with both high transconductance and short response time.
Improving transconductance is critical to achieving high performance OECT. There are two strategies for improving the transconductance of OECT. One is to optimize the geometry of the channel layer. Especially, the transconductance can be greatly improved by reducing the channel length; however, there are limitations in the manufacturing technology. Another strategy is to improve the electrical properties of the channel layer, such as carrier mobility and volume capacitance. For example, synthesizing a new semiconducting polymer with higher carrier mobility and/or volumetric capacitance may improve the transconductance of OECT. The transconductance of OECT can also be improved by introducing glycol side chains onto existing semiconducting polymers. Both solvent treatment and physical doping of ethylene glycol or ionic liquids can improve the transconductance of OECTs, especially those based on poly (3, 4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS). Solvent treatment or physical doping can help expose more of the PEDOT portion, thereby improving the electrical properties of the channel. Compared with other methods, the solvent treatment and physical doping are very simple and convenient, and have potential application prospects in many application scenes.
Response time is another important parameter of OECT. Typically, a shorter response time means faster and more sensitive detection. Increasing the surface area of ion doping/dedoping is an effective strategy to improve OECT response time. Savva et al have greatly shortened the response time of the obtained OECT by facilitating ion transport of the organic semiconductor through the introduction of hydrophilic side chains. However, swelling of the semiconducting polymer may negatively affect other properties of the OECT. Recently Zhang et al prepared porous channels using a respiratory pattern method and achieved a reduction in response time to 4.6 seconds. Due to the geometrical advantage of the porous structure, doping/dedoping of ions is promoted, thereby explaining the shortening of the response time. However, this method cannot precisely control the size and density of the holes, resulting in low controllability.
To the applicant's knowledge, while there are many methods of optimizing transconductance and response time, improving transconductance and shortening response time at the same time remains a significant challenge. The domain induced by phase separation of the [ EMIM ] [ PF6] ionic liquid is used as a template for the foam structure. Due to the presence of the foam structure, the transport of electrons and ions is improved.
Disclosure of Invention
The invention solves the technical problems that: the method for preparing the foam structure channel by taking the domain induced by phase separation of the [ EMIM ] [ PF6] ionic liquid as the template of the foam structure channel is simple to operate, high in repeatability and high in controllability, and the transconductance and the response time of OECT are effectively improved.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a high-performance organic electrochemical transistor based on a foam structure channel of a template sacrificial method comprises the following steps:
(1) The volume ratio of the [ EMIM ] [ PF6] (1-ethyl-3-methylimidazole hexafluorophosphate) solution to the solution is 1:3 water and ethanol were mixed to prepare 49 μl of a solution, wherein [ EMIM ] [ PF6] was 1.3wt.% in the aqueous alcohol solution, 2.5 μl of 0.5vol.% (volume fraction of PEDOT: PSS solution) of a gos silane coupling agent solution and 2.5 μl of a 90% strength aqueous solution of DBSA dodecylbenzenesulfonic acid were added, and 500 μl of a PEDOT: PSS (3, 4-ethylenedioxythiophene): poly (styrene sulfonate) solution (PEDOT: PSS was 1.5wt.% in deionized water) were mixed to prepare a film precursor having a pore content of 15 vol.%, and the mixture was stirred at 300rpm for 30 minutes;
(2) Preparation of organic electrochemical transistor OECT:
firstly, preparing a source electrode and a drain electrode gold electrode on a PET substrate by using a template mask sputtering method; sputtering was performed on an ion sputtering apparatus (SBC-12, KYKY); the channel length and width were controlled to 500 μm (L) and 7000 μm (d), respectively; the grid electrode is tested by adopting external Ag/AgCl.
Then, the mixture of PEDOT: PSS prepared in step (1) was dropped on the electrode-coated PET substrate, followed by thermal annealing, 15. Mu.L of the mixture was dropped on the substrate previously coated with the gold electrode, the dropped film was annealed at 50℃for 30 minutes, and then at 120℃for 30 minutes, and the resulting substrate was washed with a mixture of water and ethanol (volume ratio of 1:3) by immersing and washing in the mixture, and the resulting foam structure film had a thickness of 1. Mu.m.
In order to solve the technical problems, another technical scheme provided by the invention is as follows: the high-performance organic electrochemical transistor of the foam structure channel prepared by the method.
In order to solve the technical problems, another technical scheme provided by the invention is as follows: the high-performance organic electrochemical transistor application of the foam structure channel can be used in various flexible wearable fields.
In order to solve the technical problems, another technical scheme provided by the invention is as follows: can be used for biological detection or health monitoring.
Preferably, it can be used for H 2 O 2 And glucose detection.
The invention has the beneficial effects that:
a method for preparing foam structure channels by using ionic liquid as a template. In this method, the domain induced by the phase separation of the [ EMIM ] [ PF6] ionic liquid is used as a template for the foam structure by a template sacrificial method. Due to the presence of the foam structure, the transport of electrons and ions is improved. By using the PEDOT: PSS film of such a foam structure as a channel layer, OECT with improved transconductance and shortened response time can be obtained. The present process has proven successful in preparing high performance OECTs for foam structure channels.
The separated ionic liquid is used as a template for preparing a foam structure film. The conductivity of the foam structure PEDOT-PSS film is improved from 0.2 to 573.7S cm compared with the dense PEDOT-PSS film -1 The volume capacitance is increased by 5 times to 71.80F cm -3 . In addition, ion doping/dedoping becomes more efficient in the PEDOT: PSS film of the foam structure. The results show that the transconductance rate of OECT based on the foam structure PEDOT: PSS increases from 90 μS to 18mS and the response time decreases from 1000 milliseconds to 300 milliseconds. OECT is very sensitive to detection of chemicals and metabolites (such as hydrogen peroxide and glucose) due to improved transconductance and shortened response time.
Drawings
The invention is further described below with reference to the accompanying drawings.
In fig. 1, a schematic diagram of a channel of a foam structure prepared by an ionic liquid template is shown.
In FIG. 2, OECT preparation of the PEDOT-PSS film was performed based on the foam structure.
The morphology of the foamed PEDOT: PSS films of different cell contents is shown in FIG. 3. (a) Scanning Electron Microscope (SEM) image of dense PEDOT: PSS film. (b-f) SEM images of foam structure PEDOT: PSS films having 8, 10, 15, 20 and 25vol% cell content. (g) Atomic Force Microscope (AFM) height and phase image of the foam structure PEDOT: PSS film with 15vol% cell content. (h) Cross-sectional SEM image of a foam structure PEDOT: PSS film having a pore content of 15 vol%. (i) Relationship between pore size and density and pore content of the foam structure PEDOT: PSS film.
FIG. 4 electrical properties of PEDOT: PSS film with foam structure. (a) PEDOT: PSS film conductivity varies with pore content. (b) CV curves of PEDOT: PSS films having different pore contents. (c) PEDOT: PSS film volume capacitance varies with pore content.
FIG. 5 shows the spectroelectrochemical properties and doping kinetics of the PEDOT: PSS film of foam structure. (a) is a schematic diagram of a measuring device. (b-c) foam structure and dense PEDOT: PSS film ultraviolet-visible-near infrared spectrum, the bias applied was varied from 0 to 1.0V during the measurement. (d) Peak strength (about 650 nm) of foam and dense PEDOT: PSS films varies with applied bias. (e-f) foam structure and doping kinetics of dense PEDOT: PSS film.
FIG. 6 is the kinetic absorption spectrum of the dense PEDOT: PSS film.
Fig. 7 is based on the OECT output performance of the foam structure channels. Schematic of the OECT prepared in (a). (b-c) OECT output curves based on dense and foam structured PEDOT: PSS films. (d-e) application of a drain voltage of 300mV based on the OECT transfer curve of dense and foam structured PEDOT: PSS films. (f-g) applying a pulsed gate voltage of 20mV based on the OECT response time of the dense and foam structure PEDOT: PSS film. (h) The applied gate voltage was varied between 0 and 20mV based on the stability of the foam structure PEDOT: PSS film OECT over 400 seconds.
FIG. 8 is based on the flexibility of the foam structure PEDOT: OECT of the PSS channels. (a) schematic representation of OECT under different bending conditions. (b) A transfer curve under different bending conditions with a gate voltage of 300mV applied. (c-d) change in relative conductivity at different radii of curvature and over 100 bending cycles.
FIG. 9OECT H 2 O 2 And glucose detection examples. (a) For H 2 O 2 Schematic representation of the detected OECT. (b) At different concentrations of H 2 O 2 Transmission curves obtained in solution. Vd=100 mV. (c) ΔID and H 2 O 2 Graph of the relationship between logarithms of the concentrations. (d) schematic of OECT for glucose detection. (e) Transmission curves obtained in glucose solutions of different concentrations. Glucose was dissolved in 0.9% sodium chloride solution. (f) graph of ΔID versus logarithm of glucose concentration.
Detailed description of the preferred embodiments
Example 1 OECT for designing foam Structure channels
Fig. 1 is a schematic diagram of a channel of an ionic liquid template preparation foam structure to increase the transconductance of the corresponding OECT and shorten the response time.
In FIG. 2, OECT preparation of the PEDOT-PSS film was performed based on the foam structure. Gold electrodes of the source and drain electrodes were prepared by ion sputtering (masking method). The mixture of PEDOT, PSS and ionic liquid was applied drop wise and thermally annealed at 50℃for 30 minutes and then at 120℃for 30 minutes. The ionic liquid in the film was then washed off with a mixture of water and ethanol (volume ratio 1:3).
As shown in fig. 1 and 2, ion doping/dedoping of the channel layer at the gate voltage is a key step in the OECT operation, having an important effect on its output performance and sensing capability. To improve the ion doping/dedoping effect, we used a template sacrificial method to prepare the channels of the foam structure and assemble them into high performance OECTs.
The preparation method comprises the following steps:
preparation of a foam structure film:
the volume ratio of the [ EMIM ] [ PF6] (1-ethyl-3-methylimidazole hexafluorophosphate) solution to the solution is 1:3 Water and ethanol were mixed to prepare 49. Mu.L of a solution in which [ EMIM ] [ PF6] was 1.3wt.% in an aqueous alcohol solution, 2.5. Mu.L of a 0.5vol.% (based on the volume fraction of PEDOT: PSS solution) GOPS silane coupling agent solution and 2.5. Mu.L of a 90% strength aqueous DBSA dodecylbenzenesulfonic acid solution were added, and 500. Mu.L of a PEDOT: PSS (3, 4-ethylenedioxythiophene): poly (styrene sulfonate) solution (PEDOT: PSS was 1.5wt.% in deionized water) were mixed to prepare a film precursor having a pore content of 15 vol.%, and the mixture was stirred at 300rpm for 30 minutes.
Then, 15. Mu.L of the mixture was dropped on a substrate previously coated with a gold electrode. The drop-coated film was annealed at 50℃for 30 minutes and then at 120℃for 30 minutes. The resulting substrate was rinsed with a water and ethanol (1:3) mixture by soaking and rinsing in the mixture. The thickness of the resulting foam structure film was about 1. Mu.m. The volume (8%, 10%, 15%, 20%, 25% of pores are the volume fraction of the corresponding ionic liquid [ EMIM ] [ PF6] in the film precursor to PEDOT: PSS, and the volume fraction of the ionic liquid to PEDOT: PSS after the deionized water in the solution is removed after annealing is adjusted according to the requirements to prepare the foam structure film with different pore contents.
Preparation of OECT: first, source and drain gold electrodes were prepared on a PET substrate using a stencil mask sputtering method. Sputtering was performed on an ion sputtering apparatus (SBC-12, KYKY). The channel length and width were controlled to 500 μm and 7000 μm, respectively. The above mixture containing PEDOT: PSS was then dropped onto the electrode coated PET substrate and then thermally annealed. The grid electrode is tested by adopting external Ag/AgCl. The mixture of PEDOT: PSS prepared in the above method (i.e., the above-mentioned film precursor mixture of 15vol% pore content) was dropped on an electrode-coated PET substrate, followed by thermal annealing, 15. Mu.L of the mixture was dropped on a substrate previously coated with a gold electrode, the dropped film was annealed at 50℃for 30 minutes, and then at 120℃for 30 minutes, and the resulting substrate was washed with a mixture of water and ethanol (volume ratio 1:3) by immersing and rinsing in the mixture, and the thickness of the resulting foam structure film was 1. Mu.m.
EXAMPLE 2 foam Structure PEDOT: PSS film morphology
As shown in FIG. 3, to confirm that the PEDOT: PSS film of the foam structure was successfully prepared, we used Scanning Electron Microscopy (SEM) for morphological characterization. It is evident that the formation of the foam structure PEDOT: PSS is highly dependent on the content of ionic liquid template in the PEDOT: PSS film. When no ionic liquid [ EMIM ] [ PF6] solution was added, the PEDOT: PSS film surface was smooth. When 8% by volume of ionic liquid was added as a template, uniform high density pores with a size of 500±200nm were formed on the membrane surface. When the pore content (determined by the ionic liquid template content before washing) was increased to 15% by volume, the pore size increased to 1000±300nm. Further increases in the content of the ionic liquid template result in further increases in pore size and the pore size becomes non-uniform. Eventually, when the pore content reaches 25% by volume, the pore size reaches saturation. In addition, the pore density decreases with increasing pore content. High pore density and proper pore size are necessary for optimization of ion transport. A pore content of 15vol% was used in example 1 because the sample has a higher output performance, as will be explained in the examples below.
The foam structure PEDOT: PSS film with a pore content of 15% by volume was further characterized using an Atomic Force Microscope (AFM). AFM measurements determined pore sizes of 1000.+ -.300 nm, consistent with SEM measurements. The pore depth of 180.+ -.60 nm was determined by the profile of the typical pore. The cross-sectional image of the film shows that the pores are not only distributed at the surface but also uniformly throughout the PEDOT: PSS film.
Example 3 electrical Properties of foam Structure PEDOT: PSS film
PEDOT: PSS film of the foam structure of this embodiment was prepared from example 1.
The electrical properties of the channels can greatly affect the performance of OECT. Therefore, it is necessary to study the electrical characteristics of the foam structure PEDOT: PSS film, including conductivity and volume capacitance.
As shown in FIG. 4, first, we studied the conductivity of the foam structure PEDOT: PSS film. As the pore content increases from 0 to 25% by volume, the conductivity of the film increases dramatically, increasing from 0.2 to 573.7S cm-1 by 3 orders of magnitude. In the formation of high density pores, the field of ionic liquids is used as templates, which may dissolve excess PSS. Dissolution of PSS results in exposure of more conductive PEDOT moieties, thus accounting for the improvement in conductivity. Further increases in pore content result in reduced conductivity, possibly due to the pores interrupting the conductive path of the PEDOT.
The volumetric capacitance of the channel also greatly determines the performance of the corresponding OECT. We estimated the volumetric capacitance of the foam structure PEDOT: PSS film by calculating the reversible storage capacity revealed by Cyclic Voltammetry (CV) curves. It can be seen from fig. 4a, 4b, 4c that the 15vol% pore content performs best compared to the other pore contents, with higher electrical and output properties.
Example 4 foam Structure PEDOT: doping kinetics of ions in PSS film
PEDOT: PSS film of the foam structure of this embodiment was prepared from example 1.
The test method is as follows: for photoelectrochemical measurements, the channel film was prepared on a transparent PET substrate. The coated PET film was then immersed in a cuvette containing PBS solution (0.1M). A positive bias was applied to the portable electrochemical analyzer (PalmSens 4) using an Ag/AgCl electrode immersed in the PBS solution as a counter electrode. During the bias voltage increase from 0 to 1V, the absorption spectrum of the coated PET was continuously recorded, using an ultraviolet-visible-near infrared spectrometer (UV-3600, shimadzu, japan). FIG. 5 is a spectroelectrochemical and doping kinetics comparison of the foam structure PEDOT: PSS with the dense PEDOT: PSS. . FIG. 6 is the kinetic absorption spectrum of the dense PEDOT: PSS film. A bias of 1.0V was applied at 20s and a kinetic absorption spectrum was obtained after 50 seconds.
As shown in FIG. 5 and FIG. 6, we next studied the doping of ions in PEDOT: PSS films of foam structures under bias using ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy. For measurement, we prepared a PEDOT: PSS film of foam structure on a partially metallized transparent PET substrate, and then immersed the substrate in a Phosphate Buffered Saline (PBS) electrolyte. For comparison, we first examined the spectroelectrochemical properties of the dense PEDOT: PSS film. As the bias voltage increases from 0 to 1.0V, the absorption peak intensity at about 600nm increases, while the broad absorption peak intensity in the 800-1100nm range decreases. The peak around 600nm is the neutral state (PEDOT) 0 ) While the absorption peak around 970nm is a Polarizer (PEDOT) + ) Is to be used in the absorption of (a),>the absorption at 1000nm is due to the bipolar (PEDOT) 2+ ) Is not limited to the absorption of (a). The above results indicate that PEDOT increases with increasing bias + The number of PEDOT0 increased, indicating a change from PEDOT under positive bias + To PEDOT 0 Is a transition of (2). Similar changes were also observed in the foam structured PEDOT PSS film, although the rate of change was faster than the dense PEDOT PSS film. For quantitative analysis, we plotted the dense and foam structure PEDOT-PSS film PEDOT under bias 0 Profile of peak absorption change. As the bias voltage increases from 0 to 0.2V, the absorption strength increases slightly. Further increasing the bias voltage from 0.2 to 0.8V, the absorption intensity increases dramatically. As the bias voltage increases from 0.8 to 1.0V, the absorption gradually reaches saturation. More interestingly, the absorption strength of the foam structure PEDOT: PSS film increased significantly faster than the dense PEDOT: PSS film. The increase in absorption intensity can be attributed to PEDOT + Is saturated by (A) and (B)The intensity indicates that neutralization has reached saturation. The faster strength increase observed in the foam structure PEDOT: PSS film suggests that the doping of ions in the film is more advantageous, probably due to the presence of the porous structure, increasing the interfacial area, facilitating the doping of ions. These results indicate that our foam structure PEDOT: PSS film is advantageous for ion doping in the corresponding OECTs channels, thus improving device performance.
To further investigate the kinetic differences between the dense and foam structure PEDOT: PSS films, we applied a sharply increasing bias to investigate the rate and mechanism of ion doping. At about 20 seconds we applied a positive bias of 1V to the film. The absorption spectrum of the dense PEDOT PSS film starts to drop slowly after biasing, and the whole drop process is not completed after 50 seconds. The whole process does not reach saturation until 300 seconds later. In contrast, the absorption spectrum of the foam structure film drops sharply and reaches saturation soon. The significant decrease in the fall time in the foam structured film suggests that the rate of cation implantation into the foam is faster, as is the transition from polarons to the neutral state PEDOT0, possibly due to the porous nature of the film. This rapid cation doping will result in a faster response time in the corresponding OECTs, as will be discussed later.
Example 5 output Properties of OECT based on foam Structure channel
OECT of the foam structure channels of this embodiment was prepared from example 1.
The test method is as follows: the output characteristics of OECT were measured on a semiconductor analyzer (B1500A, keysight). When the output curve is acquired, the gate voltage is scanned from 0 to 1V, and the drain voltage is set to 0 to 0.5V. When the transfer curve is collected, the drain voltage is kept at-0.3V, and the gate voltage is scanned within the range of-1 to 1V. For H 2 O 2 And glucose sensing test, wherein the drain voltage is kept at 0.3V, and the gate voltage is scanned within the range of-0.5-1V. H 2 O 2 The curve fitting formula is y=0.8478+0.00826x. The curve formula for the glucose test is y=0.10936+0.00856x. For photoelectrochemical measurements, the channel film was prepared on a transparent PET substrate. The coated PET film is then immersed in a liquid containingIn a cuvette of PBS solution (0.1M). A positive bias was applied to the portable electrochemical analyzer (PalmSens 4) using an Ag/AgCl electrode immersed in the PBS solution as a counter electrode. During the bias voltage increase from 0 to 1V, the absorption spectrum of the coated PET was continuously recorded, using an ultraviolet-visible-near infrared spectrometer (UV-3600, shimadzu, japan).
As shown in FIG. 7, we prepared high performance OECT using a foam structure PEDOT: PSS film as a channel layer. First, we deposit source and drain gold electrodes on PET film using mask-assisted ion sputtering. The length and width of the channels were controlled to 500 microns and 7 mm, respectively. Then, we coated the foam structure PEDOT: PSS film on the electrode-coated substrate by dropping a mixture of PEDOT: PSS and ionic liquid, and washed out the ionic liquid.
Next, we compared the output performance of OECT based on dense and foam structure PEDOT: PSS channels. As shown, the leakage current increases with increasing source-drain voltage, whether based on the dense or foam structure PEDOT: PSS channel OECT. Furthermore, as the gate voltage increases, the leakage current decreases, which is a typical feature of PEDOT: PSS-based OECT, which operates in depletion mode. These results indicate that at low gate voltages, the OECT is in an on state and at high gate voltages, the OECT is in an off state. When a forward gate voltage is applied, the hole carriers in PEDOT: PSS are annihilated by the introduced cations, resulting in OECT turning off. Although OECTs based on dense and foam structures PEDOT to PSS exhibit similar characteristics on the output curves, leakage currents of the channels based on foam structures PEDOT to PSS are generally greater (approximately 7 times) than OECTs based on dense PEDOT to PSS. This increase in leakage current may be due to the improved conductivity and volume capacitance of the foam structure PEDOT: PSS film, as discussed above.
We further compared the transmission curve and transduction conductance of the PEDOT: PSS channel based on dense and foam structures. As the gate voltage increases, the leakage current decreases, further confirming the depletion mode of operation. In both OECTs, the leakage current drops sharply near zero gate voltage. More importantly, OECT based on the foam structure PEDOT: PSS exhibited a higher transconductance (18 mS) of approximately 200 times that of OECT based on dense PEDOT: PSS. The improved transduction can be explained by improving the electrical properties of the foam structure PEDOT: PSS channel, as already discussed above. In addition, the presence of the porous structure increases the interfacial area between the electrolyte and the organic semiconductor channel, facilitating the ion doping/dedoping process. In addition to the high transconductance, shorter response times were observed for OECT based on the foam structure PEDOT: PSS channels. At a pulse voltage of 20mV, the rise and fall response times of OECT based on dense PEDOT: PSS were 1000 and 1200 milliseconds, respectively, while OECT based on foam structure PEDOT: PSS was shortened to 300 and 500 milliseconds, respectively. The response time of OECT based on foam structure PEDOT to PSS is only 30% of that of the dense PEDOT to PSS film, which shows that the ion doping/dedoping process of PEDOT to PSS channel is greatly accelerated and the speed is improved by about 3 times. This improvement in response time may be due to the porous structure, which makes ion doping and dedoping more efficient because of the significant increase in surface area.
The cyclic stability is another important parameter of OECT, especially in practical applications. By repeatedly applying a pulsed gate voltage, we tested the cycling performance of the OECT based on the foam structure PEDOT: PSS. OECT exhibits a highly stable performance during long operation (400 seconds). The leakage current variation in the first few cycles is very consistent with the latter few cycles, indicating that our OECT has a high degree of operational stability. Thus, our OECT may be used in the near future for practical applications.
Example 6 Flexible Properties of OECT based on foam Structure channels
The OECT based on foam structure channels of this implementation was prepared from example 1.
As shown in fig. 8, flexibility performance is another important parameter of OECT, especially for wearable sensing applications. OECTs need to work stably under various bending conditions when mounted on the human body, and their performance needs to remain stable after multiple bending cycles. In our case, OECT is fabricated on a flexible PET substrate, the channel layer being porous. All these features enable our OECT to work stably under bending conditions. We studied the flexibility of our OECT by measuring its output properties under bending conditions. The transmission curve remains stable at different bending angles and is similar to the transmission curve in the unbent condition, indicating that our OECT has very high stability in the bent condition. We then compare the transconductance of OECTs curved at different radii of curvature (r=10, 15, 30 mm). When OECT is changed from a flat state to a curved state with a radius of 30mm, the transconductance of OECT is slightly lowered and kept around 90% of the original value. In addition, the transconductance remains stable after 100 repeated bends in a bending state with a radius of 15mm, demonstrating that our OECT has a high degree of mechanical flexibility. Thus, our OECT may be applied in the wearable electronics field in the near future.
Example 7 pair H using OECT 2 O 2 And sensitive detection of glucose
OECT of the foam structure channels of this embodiment was prepared from example 1.
As shown in FIG. 9, we can sensitively detect many chemical species using OECT based on the foam structure PEDOT: PSS. As discussed previously, OECT has a high transconductance and a short response time, both of which are advantageous for sensitive detection of chemical species. Furthermore, the maximum transconductance of OECT is obtained substantially around zero gate voltage, which helps to reduce the power consumption and simplify the integration requirements. This zero gate characteristic may also improve the stability of the OECT sensor because many biological elements tend to degrade on the gate when high voltages are applied.
As a proof of concept, we detected hydrogen peroxide using OECT (H 2 O 2 ). During the detection process, H 2 O 2 Electrochemical oxidation reactions occur at the gate electrode, during which electrons generated during oxidation are transferred to the nearby gate electrode and protons enter the channel layer. The transfer of electrons results in a decrease in the potential near the gate, which in turn results in a further change in the drain current. By adding H at different concentrations 2 O 2 Solution in positive gridDifferent numbers of protons and electrons are generated under the drive of the polar voltage, resulting in different potential drops. Based on this principle, H can be quantitatively determined 2 O 2 Is a concentration of (3). As shown, our OECT has drain current versus different concentrations of H 2 O 2 The solution showed a clear response. Reduction of drain current on transmission curve (Δi D ) Is used to quantify H 2 O 2 Is a concentration of (3). ΔI D With H 2 O 2 The increase in concentration increases. When H is 2 O 2 At a concentration of 1nM, a low concentration of H was detected 2 O 2 ，ΔI D 9.4. Mu.A, when H 2 O 2 At a concentration of 10nM, ΔI D To 22.6 mua. Clearly, ΔI is in the concentration range of 1nM to 100. Mu.M D And H is 2 O 2 The logarithm of the concentration is linear. These results indicate that our OECT can be used for quantitative detection of H 2 O 2 。
Similarly, glucose concentration can also be measured using OECT based on the foam structure PEDOT: PSS channel. The gate electrode is modified to Glucose Oxidase (GO) x ) To identify glucose. ΔI D Increasing with increasing glucose concentration. Quantitatively, a broad concentration range from 1nM to 100. Mu.M can be detected, and good linear correlation is observed in this concentration range.
The invention is not limited to the specific technical scheme described in the above embodiments, and all technical schemes formed by adopting equivalent substitution are the protection scope of the invention.
Claims (5)
1. A preparation method of a high-performance organic electrochemical transistor based on a foam structure channel of a template sacrificial method is characterized by comprising the following steps of: the method comprises the following steps:
(1) The volume ratio of the [ EMIM ] [ PF6] (1-ethyl-3-methylimidazole hexafluorophosphate) solution to the solution is 1:3 water and ethanol were mixed to prepare 49 μl of a solution, wherein [ EMIM ] [ PF6] was 1.3wt.% in the aqueous alcohol solution, 2.5 μl of 0.5vol.% (volume fraction of PEDOT: PSS solution) of a gos silane coupling agent solution and 2.5 μl of a 90% strength aqueous solution of DBSA dodecylbenzenesulfonic acid were added, and 500 μl of a PEDOT: PSS (3, 4-ethylenedioxythiophene): poly (styrene sulfonate) solution (PEDOT: PSS was 1.5wt.% in deionized water) were mixed to prepare a film precursor having a pore content of 15 vol.%, and the mixture was stirred at 300rpm for 30 minutes;
(2) Preparation of organic electrochemical transistor OECT:
firstly, preparing a source electrode and a drain electrode gold electrode on a PET substrate by using a template mask sputtering method; sputtering was performed on an ion sputtering apparatus (SBC-12, KYKY); the channel length and width were controlled to 500 μm (L) and 7000 μm (d), respectively; the grid electrode is tested by adopting external Ag/AgCl.
Then, the mixture of PEDOT: PSS prepared in step (1) was dropped on the electrode-coated PET substrate, followed by thermal annealing, 15. Mu.L of the mixture was dropped on the substrate previously coated with the gold electrode, the dropped film was annealed at 50℃for 30 minutes, and then at 120℃for 30 minutes, and the resulting substrate was washed with a mixture of water and ethanol (volume ratio of 1:3) by immersing and washing in the mixture, and the resulting foam structure film had a thickness of 1. Mu.m.
2. A high performance organic electrochemical transistor of a foam structure channel prepared according to the method of claim 1.
3. The high performance organic electrochemical transistor application of a foam structure channel of claim 1, wherein: can be used in various flexible wearable fields.
4. The high performance organic electrochemical transistor application of a foam structure channel of claim 1, wherein: can be used for biological detection or health monitoring.
5. The high performance organic electrochemical transistor application of a foam structure channel of claim 1, wherein: can be used for H 2 O 2 And glucose detection.
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