KR102317490B1 - Organic field effect transistor device comprising hybrid channel layer capable of detecting active oxygen species and active oxygen species detection sensor comprising the same - Google Patents

Abstract

The present invention is a substrate; a gate electrode formed on the substrate; an insulating layer formed on the gate electrode; a source electrode formed on the insulating layer; a drain electrode formed on the insulating layer to be spaced apart from the source electrode; and a hybrid channel layer formed on the insulating layer and positioned between the source electrode and the drain electrode, wherein the hybrid channel layer includes a p-type conductive polymer, a phenolic compound, and a halloysite nanoclay. It relates to an active oxygen species detection sensor including an organic field effect transistor device, characterized in that part or all of the hydroxyl groups included in the phenolic compound are exposed to the outside. According to the present invention, it is possible to provide an organic field effect transistor device including a hybrid channel layer having excellent mass productivity because the production process is simple and mass production is possible at low cost without additional equipment. In addition, the reactive oxygen species detection sensor of the present invention including the organic field effect transistor device has an effect that can repeatedly and continuously measure even a low concentration of active oxygen species.

Description

Organic field effect transistor device including a hybrid channel layer capable of detecting reactive oxygen species, and reactive oxygen species detection sensor including the same THE SAME}

The present invention relates to an organic field effect transistor device including a hybrid channel layer capable of detecting reactive oxygen species, and more particularly, to an active oxygen species detection sensor and the reactive oxygen species detection sensor including the organic field effect transistor device. It relates to a reactive oxygen species detection device comprising a.

With the continuous extension of life expectancy, public interest in improving the quality of life is on the rise. Specifically, not only diseases and aging, but also exploration and technology development in various fields that affect the quality of life, from health and beauty, are expanding. In particular, with the development of biochemistry and life science, various compounds that affect individual health have been identified.

Recent research results confirmed that among various compounds, reactive oxygen species, in particular, have a significant effect on personal health, disease, and aging. Hydrogen peroxide (H ₂ O ₂ ), superoxide ions (O ₂ ⁻ ), reactive oxygen species including hydroxyl radicals (OH), etc. are known to have very high chemical reactivity because they exist in an unstable state.

When these reactive oxygen species are introduced into the human body in excess of the normal level, they not only damage cell membranes, but also cause structural changes in DNA, RNA, lipids, proteins, and the like in cells. In severe cases, it has been found that it can cause heart disease, such as diabetes, cancer, heart disease, stroke, arteriosclerosis, Alzheimer's disease, and Parkinson's, which can have a fatal effect on organs.

In order to effectively detect reactive oxygen species, the need for a portable sensor system is increasing, and up to now, reactive oxygen species have been mainly detected using fluorescence, chemiluminescence, electron spin resonance and electrochemical measurement techniques. However, these detection methods have some difficulties in miniaturization, which is an essential condition for commercialization as a portable sensor system. In addition, Korea Patent No. 10-1683700 discloses a sensor having a reactive oxygen species detection function, but the sensor uses a toxic substance (Te, etc.) for the detection of reactive oxygen species as well as an expensive fluorescent material. It has the disadvantage of having to include

On the other hand, Korean Patent Registration No. 10 relating to an organic field effect transistor device including a channel layer in which some or all of the hydroxyl groups of the flavonol-based compound developed by the present inventors are exposed to the outside and reacts with active oxygen species -2001766 has the effect of repeatedly and continuously detecting reactive oxygen species, but there was a problem in that it could not detect a lower concentration of reactive oxygen species.

Accordingly, as a result of continuous research, the present inventors developed an organic field effect transistor device including a hybrid channel layer that is simple in configuration and excellent in mass production while being able to detect a lower concentration of active oxygen species, and a reactive oxygen species detection sensor including the same did.

Korean Patent No. 10-1683700 Korean Patent Registration No. 10-2001766

The present invention has been devised to solve the above-described problems, and a first object of the present invention is to provide an organic field effect transistor including a hybrid channel layer having a simple configuration and excellent mass productivity.

In addition, it is a second object to provide a reactive oxygen species detection sensor capable of detecting even a low concentration of active oxygen species by including the organic field effect transistor.

As a means for solving the above problems, the present specification provides a substrate; a gate electrode formed on the substrate; an insulating layer formed on the gate electrode; a source electrode formed on the insulating layer; a drain electrode formed on the insulating layer to be spaced apart from the source electrode; and a hybrid channel layer formed on the insulating layer and positioned between the source electrode and the drain electrode, wherein the hybrid channel layer includes a p-type conductive polymer, a phenolic compound, and a halloysite nanoclay. It includes, and discloses an organic field effect transistor device, characterized in that some or all of the hydroxyl groups included in the phenolic compound are exposed to the outside.

Here, the phenol-based compound may include two or more hydroxyl groups.

Here, the phenol-based compound is an alkylphenol-based compound, a benzenediol-based compound, a benzenetriol-based compound, a phenol glycoside-based compound, and a polyphenol-based compound. , aminophenol-based compounds, cresol-based compounds, bisphenol-based compounds, and flavonol-based compounds may be any one or more phenol-based compounds selected from the group consisting of compounds.

Here, the phenol-based compound may be a compound including a catechol moiety.

Here, the phenol-based compound may be a compound including a resorcinol moiety.

Here, the compound containing the catechol moiety is a flavonol-based compound, quercetin, kaempherol, apigenin, luteolin, myricetin, Chrysin (5,7-dihydroxyflabvone), baicalein (5,6,7-trihydroxyflavone), scutellarein (5,6,7,4'-tetrahydroxyflavone), ugonine ( wogonin (5,7-dihydroxy-8-methoxyflavone)), 3-hydroxyflavone (3-Hydroxyflavone), Azaleatin, Fisetin, Galangin, Gossypetin, Kaempferide, Isorhamnetin, Morin, Pachypodol, Rhamnazin, Rhamnetin, Astragalin, Azalein, Hypero Side (Hyperoside), Isoquercitin (Isoquercitin), Kaempferitrin (Kaempferitrin), Myricitrin (Myricitrin), Quercitin (Quercitrin), Robinin (Robinin), Rutin (Rutin), Spiraeoside (Spiraeoside) , Xanthorhammin (Xanthorhamnin), and may be one comprising any one or more selected from the group comprising amurensin (Amurensin).

Here, the flavonol-based compound is azalein, hyperoside, isoquercitin, myricitrin, quercitrin, and rutin. , And it may be any one or more compounds selected from the group comprising xanthorhammin (Xanthorhamnin).

Here, the weight ratio of the p-type conductive polymer, the phenol-based compound 31, and the halloysite nanoclay in the hybrid channel layer may be 10:1:0.5 to 10:1:3.

Here, the p-type conductive polymer may be poly(3-hexylthiophene) (P3HT) or poly(3,4-ethylenedioxythiophene) (PEDOT).

On the other hand, the present specification is a substrate; a gate electrode formed on the substrate; an insulating layer formed on the gate electrode; a source electrode formed on the insulating layer; a drain electrode formed on the insulating layer to be spaced apart from the source electrode; and a hybrid channel layer formed on the insulating layer and positioned between the source electrode and the drain electrode, wherein the hybrid channel layer includes a p-type conductive polymer, a phenolic compound, and a halloysite nanoclay. It further discloses an active oxygen species detection sensor, characterized in that two or more organic field effect transistor devices to which some or all of the hydroxyl groups included in the phenolic compound are exposed to the outside are connected in parallel.

On the other hand, the present specification is a substrate; a gate electrode formed on the substrate; an insulating layer formed on the gate electrode; a source electrode formed on the insulating layer; a drain electrode formed on the insulating layer to be spaced apart from the source electrode; and a hybrid channel layer formed on the insulating layer and positioned between the source electrode and the drain electrode, wherein the hybrid channel layer includes a p-type conductive polymer, a phenolic compound, and a halloysite nanoclay. Including, the organic field effect transistor device to which some or all of the hydroxyl groups contained in the phenolic compound are exposed to the outside, characterized in that it comprises two or more reactive oxygen species detection sensors connected in parallel, active oxygen A species detection device is further disclosed.

The organic field effect transistor device including the hybrid channel layer of the present invention according to the above-described method has a simple production process and excellent mass productivity as it can be mass-produced at low cost without additional equipment.

In addition, the reactive oxygen species detection sensor of the present invention including the organic field effect transistor device has an effect that can repeatedly and continuously measure even a low concentration of active oxygen species.

Furthermore, the reactive oxygen species detection device of the present invention including the reactive oxygen species detection sensor can be miniaturized and portable, and has the effect of being convenient and versatile.

1 is a schematic diagram illustrating the structure of an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention.
2 illustrates a structure of an organic field effect transistor device including a hybrid channel layer and a mechanism for detecting reactive oxygen species according to an embodiment of the present invention.
3 is a detailed view of the structure of an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention.
4 is a graph showing the standardized optical density measurement result for the hybrid channel layer according to the weight ratio in the reactive oxygen species detection sensor including the organic field effect transistor device including the hybrid channel layer according to an embodiment of the present invention. will be.
FIG. 5 is a diagram illustrating 2D GIXD image measurement results for a hybrid channel layer according to a weight ratio in the reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention.
6 is a graph showing the 1D GIXD profile measurement result for the hybrid channel layer according to the weight ratio in the reactive oxygen species detection sensor including the organic field effect transistor device including the hybrid channel layer according to an embodiment of the present invention; it will be shown
7 is an output of an organic field effect transistor device including a hybrid channel layer according to a weight ratio in the reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention; and a graph showing the result of the transfer (transfer) characteristic.
_{8 is a graph showing the change in hole mobility (μ h} ) as a function of the weight ratio of the nanoclay in the hybrid channel layer on the organic field effect transistor device according to an embodiment of the present invention and the calculated in the hybrid layer as a function of the weight ratio of the nanoclay. It is a graph showing the content of P3HT.
9 is an active oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention and an organic field effect transistor device including a channel layer according to a comparative example of the present invention. It is a graph showing the output (output) and transfer (transfer) characteristic results of the transistor device in the reactive oxygen species detection sensor including.
10 is an active oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention and an organic field effect transistor device including a channel layer according to a comparative example of the present invention. It is a graph showing the change in drain current with time of the transistor element in the active oxygen species detection sensor including the graph.
11 is a transistor shown when in contact with a PBS stream containing a peroxide solution of 0 to 10 nM concentration in the reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention; It is a graph showing the change of drain current with time of the device.
12 is an organic field including a hybrid channel layer of a reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention and a channel layer according to a comparative example of the present invention; A scanning electron microscope (SEM) image of the channel layer of the reactive oxygen species detection sensor including the effect transistor device is shown.
13 is an organic field including a hybrid channel layer of a reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention and a channel layer according to a comparative example of the present invention; A scanning electron microscope (SEM) image of the channel layer of the reactive oxygen species detection sensor including the effect transistor device is shown.

The terms used in this application are only used to describe specific examples. Therefore, for example, a singular expression includes a plural expression unless the context clearly requires it to be singular. In addition, terms such as "comprises" or "comprises" used in the present application are used to clearly indicate that there is a feature, step, function, component, or a combination thereof described in the specification, and other features It should be noted that it is not intended to preliminarily exclude the existence of elements, steps, functions, components, or combinations thereof.

Meanwhile, unless otherwise defined, all terms used herein should be regarded as having the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs. Accordingly, unless explicitly defined herein, certain terms should not be construed in an unduly idealistic or formal sense.

1 is a schematic diagram illustrating the structure of an organic field effect transistor device 1 including a hybrid channel layer according to an embodiment of the present invention. Referring to FIG. 1, the structure of the organic field effect transistor device of the present invention will be described as follows.

The present specification includes a substrate 10; a gate electrode 41 formed on the substrate 10; an insulating layer 20 formed on the gate electrode 41; a source electrode 42 formed on the insulating layer 20; a drain electrode 43 formed on the insulating layer 20 to be spaced apart from the source electrode 42; and a hybrid channel layer 30 formed on the insulating layer 20 and positioned between the source electrode 42 and the drain electrode 43, wherein the hybrid channel layer 30 is a p-type ( p-type) comprising a conductive polymer, a phenolic compound (31) and a halloysite nanoclay (32), characterized in that some or all of the hydroxyl groups included in the phenolic compound (31) are exposed to the outside, An organic field effect transistor device is disclosed.

Hereinafter, each detailed component of the organic field effect transistor device will be described in detail. Each component may be described by way of example, and such description may be exaggerated or reduced in some cases.

<Substrate (10)>

Since the detailed components of the organic field effect transistor device are sequentially stacked on one surface of the substrate 10, the substrate 10 functions as an initial base for stacking. The substrate 10 of the present invention may or may not be transparent, and likewise may or may not be flexible.

As an example of the substrate 10 , a semiconductor-based substrate such as silicon, a glass substrate, a plastic substrate, or the like may be considered. In particular, in the case of a plastic substrate, it is possible to prepare a substrate having both flexibility and permeability. For example, polyethylene terephalate (PET), polyethylene naphthelate (PEN), polycarbonate (PC), polyimide (PI), etc. may be considered as the substrate 10 .

<Gate electrode 41>

The gate electrode 41 is formed on one surface of the substrate 10 . The gate electrode 41 is mainly formed of a conductive material. When a voltage is applied to the gate electrode 41 to form a magnetic field, the flow of electrons or holes is induced between the source electrode 42 and the drain electrode 43 spaced apart from the gate electrode 41 .

An example of a method of manufacturing the gate electrode 41 is as follows. The gate electrode 41 is formed by forming a conductive film on the substrate 10, by forming a conductive film and then patterning, or by covering the substrate 10 with a patterned mask and forming a conductive film. can The gate electrode 41 may be formed by a process such as, for example, thermal evaporation, E-beam evaporation, sputtering, micro contact printing, or nano imprinting. can be formed by

In addition, the following examples may be considered as a material constituting the gate electrode 41 . It is formed of a metal material such as aluminum (Al), chromium (Cr), molybdenum (Mo), copper (Cu), titanium (Ti), tantalum (Ta), or a conductive non-metal material such as indium-tin oxide ( ITO), fluorine doped tin oxide (FTO) and indium zinc oxide (IZO), aluminum doped zinc oxide (Al-doped zinc oxide, AZO), zinc oxide (ZnO) , Indium Zinc Tin Oxide (IZTO) or a mixture thereof may be formed.

<Insulation layer 20>

The insulating layer 20 is formed on the gate electrode 41 . The insulating layer 20 is a layer introduced to separate the gate electrode 41 from the source electrode 42 , the drain electrode 43 , and the channel layer 30 , which will be described later. However, the separation is only physically separated, and the magnetic field formed by the gate electrode 41 must be able to pass through the insulating layer 20 to affect the source electrode 41 and the drain electrode 43 . do. The insulating layer 20 is preferably formed to completely cover one surface of the gate electrode 41 so that the gate electrode 41 is not exposed to the outside.

The insulating layer 20 is formed of an insulating material by, for example, a spin coating method or a spraying method using a dispenser, followed by heat curing or ultraviolet-ray curing. curing) and the like.

In addition, the insulating layer 20 is a material such as methyl methacrylate, poly methyl methacrylate (PMMA), polyimide, polyvinyl alcohol (polyvinylalcohol), polystyrene (polystyrene), etc. , or an inorganic/organic hybrid insulating material such as aluminum oxide/polystyrene (Al ₂ O _{3 /PS).}

<Source electrode 42 and drain electrode 43>

The source electrode 42 and the drain electrode 43 are formed on the insulating layer 20 . Preferably, the source electrode 42 and the drain electrode 43 are spaced apart from each other by a predetermined distance. The source electrode 42 means an electrode that supplies electrons or holes, and the drain electrode 43 means an electrode that absorbs electrons or holes. When the channel layer 30 is a p-type conductive polymer, when a negative charge is applied to the gate electrode 41, the source electrode 42 provides holes and the drain electrode 43 absorbs the holes. do. Conversely, when the channel layer is an n-type semiconductor, when a (+) charge is applied to the gate electrode 41 , the source electrode 42 provides electrons and the drain electrode 43 absorbs electrons.

The source electrode 42 and the drain electrode 43 may be formed by thermal evaporation, E-beam evaporation, sputtering, micro contact printing, or nano imprinting. It may be formed by a process such as

As examples of the source electrode 42 and the drain electrode 43 , copper (Cu), nickel (Ni), platinum (Pt), ruthenium (Ru), rhodium (Rh), gold (Au), tungsten (W), cobalt (Co), palladium (Pd), titanium (Ti), tantalum (Ta), iron (Fe), molybdenum (Mo), hafnium (Hf), lanthanum (La), iridium (Ir) and silver (Ag) It may include one or more selected from the group consisting of.

In addition, the source electrode 42 and the drain electrode 43 may further include a conductive material. For example, when a material having flexibility due to the properties or nano dimensions of the material itself, such as carbon nanotubes, carbon nanowires, and silver nanowires, is further included in the source electrode 42 to the drain electrode 43, the electrode itself Not only can the conductivity of the material increase, but also the flexibility can be further increased.

<Hybrid Channel Layer 30>

The hybrid channel layer 30 is positioned between the source electrode 42 and the drain electrode 43 . The hybrid channel layer 30 is physically and electrically connected to the source electrode 42 , and is also physically and electrically connected to the drain electrode 43 . Electrons and holes emitted from the source electrode 42 move through the hybrid channel layer 30 and are absorbed by the drain electrode 43 , thereby causing a current to flow. The hybrid channel layer 30 is an essential component in the operation of the organic field effect transistor device. As the hybrid channel layer 30 reacts more sensitively to the magnetic field change of the gate electrode 41, the performance of the organic field effect transistor device increases.

When a voltage is applied to the gate electrode 41 , an inversion layer is formed in a portion of the hybrid channel layer 30 located between the source electrode 42 and the drain electrode 43 . The inversion layer refers to a layer that electrically connects the source electrode 42 and the drain electrode 43 . The increase in the thickness of the inversion layer means that the movement of electrons or holes between the source electrode 42 and the drain electrode 43 increases.

In particular, when the hybrid channel layer 30 is a p-type conductive polymer, holes move through the inversion layer as described above. In this case, the following two cases may be considered as a method of increasing the thickness of the inversion layer. The first is to position a relatively strong (-) charge on the gate electrode 41 . This causes a strong (-) charge to be induced in the bonding surface of the insulating layer 20 and the hybrid channel layer 30 of the insulating layer 20 , and as a result, the source electrode 42 and the drain electrode 43 . ) to increase the flow of holes between them.

The second is to position a strong (-) charge on the opposite side of the gate electrode 41 with respect to the hybrid channel layer 30 . Contrary to the former method, an additional (-) charge is formed on the surface exposed to the outside of the hybrid channel layer 30, and is located only on the junction surface of the insulating layer 20 and the hybrid channel layer 30. It is a method of widening the flow of holes. As a result, the thickness of the inversion layer between the source electrode 42 and the drain electrode 43 increases, thereby increasing the flow of holes.

2 illustrates a structure of an organic field effect transistor device including a hybrid channel layer and a mechanism for detecting reactive oxygen species according to an embodiment of the present invention. More specifically, FIG. 2a shows the reaction of a hydroxyl group (OH) with reactive oxygen species in the rutin molecule of the rutin-haloysite nanoclay complex (aggregate), and FIG. 2b is a hole formed by the oxygen anion generated as a result of the reaction. ) shows the generation and diffusion of charges, and FIG. 2c shows that when reactive oxygen species are removed from the PBS stream, oxygen anions combine with hydrogen cations to form hydroxyl groups (OH) again. In FIG. 2 , S, D, and G denote a source electrode 42 , a drain electrode 43 , and a gate electrode 41 , respectively.

In more detail, the lowermost layer in FIG. 2 means the gate electrode 41 , and the layer formed on the gate electrode 41 means the insulating layer 20 . A source electrode 42 and a drain electrode 43 are respectively formed on the insulating layer 20 , and a hybrid channel layer 30 is formed between the source electrode 42 and the drain electrode 43 . In other words, the source electrode 42 and the drain electrode 43 are spaced apart from each other and formed in the hybrid channel layer 30 .

A mechanism for detecting reactive oxygen species by the organic field effect transistor device of the present invention will be described with reference to FIG. 2 . Regardless of the presence or absence of reactive oxygen species, once a negative charge is applied to the gate electrode 41 , holes emitted from the source electrode 42 are absorbed by the drain electrode 43 . A constant current value is measured by the flow of the holes. At this time, when the surface exposed to the outside of the hybrid channel layer 30 and the active oxygen species come into contact, an acid-base between the hydroxyl group of the phenolic compound 31 included in the hybrid channel layer 30 and the active oxygen species The reaction takes place. As a result of the acid-base reaction, a conjugate acid such as hydrogen peroxide is generated, and the hydroxyl group of the phenolic compound 31 included in the hybrid channel layer 30 has a negative charge or a radical. (-) charges or radicals formed through the above-described process induce an additional flow of holes between the source electrode 42 and the drain electrode 43 as shown in FIG. 2 , and the electric field of the hybrid channel layer 30 . Increasing the effective charge increases the drain current signal.

Afterwards, when the peroxide corresponding to the active oxygen species is removed from the PBS stream, the oxygen anion of the rutin molecule corresponding to the phenolic compound 31 is combined with the hydrogen cation supplied on the PBS stream to form a hydroxyl group (OH) again, Accordingly, the drain current signal decreases. That is, the once deprotonated phenolic compound 31 may be protonated by again undergoing an acid-base reaction. When the hydroxyl group is recovered by the protonation, it is possible to detect additional reactive oxygen species. Therefore, if it is assumed that reactive oxygen species are dissolved in a protic solvent, it can be assumed that continuous detection of reactive oxygen species will be possible. In addition, even if the hydroxyl groups of the phenol-based compound 31 are all deprotonated and the detection of additional reactive oxygen species is stopped, it can be confirmed that it is easy to recover the detection ability by protonation again.

On the other hand, although the halloysite nanoclay molecule itself contains a hydroxyl group (OH), it does not cause a change in drain current in the organic field effect transistor device according to the present invention. The reason is due to the principle that the peroxide corresponding to the reactive oxygen species selectively reacts with the phenolic hydroxyl group. As such, the improved ability to detect active oxygen species in the organic field effect transistor device according to the present invention is a halloysite nanoclay (32) together with a p-type conductive polymer and a phenolic compound (31) in the hybrid channel layer (30). ) because the phenolic compound 31 for reacting with the active oxygen species is more present on the surface of the hybrid channel layer 30 as it is included.

Considering the above-described mechanism, it can be inferred that as the rate of deprotonation of the phenol-based compound 31 included in the hybrid channel layer 30 increases, the width at which additional holes are induced increases. Therefore, the organic field effect transistor device of the present invention can not only simply check the presence or absence of reactive oxygen species, but also measure the concentration of active oxygen species based on the measured current value. This point will be further described later.

Summarizing the above, since the phenolic compound 31 included in the hybrid channel layer 30 of the present invention reacts with the active oxygen species to be measured and takes on a negative charge, the hybrid channel layer 30 of the present invention. The silver preferably includes a p-type conductive polymer. Polythiophene-based polymers such as poly(3-hexylthiophene) (P3HT) and poly(3,4-ethylenedioxythiophene) (PEDOT) may be considered as the p-type conductive polymer.

Meanwhile, the hybrid channel layer of the present invention may include a p-type conductive polymer, a phenol-based compound, and a halloysite nanoclay. Here, the p-type conductive polymer is poly(3-hexylthiophene) (P3HT), the phenolic compound 31 is rutin, and the halosite nanoclay is Al ₂ Si ₂ O ₅ (OH ) ₄ ·H 2 O is more preferable. At this time, in the hybrid channel layer 30 of the present invention, the phenolic compound 31 and the halosite nanoclay 32 may be combined to form a complex or an aggregate.

In addition, in the hybrid channel layer 30, the weight ratio (P:R:N) of the p-type conductive polymer, the phenol-based compound 31, and the halloysite nanoclay 32 is 10: 1: 0.5 to 10: 1:3 is preferable. For example, when the weight ratio of the p-type conductive polymer, the phenolic compound 31, and the halloysite nanoclay 32 is lower than the weight ratio (P:R:N) of 10:1:0.5 of the halloysite nanoclay In the organic field effect transistor device according to the present invention, there is a problem in that the sensitivity or reactivity for detecting reactive oxygen species is reduced, and on the contrary, the p-type conductive polymer, the phenolic compound (31) and the halloysite nanoclay (32) ) of the phenolic compound partially or entirely exposed to the outside in the organic field effect transistor device according to the present invention when the weight ratio of the halloysite nanoclay is higher than the weight ratio (P: R: N) of 10: 1: 3 A problem in which the hydroxyl group is reduced may occur, resulting in a problem in which the sensitivity or reactivity for detecting reactive oxygen species is lowered. Specific details in this regard will be described later in the following Examples and Experimental Examples.

On the other hand, as a method for forming the hybrid channel layer 30 on the insulating layer 20, spin coating, spray coating, roll coating, dip coating, etc. ), ink-jet coating, etc. may be considered.

<Phenolic compound 31 included in hybrid channel layer 30>

In the phenolic compound 31 included in the hybrid channel layer 30 , some or all of the hydroxyl groups included in the phenolic compound 31 are exposed to the outside. The phenolic compound 31 exposed to the outside undergoes a chemical reaction with active oxygen species. Reactive oxygen specices (ROS) refer to oxygen species including radicals or anions. Reactive oxygen species have very high chemical reactivity and are pointed out as one of the main causes of body aging.

The active oxygen species and the phenol-based compound 31 may undergo an acid-base reaction or a radical reaction. The phenol anion formed as a result of the acid-base reaction and the phenol radical formed as a result of the radical reaction are both stabilized by the resonance structure. In particular, since negative charges or radicals may be delocalized throughout the benzene ring, the phenol-based compound 31 exhibits high reactivity with active oxygen species.

The phenolic compound 31 included in the hybrid channel layer 30 reacts with active oxygen to have a negative charge or a radical, so that as described above, the source electrode 42 and the drain electrode 43 ) widens the inversion layer between them. Therefore, when the phenolic compound 31 included in the organic field effect transistor device of the present invention reacts with active oxygen, a change appears in the value of the current flowing through the organic field effect transistor device.

In other words, in order for the phenol-based compound 31 to react with the active oxygen species, some or all of the hydroxyl groups included in the phenol-based compound 31 must be exposed to the outside. The fact that the hydroxyl group of the phenolic compound 31 is exposed to the outside necessarily means that the phenolic compound 31 is positioned on the opposite side to the gate electrode 41 with respect to the hybrid channel layer 30 . . In the above case, the reaction with the reactive oxygen species always results in a change in the current value, although there is a difference between the high and low.

Accordingly, the present specification considers the phenol-based compound 31 as a compound that reacts with the active oxygen species, but the above-mentioned concept is not limited to the phenol-based compound 31 simply. Any compound capable of reacting with reactive oxygen species to have a negative charge or radical may be included in the hybrid channel layer 30 to provide a similar effect to the case in which the phenol-based compound 31 is included.

As an example that can enjoy a similar effect, both organic acids and inorganic acids can be considered. More specifically, anil compounds and derivatives thereof, ascorbic acid and derivatives thereof, naphthol compounds and derivatives thereof, phenanthrenoid compounds, silicone compounds, and the like may be considered.

As an example of the phenol-based compound 31, an alkylphenol-based compound, a benzenediol-based compound, a benzenetriol-based compound, a phenol glycoside-based compound, a polyphenol )-based compounds, aminophenol-based compounds, cresol-based compounds, bisphenol-based compounds, and flavonol-based compounds may be considered.

In addition, the phenolic compound 31 including two or more hydroxyl groups is more preferable as the phenolic compound 31 included in the hybrid channel layer 30 of the present invention than simple phenol. This is because as the number of hydroxyl groups increases, the probability of reacting with reactive oxygen species increases. However, it is most preferable that two or more hydroxyl groups are positioned in Ortho to each other, and then preferably positioned in Meta to each other, and may not be preferably positioned in Para to each other.

A compound in which two hydroxyl groups substituted on the benzene ring are positioned at ortho sites with each other is called a catechol. The hydroxyl group of catechol is particularly highly reactive with reactive oxygen species. This is because the anion or radical obtained by reacting any one of the hydroxyl groups of catechol with the reactive oxygen species is very stable.

The catechol anion or radical is more stable than the anion or radical of phenol having only one hydroxyl group, and the reason can be found in the hydrogen bond in the molecule as follows. Anions or radicals obtained as a result of the reaction between active oxygen species and catechol are particularly stable due to the hydrogen bonding in the molecule in the form of a pentacyclic ring. Therefore, a reaction in which a catechol anion or radical is generated in chemical equilibrium is more favorable. Therefore, when a compound including a catechol moiety is included in the hybrid channel layer 30 of the present invention, a lower concentration of active oxygen species is also detected than when phenol is included in the hybrid channel layer 30 . This is possible.

In view of the above, the present specification describes a compound containing a catechol moiety, but this does not exclude compounds such as the examples below. For example, ortho-aminophenol-based compounds and derivatives thereof, ortho-phenylenediamine-based compounds and derivatives thereof may be considered as alternatives to the catechol.

A compound in which two hydroxyl groups substituted on the benzene ring are meta-located to each other is called resorcinol. Resorcinol is also an example of the phenolic compound 31 included in the hybrid channel layer 30 of the present invention. Resorcinol has excellent reactivity with reactive oxygen species due to a physical reason different from the catechol.

Anions or radicals produced by reacting reactive oxygen species with a hydroxyl group of resorcinol may be stabilized by other hydroxyl groups of resorcinol. This is because the electronegativity of oxygen included in the hydroxyl group is very high. Oxygen with high electronegativity stabilizes negative charges or radicals through an inducer effect. Therefore, when a compound containing a resorcinol moiety is included in the hybrid channel layer 30 of the present invention, a lower concentration of active oxygen species than when phenol is contained in the hybrid channel layer 30 is also detection is possible.

In view of the above, the present specification describes a compound containing a resorcinol moiety, but this does not exclude compounds such as the examples below. For example, meta-aminophenol-based compounds and derivatives thereof, meta-phenylenediamine-based compounds and derivatives thereof, and the like can be considered as alternatives to resorcinol.

A compound in which two hydroxyl groups substituted on the benzene ring are located at the para site is called a hydroquinone. Hydroquinone has a pKa value similar to or higher than that of phenol, unlike catechol or resorcinol. This is because the anions or radicals produced by reacting reactive oxygen species with a hydroxyl group of resorcinol may be destabilized by other hydroxyl groups. The specific destabilization pattern can be inferred through the resonance structure.

However, it is preferable to view hydroquinone as a type of the phenolic compound 31 included in the hybrid channel layer 30 of the present invention in that both hydroxyl groups have room for reactive oxygen species reaction. By including hydroquinone, an effect similar to that of including phenol can be enjoyed.

In view of the above, the present specification describes a compound containing a hydroquinone moiety, but this does not exclude compounds such as the examples below. For example, a para-aminophenol (p-aminophenol)-based compound and its derivatives, a para-phenylenediamine-based compound and its derivatives, and the like can be considered as an alternative to the hydroquinone.

In addition, as described above, the phenol-based compound 31 may be included in the hybrid channel layer 30 of the present invention. The following are flavonol-based compounds as an example of the phenol-based compound (31). Flavonol-based compounds often contain a catechol moiety and a resorcinol moiety in one molecule at the same time, and they can be prepared at a relatively low cost, so they are suitable as an example of the phenol-based compounds of the present invention.

As a flavonol-based compound, quercetin, kaempherol, apigenin, luteolin, myricetin, chrysin (chrysin(5,7-dihydroxyflabvone)), baicalin (baicalein (5,6,7-trihydroxyflavone)), scutellarein (5,6,7,4'-tetrahydroxyflavone)), wogonin (5,7-dihydroxy-8-methoxyflavone)), 3 -Hydroxyflavone (3-Hydroxyflavone), Azaleatin (Fisetin), Galangin (Galangin), Gossypetin (Gossypetin), Kempferide (Kaempferide), Isorhamnetin (Isorhamnetin), Morin ( Morin), patch podol (Pachypodol), ramnazin (Rhamnazin), and rhamnetin (Rhamnetin) is included in the channel layer 30 of the present invention, reactive oxygen species can be detected.

In particular, among the flavonol compounds, quercetin, luteolin, myricetin, baicalein (5,6,7-trihydroxyflavone), scutellarein (5,6,7) , 4'-tetrahydroxyflavone)), azeleatin, fisetin, gossypetin, and rhamnetin. increased sensitivity to the detection of species. This is because the above-described flavonol-based compounds contain all catechol moieties.

Flavonol glycoside, a type of flavonol-based compound, refers to a compound in which a flavonol-based compound and a sugar are combined. Since the saccharides contained in the flavonol glycoside compound contain a large amount of hydroxyl groups, it is generally known that the flavonol glycoside compound is well agglomerated.

In the present invention, in order to detect the reactive oxygen species to be measured, acid-base reaction with the reactive oxygen species and the like must be carried out, so there is a limiting condition that a site that reacts with the reactive oxygen species must be exposed to the outside. The flavonol glycoside-based compound is not completely dissolved in the hybrid channel layer 30, and it is possible to secure a certain thickness through self-aggregation. Therefore, it can be said that a flavonol glycoside-based compound, which is easily exposed to reactive oxygen species, is a more preferable option as a molecule for detecting reactive oxygen species of the present invention.

As an example of a flavonol glycoside-based compound, the hybrid channel layer 30 of the present invention is aztragalin, azalein, hyperoside, isoquercitin, camperitin. (Kaempferitrin), Myricitrin, Quercitrin, Robinin, Rutin, Spiraeoside, Xanthorhamnin, and Amurensin. It may include one or more compounds selected from the group comprising.

In particular, Azalein, Hyperoside, Isoquercitin, Myricitrin, Quercitrin including a catechol moiety among the flavonol glycoside compounds ), rutin, and Xanthorhamnin, most preferably comprising at least one compound selected from the group consisting of. On the other hand, in the case of rutin, it is possible to extract from a variety of grains, and there is an additional advantage that the production cost can be significantly lowered.

<Halloysite nanoclay 32 included in hybrid channel layer 30>

The halloysite nanoclay 32 included in the hybrid channel layer 30 may form an aggregate together with the phenolic compound 31 in the hybrid channel layer 30 .

Here, the nanoclay is characterized in that it is composed of a combination of a silica tetrahedral sheet and an alumina octahedral sheet. According to the composition ratio of the silica tetrahedron and the alumina octahedron, various structures of the nanoclay are possible. For example, the nanoclay preferably forms a structure such as mica, vermiculite, chlorite, montmorillonite (MMT), nontronite, saponite, hectorite, but is not limited thereto.

In an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention, the hybrid channel layer is formed of a p-type conductive polymer, a phenolic compound 31 and a halosite nanoclay 32 . wherein the p-type conductive polymer is poly(3-hexylthiophene) (P3HT), the phenolic compound 31 is rutin, and the halosite nanoclay is Al ₂ Si ₂ It is preferably O ₅ (OH) _{4 .H2O.} In this case, in the hybrid channel layer 30 of the present invention, the phenolic compound 31 and the halloysite nanoclay 32 may be combined to form an aggregate. By forming such agglomerates in the hybrid channel layer 30, a part or all of the hydroxyl groups contained in the phenol-based compound 31 exposed to the outside may exhibit an effect of increasing, and accordingly, when in contact with active oxygen species The ratio of the phenol-based compound 31 that undergoes a chemical reaction with the active oxygen species may be increased.

That is, in the hybrid channel layer 30 of the present invention, the halloysite nanoclay 32 induces a more even distribution of the phenolic compound 31, for example, in the hybrid channel layer 30 of rutin, and hydroxyl groups ( OH) by exposing some or all of it to the outside, it is possible to improve the performance of the organic field effect transistor device including the hybrid channel layer of the present invention and the ability of the reactive oxygen species detection sensor.

In the organic field effect transistor device including the hybrid channel layer of the present invention, the halloysite nanoclay included in the hybrid channel layer 30 refers to a halloysite-based material having a nano-particle size, and the phenolic compound 31 and It is sufficient if it can form a complex|complex or aggregate.

Furthermore, the halloysite nanoclay 32 included in the hybrid channel layer 30 of the present invention is (Al _2-x Mg _x )(Si ₄ )O ₁₀ (OH) ₂ M ⁿ⁺ _x/n * mH ₂ O) (provided that the chemical formula of 0 ≤ x < 2, m > 0, n > 0) is satisfied, and a complex or aggregate can be formed with the phenolic compound 31 included in the hybrid channel layer 30 of the present invention. It is preferable to have

For example, the halloysite nanoclay included in the hybrid channel layer 30 of the present invention _{is preferably Al 2} Si ₂ O ₅ (OH) ₄ ·H 2 O, but is not limited thereto.

<Reactive oxygen species detection sensor and detection device thereof of the present invention>

The specification further describes a substrate 10; a gate electrode 41 formed on the substrate 10; an insulating layer 20 formed on the gate electrode 41; a source electrode 42 formed on the insulating layer 20; a drain electrode 43 formed on the insulating layer 20 to be spaced apart from the source electrode 42; and a hybrid channel layer 30 formed on the insulating layer 20 and positioned between the source electrode 42 and the drain electrode 43, wherein the hybrid channel layer 30 is a p-type ( p-type) an organic field effect transistor device containing a conductive polymer, a phenolic compound 31, and a halloysite nanoclay 32, wherein some or all of the hydroxyl groups included in the phenolic compound 31 are exposed to the outside Discloses two or more reactive oxygen species detection sensors connected in parallel.

Examples of the reactive oxygen species include O ^- , O ₂ ^- , O ₃ ^- , HO ^- , HO ₂ ^- , HO ₃ ^- , HO ₄ ^- , O ₂ ^2- , OH radicals, OH ₂ radicals, and the like. In order to react with the phenol-based compound 31 contained in the hybrid channel layer 30 of the present invention, it is sufficient to have a radical or an anion.

In addition, the organic field effect transistor device of the present invention is not capable of detecting only reactive oxygen species. When reviewed based on the above-described mechanism, it can be seen that the phenolic compound 31 included in the hybrid channel layer 30 of the present invention is not deprotonated only by active oxygen species. All general Lewis bases can be detected by the organic field effect transistor device of the present invention. This is because, if it is a Lewis base, it is obvious that an acid-base reaction with the phenolic compound (31) will proceed. Therefore, it can be seen that the organic field effect transistor device of the present invention is not limited by what the measurement target is.

The organic field effect transistor device of the present invention can individually detect the above-mentioned reactive oxygen species and the like. In addition, by connecting a plurality of the organic field effect transistor device, it is possible to increase the accuracy of detecting reactive oxygen species. In particular, by connecting a plurality of organic field effect transistor devices in parallel, the result of measuring the concentration of active oxygen species can be collected at once.

On the other hand, the reactive oxygen species detection sensor according to the present invention is characterized in that it has flexibility. Therefore, the reactive oxygen species detection sensor does not necessarily have to be installed on a flat surface, and has an additional advantage that it can be installed on a curved surface. In addition, considering the operation and flexibility of the reactive oxygen species detection sensor, even when the curvature of the reactive oxygen species detection sensor changes due to a physical external force, it can be inferred that there will be no hindrance to its function.

In addition, the reactive oxygen species detection sensor of the present invention can be produced in a size smaller than the palm of an adult. Since the size of the reactive oxygen species detection sensor is dependent on the size of the organic field effect transistor device of the present invention, it is possible to actually integrate it into a smaller size.

In addition, the present specification discloses a reactive oxygen species detection device including the reactive oxygen species detection sensor. More specifically, the present specification includes a substrate 10; a gate electrode 41 formed on the substrate 10; an insulating layer 20 formed on the gate electrode 41; a source electrode 42 formed on the insulating layer 20; a drain electrode 43 formed on the insulating layer 20 to be spaced apart from the source electrode 42; and a hybrid channel layer 30 formed on the insulating layer 20 and positioned between the source electrode 42 and the drain electrode 43, wherein the hybrid channel layer 30 is a p-type ( p-type) an organic field effect transistor device containing a conductive polymer, a phenolic compound 31, and a halloysite nanoclay 32, wherein some or all of the hydroxyl groups included in the phenolic compound 31 are exposed to the outside It further discloses a reactive oxygen species detection device, characterized in that it includes two or more reactive oxygen species detection sensors connected in parallel.

Considering the size of the reactive oxygen species detection sensor of the present invention and the fact that the reactive oxygen species detection device of the present invention has the reactive oxygen species detection sensor as an essential component, it is possible to miniaturize and carry the reactive oxygen species detection apparatus of the present invention. can be inferred

In addition, as described above, the reactive oxygen species detection apparatus of the present invention may be used not only for the detection of reactive oxygen species, but also for the detection of other Lewis bases. This is a fact inferred from the operation mode of the organic field effect transistor device of the present invention.

In addition, the reactive oxygen species detection apparatus of the present invention can be used for various purposes. For example, it can be used for medical, home, and industrial purposes. Specifically, it is possible to utilize the reactive oxygen species detection device to measure the concentration of active oxygen species in the blood for medical purposes. In a similar context, it is possible to utilize the reactive oxygen species detection device of the present invention to monitor the concentration of reactive oxygen species in the sterilization solution.

Hereinafter, with reference to the accompanying drawings and embodiments will be described in more detail with respect to what the present specification claims. However, the drawings and examples presented in this specification may be modified in various ways by those skilled in the art to have various forms, and the description of the present specification is not intended to limit the present invention to a specific disclosed form. It should be considered to include all equivalents or substitutes included in the spirit and scope of the present invention. In addition, the accompanying drawings are presented to help those of ordinary skill in the art to more accurately understand the present invention, and may be exaggerated or reduced than in reality.

{Examples and Experimental Examples}

Preparation of materials and solutions

Halloysite nanoclay (Al ₂ Si ₂ O ₅ (OH) ₄ H2O, hereinafter referred to as 'nanoclay'), potassium superoxide (KO ₂ ), sodium pgosphate dibasic, Na ₂ HPO ₄ ), anhydrous dimethyl sulfoxide (DMSO) and sodium phosphate monobasic (NaH ₂ PO ₄ ) were purchased from Sigma Aldrich, USA. Rutin hydrate was supplied by Tokyo Chemical Industry Co., Ltd. P3HT (weight average molecular weight = 70 kDa, polydispersity index = 1.7, regioregularity > 97 %) and polymethyl methacrylate (PMMA, weight average molecular weight = 120 kDa, polydispersity index = 2.2) were obtained from Rieke Metals, USA and Sigma-Aldrich, USA. did. N-butyl acetate was used as a solvent for the preparation of a pure PMMA solution (concentration = 80 mg/ml).

Binary and ternary mixed solutions containing P3HT, rutin and halloysite nanoclay were prepared at a solid concentration of 18 mg/ml in toluene. The weight ratios of P3HT:rutin:nanoclay (P:R:N) were P:R:N = 10:1:0.5, 10:1:1, 10:1:2 and 10:1:3. All solutions were continuously stirred at 60 °C for 24 h before coating.

Na ₂ HPO ₄ and NaH ₂ PO ₄ were dissolved in deionized water (phosphate buffer solutions, PBS, 5mM, pH7.4) was prepared. _{Dissolving KO 2} (10 mg) in DMSO (anhydrous, 1.41 ml) and sonicating for at least 5 minutes at room temperature _{to prepare a superoxide (O 2} ^- ) solution (100 mM) corresponding to reactive oxygen species, and this It was injected into 5 mM PBS solution in a perfusion system. The concentration of peroxide corresponding to the reactive oxygen species in the PBS solution was controlled by finely adjusting the injection amount.

Detection and measurement instruments and methods

A UV / VIS / NIR spectrometer (Lambda 750, Perkin Elmer) was used to measure the light absorption spectrum, and the thickness of each layer of the organic field effect transistor device was confirmed with a surface profilometer (Dektak XT, Bruker). . Hybrid channels in organic field-effect transistor devices using a field-emission scanning electron microscope (FE-SEM, SU 8230, Hitachi) and a high-resolution optical microscope (SV-55, SOMETECH) The morphology of the layers was examined. Element mapping was performed using an energy dispersive spectrometer (EDS, SU-8230, Hitachi) attached to an FE-SEM instrument.

The crystalline nanostructure of the hybrid channel layer in the organic field effect transistor device is a synchrotron radiation grazing incidence X-ray diffraction system (GIXD, wavelength = 1.212969 Å, 3C, SAXS-I beamline, Pohang). Accelerator Laboratories). The organic field effect transistor characteristics were measured using a semiconductor parameter analyzer (4200 SCS, 2636B, Keithley). Real-time detection of reactive oxygen species perfusion equipped with a specialized liquid-flow sample holder and peristaltic pump system (CP-100 Drive, DP-100 Head, Dongseo Science Co. Ltd.) This was performed using a home-built perfusion system. The PBS stream containing the peroxide solution corresponding to the reactive oxygen species was controlled by adjusting the flow rate (about 0.5 ml/min).

Example 1. Active oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer having a weight ratio of P3HT: rutin: nanoclay (P: R: N) of 10: 1: 0.5

Typical photolithography processes to obtain patterned ITO electrodes (1 mm x 30 mm) from indium-tin oxide (ITO) coated glass (sheet resistance = ~ 10 Ω/cm ^{2 )} This was applied. Next, using isopropyl alcohol (IPA) and acetone (acetone) to clean the patterned ITO-coated glass inside the ultrasonic cleaner (CPX5800H-E, Emerson). The wet-cleaned ITO-coated glass was subjected to UV-ozone (UVO) treatment at a UV output of ^{28 mW/cm 2} for about 20 minutes using a UVO system (Altech, Korea) to remove impurities. Here, the glass corresponds to the substrate 10 in the organic field effect transistor device of the present invention, and the ITO corresponds to the gate electrode 41 in the organic field effect transistor device of the present invention. The PMMA solution was spin coated on the substrate 10 and the gate electrode 41 formed on the substrate 10, followed by thermal annealing at 120° C. for 30 minutes to form the insulating layer 20. . Here, the PMMA corresponds to the insulating layer 20 in the organic field effect transistor device of the present invention, and the thickness of the insulating layer 20 was uniform at about 450 nm. After loading into the thermal evaporation chamber, silver (Ag, thickness = 60 nm) corresponding to the source electrode 42 and the drain electrode 43 is deposited on the insulating layer 20 using a metal shadow mask in a thermal deposition process. was carried out for deposition. Each of the source electrode 42 and the drain electrode 43 had a thickness of 60 nm. Next, a ternary mixed solution containing P3HT, rutin, and halloysite nanoclay (Al ₂ Si ₂ O ₅ (OH) ₄ .H2O) in a weight ratio of 10: 1: 0.5 was continuously added at 60 °C for 24 hours. After stirring, a spin coating process was performed on the insulating layer 20 , the source electrode 42 , and the drain electrode 43 to form the hybrid channel layer 30 . At this time, the size of the hybrid channel layer 30 was 70 μm (length)×3 mm (width). Thereafter, the organic field effect transistor device including the hybrid channel layer according to an embodiment of the present invention by soft baking at 70 ° C. for 15 minutes to remove the residual solvent and water and improve the reactive oxygen species detection ability. A reactive oxygen species detection sensor (hereinafter referred to as 'Example 1') was obtained.

Example 2. Active oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer in which the weight ratio of P3HT: rutin: nanoclay (P: R: N) is 10: 1: 1.

In the reactive oxygen species detection sensor according to Example 1, except that the weight ratio of P3HT: rutin: nanoclay constituting the hybrid channel layer 30 was 10: 1: 1, prepared in the same manner as in Example 1, A reactive oxygen species detection sensor (hereinafter referred to as 'Example 2') including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention was obtained.

Example 3. Active oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer having a weight ratio of P3HT: rutin: nanoclay (P: R: N) of 10: 1: 2

In the reactive oxygen species detection sensor according to Example 1, except that the weight ratio of P3HT: rutin: nanoclay constituting the hybrid channel layer 30 was 10: 1: 2, prepared in the same manner as in Example 1, A reactive oxygen species detection sensor (hereinafter referred to as 'Example 3') including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention was obtained.

Example 4. Active oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer having a weight ratio of P3HT: rutin: nanoclay (P: R: N) of 10: 1: 3

In the reactive oxygen species detection sensor according to Example 1, except that the weight ratio of P3HT: rutin: nanoclay constituting the hybrid channel layer 30 was 10: 1: 3, prepared in the same manner as in Example 1, A reactive oxygen species detection sensor (hereinafter referred to as 'Example 4') including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention was obtained.

Comparative Example 1. Active oxygen species detection sensor including an organic field effect transistor device including a channel layer having a weight ratio of P3HT: rutin: nanoclay (P: R: N) 10: 1: 0

In the reactive oxygen species detection sensor according to Example 1, except that the weight ratio of P3HT: rutin: nanoclay constituting the hybrid channel layer 30 was 10: 1: 0, prepared in the same manner as in Example 1, An active oxygen species detection sensor (hereinafter referred to as 'Comparative Example 1') including an organic field effect transistor device including a channel layer according to a comparative example of the present invention was obtained.

Experimental Example 1. Standardized Optical Density Measurement and Results for Hybrid Channel Layer

A PBS stream containing a peroxide solution corresponding to reactive oxygen species was brought into contact with the reactive oxygen species detection sensor according to Examples 1 to 4 and the reactive oxygen species detection sensor according to Comparative Example 1.

3 is a detailed view of the structure of an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention. In FIG. 3, S, D, and G denote a source electrode, a drain electrode, and a gate electrode, respectively. In addition, the lower right of FIG. 3 is a photograph of an actual shape of an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention. Referring to FIG. 3 , electric field-induced charges (holes, holes) exist in the lower region of the hybrid channel layer 30 close to the insulating layer 20 and are generated by reaction with a peroxide solution corresponding to active oxygen species. It can be estimated that the charged charges diffusely migrate from the upper region of the hybrid channel layer 30 .

4 is a graph showing the standardized optical density measurement result for the hybrid channel layer according to the weight ratio in the reactive oxygen species detection sensor including the organic field effect transistor device including the hybrid channel layer according to an embodiment of the present invention. will be. More specifically, FIG. 4a is a graph showing individual light absorption spectrum measurement results for a channel layer coated with rutin, nanoclay, and P3HT on quartz, respectively, and FIG. 4b is a standardized optics for a hybrid channel layer according to weight ratio. The density (optical density, OD) spectrum measurement result is shown in a graph. Referring to FIG. 4A , it can be seen that the channel layer coated with rutin and the channel layer coated with nanoclay have relatively rough roughness. In addition, referring to FIG. 4B , it can be confirmed that the optical density at about 605 nm was measured to gradually increase according to the weight ratio of the nanoclay in the hybrid channel layer 30 as a result of the contact test of the reactive oxygen species. This result means that the relative crystallinity of the P3HT domain is increased due to the presence of nanoclay, which is due to the tendency of the diffraction peak corresponding to the (100) direction to gradually increase as shown in FIGS. 5 and 6 . It can be seen that this is supported by

FIG. 5 is a diagram illustrating 2D GIXD image measurement results for a hybrid channel layer according to a weight ratio in the reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention. In FIG. 5 , the 'OOP' direction (out-of plane direction) means top, and the 'IP' direction (in plane direction) means bottom.

6 is a graph showing the 1D GIXD profile measurement result for the hybrid channel layer according to the weight ratio in the reactive oxygen species detection sensor including the organic field effect transistor device including the hybrid channel layer according to an embodiment of the present invention; it will be shown In FIG. 6 , the 'OOP' direction (out-of plane direction) means top, and the 'IP' direction (in plane direction) means bottom. More specifically, FIGS. 6A and 6B are graphs showing the 1D GIXD profile measurement results for the hybrid channel layer according to the weight ratio, and FIG. 6C is the I _{OOP for the P3HT domain as a function of the weight ratio in the hybrid channel layer.} Changes in (100) and I _IP (100) peaks are graphically shown. 6a and 6b, (100), (200), and (300) peaks represent the diffraction peaks of the P3HT domain, and the 'N' peak represents the diffraction peaks of the nanoclay domain. 5 and 6, from the diffraction peak corresponding to the (100) direction showing a tendency to gradually increase, it can be confirmed that the relative crystallinity of the P3HT domain is increased due to the presence of nanoclay.

Experimental Example 2. Measurement and results of organic field effect transistor device characteristics including hybrid channel layer according to weight ratio in an inert atmosphere

The characteristics of the basic transistor elements of the reactive oxygen species detection sensor according to Examples 1 to 4 and the reactive oxygen species detection sensor according to Comparative Example 1 were measured under dark conditions that are inert atmospheres. These measurements were performed in an inert atmosphere by mounting the device in a sample holder filled with argon (Ar), and the measurement results are shown in Table 1 below. The measured values in Table 1 below are the values measured in the transmission curve when the _{drain voltage (V D ) = -30 V.}

7 is an output of an organic field effect transistor device including a hybrid channel layer according to a weight ratio in the reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention; and a graph showing the result of the transfer (transfer) characteristic. More specifically, FIG. 7A is a graph showing the output characteristic result of an organic field effect transistor device including a hybrid channel layer according to a weight ratio, and FIG. 7B is an organic field effect including a hybrid channel layer according to a weight ratio. A graph showing the results of the transfer characteristics of the transistor device. Referring to FIG. 7 , it can be seen that both the reactive oxygen species detection sensor according to Examples 1 to 4 and the reactive oxygen species detection sensor according to Comparative Example 1 exhibit typical p-type transistor behavior in a dark condition in an inert atmosphere. Further, the ratio by weight of nanoclay 10: 1, but the drain current (I _D) on the same gate voltage (V _G) and the drain voltage (V _D) at the output curve with the increase to 2 is gradually increased, the ratio by weight of nanoclay The drain current ( _ID ) decreased at the _{same gate voltage (V G} ) and drain voltage (V _D ) in the output curve as it increased to 10:1:3.

Similarly, the same trend was also observed in the transmission curve. As the weight ratio of the nanoclay increased to 10: 1: 2, the drain current (I _{D ) at the same drain voltage (V D} ) in the transmission curve gradually increased, but the As the weight ratio increased to 10: 1: 3, the drain current (I _D ) decreased at the _{same drain voltage (V D ) in the transmission curve.} These results in both output and transfer curves reflect that the highest drain current can be achieved in organic field-effect transistor devices comprising a hybrid channel layer with a weight ratio of P3HT:rutin:nanoclay of 10:1:2. In addition, the on/off ratio was significantly improved to ^{1.07 x 10 6} in the organic field effect transistor device including the hybrid channel layer in which the weight ratio of P3HT:rutin:nanoclay was 10:1:2. Since the amount of P3HT in the hybrid channel layer was relatively decreased by the presence of nanoclay, the on/off ratio was also expected to decrease, but the hole mobility was P3HT:rutin: Even when the weight ratio of the nanoclay was 10 : 1 : 2, μh = 2.2 x 10 ^-3 cm ² /Vs was well maintained.

_{8 is a graph showing the change in hole mobility (μ h} ) as a function of the weight ratio of the nanoclay in the hybrid channel layer on the organic field effect transistor device according to an embodiment of the present invention and the calculated in the hybrid layer as a function of the weight ratio of the nanoclay. It is a graph showing the content of P3HT. Referring to FIG. 8 , as a result of the experiment on the crystallinity of the polymer thin film, when the weight ratio of P3HT : rutin : nanoclay in the hybrid channel layer is 10 : 1 : 2, even though the content of P3HT is decreased in the hybrid channel layer, the hole It can be seen that the hole mobility is well maintained at ^{μh = 2.2 x 10 -3} cm ^{2 /Vs.} The well-maintained hole mobility can be explained by the increased edge-on chain stacking out-of-plane (OOP) with the weight ratio of the nanoclay. 6c is a graph showing the experimental results of the polymer thin film according to the weight ratio of P3HT:rutin:nanoclay in the hybrid channel layer. _{Referring to FIG. 6c , it can be seen that the I OOP} (100) value increases as the content of nanoclay increases in the hybrid channel layer of the present invention. As the nanoclay was added in the hybrid channel layer, the content of P3HT was relatively decreased (I _IP (100) value decreased), so it was expected that the performance of the organic field effect transistor device according to an embodiment of the present invention would decrease. As a result, it can be seen that the performance of the organic field effect transistor device is well maintained as the hole mobility is well maintained. It is confirmed that this is because the crystallinity of the hybrid channel layer is improved by the nanoclay added to the hybrid channel layer of the present invention from the tendency of the _{I OOP (100) value to increase.} Therefore, it is possible to compensate for the negative effect on transistor device performance due to the relatively reduced amount of P3HT in the hybrid channel layer from the nanoclay gradually added to the hybrid channel layer of the present invention.

Experimental Example 3. Measurement and results of organic field effect transistor device characteristics including hybrid channel layer according to weight ratio in pure PBS solution

A pure PBS solution without a peroxide solution corresponding to reactive oxygen species was brought into contact with the reactive oxygen species detection sensor according to Example 3 and the reactive oxygen species detection sensor according to Comparative Example 1, and the characteristics of the basic transistor device were measured. This measurement was performed on a pure PBS solution by mounting a reactive oxygen species detection sensor inside a liquid-flow sample holder in a perfusion system, and the measurement results are shown in Table 2 below. The measured values in Table 2 below are the values measured in the transmission curve when the _{drain voltage (V D ) = -20 V.}

9 is an active oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention and an organic field effect transistor device including a channel layer according to a comparative example of the present invention. It is a graph showing the output (output) and transfer (transfer) characteristic results of the transistor device in the reactive oxygen species detection sensor including. More specifically, Figure 9a is a graph showing the output (output) characteristic results of the transistor device in the reactive oxygen species detection sensor according to Example 3 and the reactive oxygen species detection sensor according to Comparative Example 1, Figure 9b is in Example The results of the transfer characteristics of the transistor device in the reactive oxygen species detection sensor according to 3 and the reactive oxygen species detection sensor according to Comparative Example 1 are graphed. 9, both the reactive oxygen species detection sensor according to Example 3 and the reactive oxygen species detection sensor according to Comparative Example 1 show excellent output characteristics compared to the performance in the inert atmosphere of Experimental Example 2 on a pure PBS solution that can be checked In addition, it can be seen that the reactive oxygen species detection sensor according to Example 3 still delivers a higher drain current than the reactive oxygen species detection sensor according to Comparative Example 1. This result was confirmed to show the same tendency in the transmission characteristic result, which shows a clear movement _{of the drain current (I D} ) according to the change of the drain _{voltage (V D ).} The hole mobility of the reactive oxygen species detection sensor according to Example 3 on a pure PBS solution ^{was measured as μh = 1.9 x 10 -3} cm ² /Vs, which was the hole mobility value in the inert atmosphere of Experimental Example 2 and Almost similar. These results show that the reactive oxygen species detection sensor including the organic field effect transistor device including the hybrid channel layer according to the present invention is suitable as a sensor for detecting reactive oxygen species such as a peroxide solution on a PBS solution.

Experimental Example 4. Measurement and results of organic field effect transistor device including hybrid channel layer according to weight ratio on PBS stream containing 0.5 mM peroxide solution

A PBS stream containing a 0.5 mM concentration of peroxide solution corresponding to reactive oxygen species was brought into contact with the reactive oxygen species detection sensor according to Example 3 and the reactive oxygen species detection sensor according to Comparative Example 1, and the characteristics of the basic transistor device were measured did. These measurements were performed on a PBS stream containing a peroxide solution by mounting a reactive oxygen species detection sensor inside a liquid-flow sample holder in a perfusion system.

10 is an active oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention and an organic field effect transistor device including a channel layer according to a comparative example of the present invention. It is a graph showing the change in drain current with time of the transistor element in the active oxygen species detection sensor including the graph. More specifically, the graph on the left of FIG. 10a shows the drain voltage (V _D ) of the transistor according to time in the reactive oxygen species detection sensor according to Example 3 and the active oxygen species detection sensor according to Comparative Example 1 when the drain voltage (V D ) is -0.3 V The current change is shown as a graph, and the graph on the right of FIG. 10a is a transistor in the reactive oxygen species detection sensor according to Example 3 and the active oxygen species detection sensor according to Comparative Example 1 when the _{drain voltage (V D ) is -0.5 V} It is a graph showing the change in drain current with time of the device. At this time, the concentration of the peroxide was fixed to 0.5 mM, and the gate voltage (V _G ) was performed in the range of 0 to 5 V. In FIG. 10a, 'O ₂ -ln' indicates the moment at which a peroxide solution corresponding to reactive oxygen species is injected into the PBS stream, and 'Reaction' indicates the point at which the reaction peak (signal) starts to increase due to the reaction between peroxide and rutin. points to

In addition, the left graph of FIG. 10b shows the drain current according to time of the transistor element in the reactive oxygen species detection sensor according to Example 3 and the active oxygen species detection sensor according to Comparative Example 1 when the _{drain voltage (V D ) is -0.3 V} is shown as a function of the gate voltage, and the graph on the right of FIG. 10b shows the reactive oxygen species detection sensor according to Example 3 and the active oxygen species detection according to Comparative Example 1 when the _{drain voltage (V D ) is -0.5 V} The net change of the drain current with time of the transistor element in the sensor is expressed as a function of the gate voltage. In FIG. 10B 'R ² ' is provided by each plot as a coefficient of determination.

_{Referring to FIG. 10A , when the drain voltage (V D} ) is -0.3 V after injecting the peroxide solution into the PBS stream for both the reactive oxygen species detection sensors according to Example 3 and Comparative Example 1, the drain current value after about 18 seconds has elapsed It can be seen that the value of the drain current starts to increase, and the drain current value reaches a maximum value after about 20 seconds, and the drain current value disappears over time as the peroxide solution passes through the sample chamber. _{Similarly, when the drain voltage (V D} ) is -0.5 V after injecting the peroxide solution into the PBS stream in both of the reactive oxygen species detection sensors according to Example 3 and Comparative Example 1, the drain current value starts to increase after about 100 seconds elapse And, it can be seen that the drain current value becomes the maximum value after about 105 seconds, and the drain current value disappears over time as the peroxide solution passes through the sample chamber. Both the reactive oxygen species detection sensor according to Example 3 and Comparative Example 1 _{exhibited a larger drain current signal when the drain voltage (V D} ) was -0.5 V than when it was -0.3 V. In addition, it was confirmed that the drain current signal of the reactive oxygen species detection sensor according to Example 3 and Comparative Example 1 gradually increased while increasing the gate voltage at the fixed drain voltage. These results indicate that the reactive oxygen species detection sensor according to the present invention can amplify the sensing current signal by controlling both the drain voltage and the gate voltage. In addition, from the results of FIGS. 10a and 10b, it can be confirmed that the reactive oxygen species detection sensor according to Example 3 delivers a higher drain current signal under the same voltage condition as compared to the active oxygen species detection sensor according to Comparative Example 1, This indicates that the function as a reactive oxygen species detection sensor is better.

Experimental Example 5. Measurement of characteristics and results of organic field effect transistor device including hybrid channel layer according to weight ratio on PBS stream containing 0 to 10 nM peroxide solution

A PBS stream containing a peroxide solution at a concentration of 0 to 10 nM (0, 1, 2, 5 and 10 nM) corresponding to the reactive oxygen species was transferred to the reactive oxygen species detection sensor according to Example 3 and the reactive oxygen species according to Comparative Example 1. A species detection sensor was contacted, and the characteristics of the basic transistor element were measured. These measurements were performed on a PBS stream containing a peroxide solution by mounting a reactive oxygen species detection sensor inside a liquid-flow sample holder in a perfusion system. The measurement results including sensitivity are shown in Table 3 below. In Table 3 below, 'C _ROS ' means the concentration of peroxide corresponding to reactive oxygen species in the PBS stream, and 'Accuracy' is an accuracy calculated from the measurement results for more than 50 reactive oxygen species sensors. In addition, the 'Sensitivity' means the drain current value (│ID│ (nA)) and the ratio of active peroxide levels for the oxygen species _(ROS C (nM)) as a sensitivity.

11 is a transistor shown when in contact with a PBS stream containing a peroxide solution of 0 to 10 nM concentration in the reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention; It is a graph showing the change in drain current with time of the device. More specifically, FIG. 11a shows that active oxygen species discontinuously contact the reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention, and the gate voltage (V _G ) = When the drain voltage (V _D ) = -0.5 V and the peroxide concentration is 0, 1, 2, 5, and 10 nM, the drain current ( _ID ) change with time in the case of a graph is shown. In addition, FIG. 11b shows that active oxygen species continuously contact in the reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention, and gate voltage (V _G ) = drain voltage. A graph showing the change in drain current when continuously injecting peroxide solutions with concentrations of 0, 1, 2, 5 and 10 nM when (V _{D ) = -0.5 V. In addition, Figure 11c is a gate voltage (V G} ) = drain voltage (V _D ) = -0.5 V in the reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention It is a graph showing the sensing stability of reactive oxygen species when continuously and repeatedly injecting peroxide solutions having concentrations of 0, 1, 2, 5 and 10 nM when . After each measurement was performed, the process of washing the reactive oxygen species detection sensor used for measurement with a weak acid solution was omitted.

Referring to FIG. 11 , in the reactive oxygen species detection sensor according to Example 3, it can be confirmed that the drain current signal is clearly measured even when the concentration of the peroxide solution in the PBS stream is decreased from 10 nM to 1 nM. More specifically, considering the operating mechanism of the reactive oxygen species detection sensor of the present invention, the higher the rate at which the phenolic compound 31 included in the hybrid channel layer 30 is deprotonated increases, the additional flow of holes is induced. It has been mentioned above that the width will increase. Referring to FIG. 11a , it can be confirmed that the reactive oxygen species sensor of the present invention can detect reactive oxygen species even at a low concentration of 1 nM. In addition, it is also worth noting that the change in the drain current value increases as the concentration of reactive oxygen species increases. This means that the reactive oxygen species sensor of the present invention can measure up to the concentration of reactive oxygen species.

For reference, in the case of the chemiluminescence method using semiconducting polymer nanoparticles for in vivo imaging of reactive oxygen species, the minimum concentration for detecting reactive oxygen species is 5 nM ~ 1 μM, and the electrochemical method uses reactive oxygen species. In view of the fact that the minimum concentration for detection is 2.5 nM, it can be estimated that the reactive oxygen species detection sensor according to the present invention is excellent in the reactive oxygen species detection ability. 11, the position of the maximum value of the drain current peak gradually shifted to a shorter time as the concentration of the peroxide solution decreased, which resulted in a decrease in the reactivity of the peroxide corresponding to rutin and reactive oxygen species in the lower concentration of the peroxide solution. It can be presumed that this is because In particular, referring to FIG. 11B , it can be seen that the reactive oxygen species detection sensor according to the present invention exhibits a clear drain current signal when peroxide solutions having different concentrations are continuously injected into the perfusion system. That is, it can be confirmed that the reactive oxygen species detection sensor of the present invention has the ability to continuously detect reactive oxygen species. In particular, it can be confirmed that the background value is maintained relatively uniformly even in the continuous measurement process, which means that the measurement reliability of the reactive oxygen species detection sensor of the present invention is high.

In addition, referring to FIG. 11c , it can be seen that the drain current signal is quite reproducible when the peroxide solution of the same concentration is continuously injected, and from this, the reactive oxygen species detection sensor according to the present invention is used for detecting active oxygen species. It can be seen that it can be operated as an efficient sensor.

Combining the results of Experimental Example 5, it can be seen that the reactive oxygen species detection sensor of the present invention can not only repeatedly and continuously detect reactive oxygen species, but also measure the concentration change with considerable reliability.

Experimental Example 6. Analysis and results of the morphology of the hybrid channel layer in the reactive oxygen species detection sensor according to an embodiment of the present invention

In order to understand the cause of the improved reactive oxygen species detection effect due to the introduction of nanoclay into the existing channel layer containing P3HT and rutin in organic field effect transistor devices, the channel layer was analyzed using a scanning electron microscope (SEM). The morphology and surface were analyzed. Hybrid channel layer included in the reactive oxygen species detection sensor according to an embodiment of the present invention, the channel layer included in the reactive oxygen species detection sensor according to a comparative example of the present invention, a channel layer including raw P3HT, and P3HT and nano Nano- and micro-sized aggregates were observed by taking an SEM image of the channel layer containing clay (Al ₂ Si ₂ O ₅ (OH) _{4 ·H 2 O).}

12 is an organic field including a hybrid channel layer of a reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention and a channel layer according to a comparative example of the present invention; A scanning electron microscope (SEM) image of the channel layer of the reactive oxygen species detection sensor including the effect transistor device is shown. More specifically, FIG. 12a is an SEM image of raw P3HT (P3HT: rutin: nanoclay = 10: 0: weight ratio of 10: 0: 0), and FIG. 12 b is a channel layer with a weight ratio of P3HT: rutin: nanoclay = 10: 1: 0. SEM image of (Comparative Example 1), FIG. 12c is an SEM image of a channel layer having a weight ratio of P3HT: rutin: nanoclay = 10: 0: 2, FIG. 11d is P3HT: rutin: nanoclay = 10: 1: 2 The SEM image of the hybrid channel layer (Example 3) having a weight ratio is shown.

13 is an organic field including a hybrid channel layer of a reactive oxygen species detection sensor including an organic field effect transistor device including a hybrid channel layer according to an embodiment of the present invention and a channel layer according to a comparative example of the present invention; A scanning electron microscope (SEM) image of the channel layer of the reactive oxygen species detection sensor including the effect transistor device is shown. More specifically, FIG. 13a is an SEM image focusing on the rutin portion in the channel layer (Comparative Example 1) having a weight ratio of P3HT: rutin: nanoclay = 10: 1: 0, FIG. 13b is P3HT: rutin: nanoclay = SEM image focused on the nanoclay portion in the channel layer having a weight ratio of 10: 0: 2, FIG. 13c is a hybrid channel layer (Example 3) having a weight ratio of P3HT: rutin: nanoclay = 10: 1: 2 The SEM image focused on the rutin-nanoclay complex portion is shown.

13A, in the channel layer (Comparative Example 1) having a weight ratio of P3HT: rutin: nanoclay = 10: 1: 0, rutin forms a cube-shaped crystalline domain having an average size of about 100 nm. It can be confirmed, and referring to FIG. 13b , it can be confirmed that nanoclays forming continuous phase aggregates in the channel layer having a weight ratio of P3HT:rutin:nanoclay=10:0:2 can be confirmed. In addition, referring to FIG. 13C , in the hybrid channel layer (Example 3) having a weight ratio of P3HT: rutin: nanoclay = 10: 1: 2, the formation of a complex aggregate including cube-shaped crystalline domains surrounded by a continuous phase was performed. can be checked These results are due to the fact that although the rutin-nanoclay complex was formed in the hybrid channel layer of the reactive oxygen species detection sensor according to the present invention, the size increased to 1-3 μm during the complexation process. In particular, it can be seen from FIG. 13c that the nanoclay induces a more even distribution in the hybrid channel layer 30 of the phenolic compound 31, for example, rutin in the hybrid channel layer 30 of the present invention. Accordingly, it is possible to improve the performance of the organic field effect transistor device including the hybrid channel layer of the present invention and the ability of the reactive oxygen species detection sensor by inducing some or all of the hydroxyl groups (OH) in the routine to be exposed to the outside. .

The organic field effect transistor device including the hybrid channel layer of the present invention according to the above-described method has a simple production process and excellent mass productivity as it can be mass-produced at low cost without additional equipment.

In addition, the reactive oxygen species detection sensor of the present invention including the organic field effect transistor device has an effect that can repeatedly and continuously measure even a low concentration of active oxygen species.

Furthermore, the reactive oxygen species detection device of the present invention including the reactive oxygen species detection sensor can be miniaturized and portable, and has the effect of being convenient and versatile.

The above description is merely illustrative of the technical spirit of the present invention, and various modifications and variations will be possible without departing from the essential characteristics of the present invention by those skilled in the art to which the present invention pertains.

Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain, and the scope of the technical spirit of the present invention is not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

1: organic field effect transistor element
10: substrate
20: insulating layer
30: hybrid channel layer
31: phenolic compound
32: halloysite nanoclay
41: gate electrode
42: source electrode
43: drain electrode

Claims (11)

Board;
a gate electrode formed on the substrate;
an insulating layer formed on the gate electrode;
a source electrode formed on the insulating layer;
a drain electrode formed on the insulating layer to be spaced apart from the source electrode; and
a hybrid channel layer formed on the insulating layer and positioned between the source electrode and the drain electrode;
The hybrid channel layer includes a p-type conductive polymer, a phenolic compound, and a halloysite nanoclay,
The phenolic compound and the halloysite nanoclay are combined with each other in the hybrid channel layer to form a complex aggregate including a cube-shaped crystalline domain surrounded by a continuous phase,
An organic field effect transistor device, characterized in that some or all of the hydroxyl groups included in the phenolic compound are exposed to the outside.
The method of claim 1,
The phenolic compound is characterized in that it contains two or more hydroxyl groups, an organic field effect transistor device.
The method of claim 1,
The phenol-based compound is an alkylphenol-based compound, a benzenediol-based compound, a benzenetriol-based compound, a phenol glycoside-based compound, a polyphenol-based compound, and an amino Organic field effect, characterized in that at least one phenolic compound selected from the group comprising a phenol-based compound, a cresol-based compound, a bisphenol-based compound, and a flavonol-based compound transistor element.
The method of claim 1,
The phenolic compound is an organic field effect transistor device, characterized in that the compound containing a catechol (Catechol) moiety.
The method of claim 1,
The phenolic compound is an organic field effect transistor device, characterized in that the compound containing a resorcinol (Resorcinol) moiety.
5. The method of claim 4,
The compound containing the catechol moiety is a flavonol-based compound,
Quercetin, kaempherol, apigenin, luteolin, myricetin, chrysin (5,7-dihydroxyflabvone), baicalein (5,6) ,7-trihydroxyflavone), scutellarein (5,6,7,4'-tetrahydroxyflavone), wogonin (5,7-dihydroxy-8-methoxyflavone)), 3-hydroxyflavone (3 -Hydroxyflavone), Azaleatin, Fisetin, Galangin, Gossypetin, Kaempferide, Isorhamnetin, Morin, Patchpodol ( Pachypodol), Rhamnazin, Rhamnetin, Astragalin, Azalein, Hyperoside, Isoquercitin, Kaempferitrin, Myrisi Any selected from the group comprising tin (Myricitrin), quercitrin (Quercitrin), robinin (Robinin), rutin (Rutin), spiraeoside (Spiraeoside), xanthorhammin (Xanthorhamnin), and amurensin (Amurensin) An organic field effect transistor device comprising one or more.
7. The method of claim 6,
The flavonol-based compound is azalein, hyperoside, isoquercitin, myricitrin, quercitrin, rutin, and An organic field effect transistor device, characterized in that any one or more compounds selected from the group comprising Xanthorhamnin.
The method of claim 1,
In the hybrid channel layer, the weight ratio of the p-type conductive polymer, the phenolic compound (31), and the halloysite nanoclay is 10: 1: 0.5 to 10: 1: 3, characterized in that the organic field effect transistor device.
The method of claim 1,
The p-type conductive polymer is P3HT (poly(3-hexylthiophene)) or PEDOT (Poly(3,4-ethylenedioxythiophene)), characterized in that the organic field effect transistor device.
Board;
a gate electrode formed on the substrate;
an insulating layer formed on the gate electrode;
a source electrode formed on the insulating layer;
a drain electrode formed on the insulating layer to be spaced apart from the source electrode; and
a hybrid channel layer formed on the insulating layer and positioned between the source electrode and the drain electrode;
The hybrid channel layer includes a p-type conductive polymer, a phenolic compound, and a halloysite nanoclay,
The phenolic compound and the halloysite nanoclay are combined with each other in the hybrid channel layer to form a complex aggregate including a cube-shaped crystalline domain surrounded by a continuous phase,
An active oxygen species detection sensor, characterized in that two or more organic field effect transistor devices to which some or all of the hydroxyl groups included in the phenolic compound are exposed to the outside are connected in parallel.
Board;
a gate electrode formed on the substrate;
an insulating layer formed on the gate electrode;
a source electrode formed on the insulating layer;
a drain electrode formed on the insulating layer to be spaced apart from the source electrode; and
a hybrid channel layer formed on the insulating layer and positioned between the source electrode and the drain electrode;
The hybrid channel layer includes a p-type conductive polymer, a phenolic compound, and a halloysite nanoclay,
The phenolic compound and the halloysite nanoclay are combined with each other in the hybrid channel layer to form a complex aggregate including a cube-shaped crystalline domain surrounded by a continuous phase,
An apparatus for detecting active oxygen species, characterized in that it comprises two or more active oxygen species detection sensors in which two or more organic field effect transistor elements to which some or all of the hydroxyl groups included in the phenolic compound are exposed to the outside are connected in parallel.

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