KR102615645B1 - Conducting polymer nanostructure based multifunction sensor and preparation method therof - Google Patents

Abstract

The present invention relates to a high tensile substrate; A patterned electrode layer formed on the high tensile substrate; and a body-worn hearing sensor including conductive polymer nanostructures formed on the patterned electrode layer and a method of manufacturing the same. The hearing sensor according to the present invention can be attached to the body using a high-tensile polymer substrate, and the inter-bridge between conductive polymer nanostructures formed on the electrode layer in the high-tensile substrate due to strain changes in the high-tensile substrate. Since auditory signals are detected through changes in electrical conductivity, it does not require accurate pronunciation or loud sounds, so disabled people who have difficulty communicating due to physical problems can communicate more conveniently through the hearing sensor.

Description

Conducting polymer nanostructure based multifunctional sensor and preparation method thereof {Conducting polymer nanostructure based multifunction sensor and preparation method therof}

The present invention relates to an auditory sensor, and more specifically, to a body-worn auditory sensor based on a conductive polymer nanostructure and a method of manufacturing the same.

An auditory sensor is a sensor that can detect input signals using electromagnetic waves in various areas instead of two-dimensional images. Hearing is a sensor that does not only consider the sound wave range, but in principle detects the state of an object using electromagnetic waves. It is a sensor that does not provide a two-dimensional image but outputs only the size of the signal, including a microphone and speaker using sound waves, a sonar sensor using ultrasonic waves, a radar sensor and RFID using microwaves, an illumination sensor using visible light, and a flame detector using ultraviolet light. , LED and photodiode sensors using infrared rays belong to this category.

Existing hearing sensors can recognize words when people speak them with correct pronunciation, but they are difficult to use for hearing-impaired people who have difficulty pronouncing correctly or who cannot make loud sounds.

Therefore, there is a need for a hearing sensor that can be useful not only for hearing impaired people but also in environments where accurate pronunciation is difficult or loud sounds cannot be made.

Meanwhile, as wearable technology and Internet of Things (IoT) technology have recently grown rapidly, interest in flexible and stretchable electronic devices and electronic devices has increased significantly. Flexible electronic devices come in various forms: bendable devices, foldable devices, rollable devices that can be rolled up, and deformable devices that can change their shape. etc. Stretchable electronic devices, also known as stretchable devices, are expected to become the next generation of electronic devices following flexible electronic devices. A stretchable electronic device is an electronic device that operates without losing its properties when stretched or bent, and can maintain its properties even when external force is removed. Expressed in terms of applied strain, a stretchable element generally refers to an element that can withstand a tensile strain of 5% or more. Stretchable devices have the advantage of being able to be attached to any surface, such as the body, human skin, or clothing, because they can maintain consistent performance despite various mechanical deformations. As a result, they can be used in displays, solar cells, wearable electronic devices, artificial skin, and robots. It can be applied to fields such as: Therefore, various researches on stretchable batteries, displays, sensors, and PCBs are being actively conducted recently. However, technological development and commercialization of elastic materials and components are still in the early stages.

Republic of Korea Patent Publication No. 10-2020-0138010

The first purpose of the present invention is to solve the above problem and provide a body-worn hearing sensor that can be usefully used even by hearing impaired people.

A second object of the present invention is to provide a method of manufacturing the body-worn hearing sensor.

In order to achieve the first object, one aspect of the present invention provides a body-worn hearing sensor based on a conductive polymer nanostructure. The body-worn hearing sensor according to the present invention includes a high-tensile substrate with a tensile strength of 50% or more; A patterned electrode layer formed on the high tensile substrate; and conductive polymer nanostructures formed on the patterned electrode layer.

The high tensile substrate may be a high tensile polymer substrate selected from the group consisting of polydimethylsiloxane (PDMS), polyurethane (PU), and Ecoflex.

The electrode layer is a metal selected from titanium (Ti), gold (Au), platinum (Pt), and silver (Ag); or polyfluorene, polyphenylene, polypyrene, polyazulene, polynaphthalene, polyacetylene (PAC), poly(p-phenylene vinylene) (PPV), polypyrrole (PPY), polycarbazole, polyindole, polya. It may be selected from zepine, polyaniline (PANI), polythiophene (PT), poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(p-phenylene sulfide) (PPS).

The electrode layer may have a pattern of a horizontal interdigitated electrode (IDE) structure including a plurality of finger electrodes spaced at predetermined intervals on a plane.

The hearing sensor may further include an adhesive layer between the high-tensile substrate and the electrode layer.

The conductive polymer nanostructure is polyfluorene; polyphenylene; polypyrene; polyazulene; polynaphthalene; polyacetylene (PAC); poly(p-phenylene vinylene) (PPV); polypyrrole (PPY); polycarbazole; polyindole; polyazepine; polyaniline (PANI); polythiophene (PT); A conductive polymer selected from poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(p-phenylene sulfide) (PPS), but may be a different conductive polymer from the electrode layer.

The conductive polymer nanostructure may be made of polyaniline (PANI).

When the conductive polymer nanostructure is grown, an inter-bridge may be formed between the conductive polymer nanostructures.

The hearing sensor can detect tensile or deformation strain through changes in electrical conductivity flowing in an inter-bridge between conductive polymer nanostructures formed on electrode layers in a high-tensile substrate.

Additionally, in order to achieve the second object, another aspect of the present invention provides a method of manufacturing the body-worn hearing sensor. The method of manufacturing a body-worn hearing sensor according to the present invention includes forming a high-tensile substrate with a tensile strength of 50% or more on an auxiliary substrate (S10); Forming a patterned electrode layer on the high tensile substrate (S20); Forming conductive polymer nanostructures on the patterned electrode layer (S30); and removing the auxiliary substrate (S40).

Forming a patterned electrode layer on the high-tensile substrate (S20) includes forming a photoresist layer on the high-tensile substrate (S21); Performing patterning on the photoresist layer (S22); Forming an electrode layer on the patterned portion (S23); and removing the photoresist layer to form a patterned electrode layer (S24).

Forming conductive polymer nanostructures on the patterned electrode layer (S30) includes forming a photoresist layer except for a plurality of finger electrode regions of the electrode layer (S31); Forming a conductive polymer nanostructure in a plurality of finger electrode regions (S32); and removing the photoresist layer (S33).

The hearing sensor according to the present invention can be attached to the body using a high-tensile polymer substrate that is harmless to the human body and is biocompatible. When the hearing sensor is attached to the neck, the hearing sensor can be attached to the body due to a change in strain of the high-tensile substrate. Since the auditory signal is detected by changes in electrical conductivity of the inter-bridge between the conductive polymer nanostructures formed on the electrode layer, the signal is detected using the tremor of the voice rather than a direct sound signal, so it is accurate. It does not require pronunciation or loud sound. In addition, since other measured tremor signals can be designated as words or meanings desired by the individual, disabled people who have felt uncomfortable in communication due to physical problems can communicate more conveniently through the hearing sensor.

In addition, when polyaniline (PANI) is used as a conductive polymer nanostructure, in addition to the hearing sensor according to the present invention, the polyaniline detects reducing gases (CH ₄ , propane, alcohol, hydrogen, etc.) and can be applied to an ultraviolet sensor. Since it is possible, it can also be used as a multifunctional sensor.

Figure 1 is a schematic diagram of a body-worn hearing sensor according to an embodiment of the present invention.
Figure 2 is a schematic diagram of a body-worn hearing sensor according to another embodiment of the present invention.
Figure 3 is a schematic diagram showing the pattern of the electrode layer of a body-worn hearing sensor according to an embodiment of the present invention.
Figure 4 is a schematic diagram showing the detection mechanism of a body-worn hearing sensor according to an embodiment of the present invention.
Figure 5 is a flowchart showing a method of manufacturing a body-worn hearing sensor according to an embodiment of the present invention.
Figure 6 is a flow chart specifying the step of forming a patterned electrode layer on a high-tensile strength substrate in the method of manufacturing a body-worn hearing sensor according to an embodiment of the present invention.
Figure 7 is a flowchart detailing the step of forming a conductive polymer nanostructure on a patterned electrode layer in the method of manufacturing a body-worn hearing sensor according to an embodiment of the present invention.

Hereinafter, embodiments will be described in detail with reference to the drawings. Various changes may be made to the embodiments described below. The embodiments described below are not intended to limit the embodiments, but should be understood to include all changes, equivalents, and substitutes therefor.

Terms used in the examples are merely used to describe specific examples and are not intended to limit the examples. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that it does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

The width and thickness of layers or regions shown in the attached drawings may be somewhat exaggerated for clarity of description. Like reference numerals refer to like elements throughout the detailed description. However, the present invention is not limited to the following examples.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by a person of ordinary skill in the technical field to which the embodiments belong. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and unless explicitly defined in the present application, should not be interpreted in an ideal or excessively formal sense. No.

In this specification, “high tensile strength” refers to the property of maintaining material properties without fracture even at a tensile strain of 50%.

1 and 2 are schematic diagrams of a body-worn hearing sensor according to an embodiment of the present invention.

Referring to Figures 1 and 2, the body-worn hearing sensor according to the present invention includes a high-tensile substrate (10); A patterned electrode layer 20 formed on the high tensile substrate; and conductive polymer nanostructures 30 formed on the patterned electrode layer.

In the present invention, the hearing sensor is characterized as being body-mountable. Accordingly, in order to enable attachment to the body, it is desirable to use a high-tensile substrate with a tensile strength of 50% or more. Specifically, the substrate may have a stretchability of 50 to 80%.

This high-tensile substrate 10 may be a high-tensile polymer substrate selected from the group consisting of polydimethylsiloxane (PDMS), polyurethane (PU), and Ecoflex.

The high-tensile substrate 10 may be a commercially available film, or may be formed by applying a high-tensile polymer onto an auxiliary substrate such as a Si substrate to form a coating film, but is not limited thereto.

In the high-tensile strength substrate 10, the thickness of the high-tensile polymer substrate may be 15 to 25 μm, but is not limited thereto.

The electrode layer 20 is formed on the high-tensile substrate and is made of an electrically conductive metal selected from titanium (Ti), gold (Au), platinum (Pt), and silver (Ag), or polyfluorene; polyphenylene; polypyrene; polyazulene; polynaphthalene; polyacetylene (PAC); poly(p-phenylene vinylene) (PPV); polypyrrole (PPY); polycarbazole; polyindole; polyazepine; polyaniline (PANI); polythiophene (PT); It may include a polyconductive polymer selected from poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(p-phenylene sulfide) (PPS).

The electrode layer 20 may be formed of a plurality of fine finger electrodes spaced at predetermined intervals on a plane. The plurality of finger electrodes may be formed to have an electrode pattern. The shape of the pattern of the electrode is not limited, and may be formed in various shapes commonly used in the art.

Figure 3 is a schematic diagram showing the pattern of an electrode layer according to an embodiment of the present invention.

As shown in FIG. 3, the electrode layer 20 may have a pattern of a horizontal interdigitated electrode (IDE) structure including a finger electrode region.

The patterning of the electrode layer can be formed using methods known in the art, for example, exposure and development methods using photoresist. Hereinafter, the specific patterning method will be described in detail in the description of the manufacturing method described later.

In the patterned electrode layer, a sensing element having a nanostructure is formed in the finger electrode area.

When forming the electrode layer 20 as a metal electrode, as shown in FIG. 2, an adhesive layer 21 may be additionally formed on the high-tensile strength substrate to improve the adhesion of the electrode layer.

A conductive polymer nanostructure 30 may be formed on the patterned electrode layer.

The nanostructure is formed on an electrode layer and used as a sensing body. At this time, since the hearing sensor according to the present invention is characterized by detecting changes in strain, the material is maintained even when refraction, distortion, tension, etc. are applied in various directions. Characteristics must not change. However, metal nanostructures such as zinc oxide (ZnO) have a problem of being easily broken because they are not flexible when a strong external strain is applied. Accordingly, it is preferable that the nanostructure used as a sensing element of a body-worn hearing sensor is a conductive polymer nanostructure that has electrical conductivity but is flexible.

The conductive polymer nanostructure is polyfluorene; polyphenylene; polypyrene; polyazulene; polynaphthalene; polyacetylene (PAC); poly(p-phenylene vinylene) (PPV); polypyrrole (PPY); polycarbazole; polyindole; polyazepine; polyaniline (PANI); polythiophene (PT); A conductive polymer selected from poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(p-phenylene sulfide) (PPS), and may be made of a different conductive polymer than the electrode layer. Specifically, the conductive polymer nanostructure is preferably made of polyaniline (PANI).

The method of forming the conductive polymer nanostructure may use methods known in the art, such as hydrothermal synthesis, thermal chemical vapor deposition, and microwave-assisted chemical vapor deposition. ), laser-assisted chemical vapor deposition, sol-gel coating, etc. can be used to grow nanostructures.

The conductive polymer nanostructure 30 is formed of one or more, and is grown in various directions, such as vertically and horizontally, on a plurality of patterned finger electrodes 20 and on the substrate 10 exposed between the finger electrodes to form a random structure. It is formed, and as a result, when the conductive polymer nanostructure grows, a connection site (inter-bridge) between the conductive polymer nanostructures is formed.

The conductive polymer nanostructures 30 include rods, wires, pillars, fibers, tubes, belts, flowers, plates, It may be in the form of a particle, helix, or urchin shape, but is preferably in the form of a rod, for example, a nanorod or nanowire.

The height of the conductive polymer nanostructures 30 is not limited and may have a nanoscale to microscale size.

Figure 4 is a schematic diagram showing the detection mechanism of a body-worn hearing sensor according to an embodiment of the present invention.

Referring to Figure 4, when the hearing sensor according to the present invention is in an untensioned state, the inter-bridge between the conductive polymer nanostructures formed on the electrode layer in the substrate acts as a path through which current flows, so that a constant current flows. When a tensile or deformation strain due to an external force acts, the cross-sectional area of the inter-bridge between the conductive polymer nanostructures changes as the high-tensile substrate is stretched, and thus, the electrode layer formed on the electrode layer in the high-tensile substrate is changed. Signals can be detected by changing the electrical conductivity (current) flowing in the inter-bridge between conductive polymer nanostructures.

In particular, when polyaniline (PANI) is used as the conductive polymer nanostructure, the PANI nanostructure changes from a conductive emerald salt to an insulating emerald base when contacted with reducing CH ₄ gas, and the adsorbed CH ₄ As the conductivity decreases due to the charge exchange between the gas and the PANI pp* conjugation system, the conductivity changes at a very fast rate, making gas sensing possible and also possible as an ultraviolet sensor, so a sensor containing polyaniline nanostructures can be used as a multifunctional sensor. can also be used.

Additionally, another aspect of the present invention provides a method of manufacturing the body-worn hearing sensor.

Figure 5 is a flowchart showing a method of manufacturing a body-worn hearing sensor according to an embodiment of the present invention.

The manufacturing method of the body-worn hearing sensor according to the present invention is

Forming a high-tensile substrate on an auxiliary substrate (S10);

Forming a patterned electrode layer on the high tensile substrate (S20);

Forming conductive polymer nanostructures on the patterned electrode layer (S30); and

and removing the auxiliary substrate (S40).

Hereinafter, the manufacturing method of the body-worn hearing sensor of the present invention will be described in detail step by step.

First, step S10 is a step of forming a high tensile substrate.

The high-tensile substrate can be formed by attaching a commercially available high-tensile polymer substrate film to a hard auxiliary substrate, such as a Si substrate, or coating it by applying a high-tensile polymer solution.

The auxiliary substrate may be a relatively hard substrate so that a high-tensile strength substrate can be easily formed, and a substrate known in the art may be used.

The auxiliary substrate may be a semiconductor material, for example, group III-V compound semiconductors such as GaN, AlN, GaP, and GaAs; There are semiconductors such as SrCu ₂ O ₂ , SiC, and Si, and these can be easily purchased commercially.

Additionally, the auxiliary substrate may include a substrate made of sapphire, glass, polymer, or other suitable material in addition to a semiconductor material.

The coating method of the high tensile polymer solution includes tape casting, dip coating, spray coating, spin coating, roll coating, and slot die coating. die coating, comma coating, and screen printing, etc., but are not limited thereto, and polymer coating methods commonly used in the industry may be used.

Next, step S20 is a step of forming a patterned electrode layer on the high tensile substrate.

Figure 6 is a flow chart specifying the step of forming a patterned electrode layer on a high-tensile strength substrate in the method of manufacturing a body-worn hearing sensor according to an embodiment of the present invention.

Referring to FIG. 6, the step (S20) of forming a patterned electrode layer on the high tensile substrate is

Forming a photoresist layer on a high-tensile substrate (S21);

Performing patterning on the photoresist layer (S22);

Forming an electrode layer on the patterned portion (S23); and

It may include a step (S24) of removing the photoresist layer to form a patterned electrode layer.

The step S21 is a step of forming a photoresist layer on a high tensile substrate.

The photoresist layer is made of polyacrylates resin, epoxy resin, phenolic resin, polyamides resin, polyimides resin, and unsaturated polyester resin. (unsaturated polyesters resin), poly(phenylenethers) resin, poly(phenylenesulfides) resin, and benzocyclobutene (BCB). It can be done, but is not limited to this.

The photoresist layer may be made of a positive material or a negative material.

In the case of the positive material, the structure of the part irradiated with light during the photolithography process is weakened, and the part irradiated with light is removed during the development process, and the negative material is the material. In the case of materials, the structure of the part exposed to light becomes hardened during the photolithography process, and the part not exposed to light is removed during the development process.

The photoresist layer may be formed on the entire surface of the high-tensile substrate by applying a photoresist of the positive or negative material to a coating method commonly used in the art, such as spin coating.

The formed photoresist layer can be pre-baked.

Next, step S22 is a step of performing patterning on the photoresist layer.

Forming a pattern (patterning) can be done by a known photoetching process. For example, exposure is performed using an ultraviolet ray exposure device, etc. using a mask with a predefined pattern for forming an electrode pattern, which will be described later. By performing a development process on the photoresist layer, it can be patterned according to the pattern of the mask.

At this time, the mask has a structure where, when the material of the photoresist layer is a negative material, the part scheduled as the electrode pattern is a blocking area, and the other area is a transparent area. Using the mask, By irradiating light (UV) to the remaining areas except for the portion scheduled for the metal electrode pattern, the structure of the portion irradiated with light becomes hardened, and the portion not irradiated with light is removed during the subsequent development process. At this time, the area where removal occurred corresponds to the area scheduled for the electrode pattern.

In addition, when the photoresist layer is a positive material, the mask has a structure in which the part scheduled to be the metal electrode pattern is a transmission area and the other area is a blocking area, and by using the mask, the metal electrode pattern is used as a transmission area. By irradiating light to the area of the part scheduled as the electrode pattern, the structure of the part irradiated with light is weakened (softening), and the area irradiated with light is removed during the subsequent development process. At this time, the area where removal occurred corresponds to the area scheduled for the electrode pattern.

Ultimately, the area in the photoresist layer where the photoresist is removed by the mask pattern corresponds to the area designated as the electrode pattern.

At this time, the mask pattern may be formed so that the electrode pattern described later can constitute a plurality of finger electrodes having a predetermined spacing on a plane, for example, a horizontal cross electrode including a finger electrode region as shown in FIG. 3 ( It may be formed in a pattern of an interdigitated electrode (IDE) structure, but is not limited thereto.

Next, step S23 is a step of forming an electrode layer on the patterned portion.

Specifically, an electrode layer can be formed in a predetermined area using an electrode pattern formed by removing part of the photoresist through photoresist patterning.

The method of forming the electrode layer is physical vapor deposition (PVD) such as direct current magnetron sputtering and radio frequency magnetron sputtering, solution deposition including sol-gel method, evaporation, chemical vapor deposition, and vapor deposition. It can be performed, but is not limited to this.

The electrode layer may be formed solely as a metal electrode or a conductive polymer electrode, and to improve adhesion with the high-tensile polymer substrate, an adhesive layer may be formed using, for example, titanium metal, and then the electrode layer may be formed.

Next, step S24 is a step of removing the photoresist layer.

This step is also called a stripping process, and is a process of removing the photoresist layer prepared in step S21.

The photoresist layer can be removed using a stripper solution or O ₂ ashing method, and can also be removed using an organic solvent such as acetone.

Through this method, a patterned electrode layer can be formed.

Next, step S30 is a step of forming conductive polymer nanostructures on the patterned electrode layer.

Figure 7 is a flowchart detailing the step of forming a conductive polymer nanostructure on a patterned electrode layer in the method of manufacturing a body-worn hearing sensor according to an embodiment of the present invention.

Referring to FIG. 7, the step (S30) of forming conductive polymer nanostructures on the patterned electrode layer is

Forming a photoresist layer except for the plurality of finger electrode regions of the electrode layer (S31);

Forming a conductive polymer nanostructure in a plurality of finger electrode regions (S32); and

It may include removing the photoresist layer (S33).

First, step S31 is a step of forming a photoresist layer except for the plurality of finger electrode regions of the electrode layer.

In order to form conductive polymer nanostructures on the electrode layer, particularly on the plurality of finger electrode regions of the electrode layer, it is necessary to mask areas other than the finger electrode regions so that conductive polymer nanostructures are not formed. Accordingly, the conductive polymer nanostructures described later can be masked by forming a photoresist layer except for the formed area, that is, the plurality of finger electrode areas.

Since the method of forming the photoresist layer is the same as described in step S21, detailed information will be omitted.

Next, step S32 is a step of forming a conductive polymer nanostructure in the plurality of finger electrode regions.

The conductive polymer nanostructure may be formed on the electrode layer using methods commonly used in the art, such as chemical oxidation polymerization, electrochemical polymerization, and metal oxide complex formation, but is not limited thereto. .

As an example, in the method of forming a conductive polymer nanostructure using a chemical oxidation polymerization method, a high-tensile substrate with a photoresist pattern is placed in a chamber containing a precursor solution containing a conductive polymer, immersed for a certain period of time, and then attached to the chamber wall. , conductive polymer nanostructures can be grown by polymerizing the polymer by applying an electric or magnetic field at about 0°C.

The grown conductive polymer nanostructure is formed as one or more, and is randomly formed by growing in various directions, such as vertically and horizontally, on a plurality of patterned finger electrodes and on a substrate exposed between the finger electrodes. As a result, the conductive polymer nanostructure is formed. When nanostructures grow, inter-bridges are formed between conductive polymer nanostructures.

The conductive polymer nanostructures include rods, wires, pillars, fibers, tubes, belts, flowers, plates, and particles. ), helix, or urchin shape, but is preferably in the form of a rod, for example, a nanorod or nanowire.

The height of the conductive polymer nanostructures is not limited and may have a size ranging from nanoscale to microscale.

The substrate on which nanostructure growth has been completed can be additionally taken out, washed with deionized water, and dried with N ₂ .

Next, step S33 is a step of removing the photoresist layer.

In this step, the remaining photoresist layer can be removed using a stripper solution or O ₂ ashing method in the same manner as described in step S24, and can also be removed using an organic solvent such as acetone.

Through this method, an auditory sensor can be manufactured by forming a conductive polymer nanostructure on the patterned electrode layer.

Next, step S40 is a step of removing the auxiliary substrate.

Methods for separating the auxiliary substrate include physical methods, methods using swelling, and chemical etching methods.

Specifically, the physical method is a method of separating the auxiliary substrate from the high-tensile substrate using physical force (mechanical force).

In addition, the method using the swelling involves swelling the high-tensile substrate by immersing the structure including the high-tensile substrate and the auxiliary substrate prepared in step S30 in a solvent having a high swelling property for the high-tensile substrate layer, thereby forming the swollen solid. This is a method in which the long-walled substrate is separated from the auxiliary substrate.

Additionally, the chemical etching method is a method of etching only the auxiliary substrate using an etching solvent that selectively etches the auxiliary substrate.

The hearing sensor manufactured in this way is harmless to the human body and can be attached to the body by using a high-tensile polymer substrate. A conductive polymer nanostructure with high tensile and shear strain characteristics is formed as a sensor on the patterned electrode, forming the substrate. Even during this tension, the nanostructure transmits current without being fractured or broken, making it possible to respond to various motility (tensile, compression, twisting, slipping, etc.).

In addition, the method of manufacturing an auditory sensor according to the present invention is suitable for mass production by using a low-cost, simple structure employing a minimum of process steps, so mass production is possible.

The high-tensile acoustic sensor manufactured in this way can be used as a sensor to detect weak mechanical vibration or tension changes in the level of acoustic vibration depending on the operating principle. For example, it can be used as a detection sensor for flexible robots, a wearable sensor attached to the body, or as a human interface for various devices.

The hearing sensor according to the present invention can measure changes in current characteristics through changes in electrical conductivity between electrodes caused by changes in connection sites between nanostructures of the horizontal interdigitated electrode (IDE) structure of the conductive polymer sensor. Since this change can be used to detect subtle mechanical change signals, it can be useful in future technology fields such as artificial electronic skin attachment sensors, flexible robot support sensors, brain tissue function research, muscle sensing, and computer interfacing. there is.

Hereinafter, the present invention will be described in more detail through manufacturing examples. The following production examples are described for the purpose of illustrating the present invention, and the scope of the present invention is not limited thereto.

<Manufacturing Example 1: Manufacturing of a body-worn hearing sensor based on a high-tensile substrate and conductive polymer nanostructure>

S10: Formation of high tensile substrate on auxiliary substrate

First, a polymer precursor solution was prepared by mixing polydimethylsiloxane base and curing agent (Sylgard 184, Dow Corning) at a weight ratio of 10:1. The polymer precursor solution was spin-coated on a Si auxiliary substrate. Before curing, bubbles inside the polydimethylsilonic acid precursor solution were removed by placing it in a vacuum chamber and alternating between vacuum and normal pressure. Afterwards, it was cured at room temperature to form a high-tensile polydimethylsiloxane (PDMS) substrate on the auxiliary substrate.

S20: Formation of patterned electrode layer on high tensile substrate

Negative photoresist (AZ5214e, MicroChemicals) was spin-coated on the manufactured high-tensile strength substrate and heat treated at approximately 95°C for 2 minutes. Afterwards, the electrode layer formation area was designated in the pattern form of Figure 3 using a mask aligner (MA6, Suss Microtech). The designated area was exposed using a light source of 405 nm, 20 mW/cm ² , and then the substrate was treated with a developer (CD-30, Shipley) for 1 minute and 30 seconds. Thereafter, the auxiliary substrate was washed with distilled water, treated with N ₂ and dried to form a patterned photoresist on the high-tensile strength substrate.

Next, titanium (Ti) was deposited through sputtering deposition on the patterned area from which the photoresist was removed to form an adhesive layer, and gold (Au) was deposited on the titanium to form an electrode layer.

After forming the electrode layer, the patterned photoresist layer was removed using a lift off process. Specifically, the substrate on which the electrode layer was formed was immersed in acetone to remove the remaining photoresist, and a patterned electrode layer was formed.

S30: Formation of conductive polymer nanostructure on patterned electrode layer

A nanostructure was formed using polyaniline (PANI) as a conductive polymer.

Specifically, 8mM to 14mM of aniline was dissolved in 1M HClO ₄ (70%) to prepare an aqueous solution of aniline (C ₆ H ₅ NH ₂ , ~99.5%). Next, an aqueous solution of APS (H ₈ N ₂ O ₈ S ₂ , ~98%) was prepared by dissolving 1M HClO ₄ at a ratio of aniline [M] / APS [M] = 1.5. Both the aniline aqueous solution and the APS aqueous solution were maintained at about 0°C. Afterwards, the APS aqueous solution was added drop by drop to the aniline aqueous solution, and the substrate prepared in S20 was attached to the wall of the beaker containing the mixed solution of the aniline aqueous solution and the APS aqueous solution, and then stirred at a speed of 200 rpm using a magnetic stirrer at about 0°C. Polyaniline nanostructures were grown by polymerizing for 24 hours while maintaining . The polyaniline nanostructure was grown in the form of a nanowire, and the diameter of the nanowire was observed to be 40 to 60 nm.

S40: Removal of auxiliary board

Afterwards, the substrate on which the polyaniline nanostructure was formed in step S30 was immersed in a solution of acetone diluted in water for about 5 minutes. Afterwards, the swollen high-tensile substrate was separated from the auxiliary substrate to manufacture a body-worn hearing sensor.

<Production Example 2>

Conductivity during the formation of conductive polymer nanostructures on the patterned electrode layer (S30) A body-worn hearing sensor was manufactured in the same manner as Preparation Example 1, except that a polyaniline nanostructure as a polymer nanostructure was manufactured in the following manner.

Specifically, an aniline solution was prepared by dissolving 0.3M aniline in 0.7MH ₂ SO ₄ (98%) aqueous solution by stirring at 500 rpm for 1 hour. In the reaction chamber, the electrode-formed substrate prepared in S20 was used as a working electrode, and a graphite rod was used as a counter electrode. The gap between the two electrodes was kept constant at 10 mm, and after adding aniline solution as an electrolyte, the counter electrode A high voltage was applied to the contrast working electrode, and the polyaniline nanostructure was polymerized for 30 seconds to 5 minutes at a fixed potential difference of 1.0 V to 2.0 V. After synthesizing the polyaniline nanostructure, the substrate was dried at 70°C for 10 minutes using a hot plate. The size of the polymerized polyaniline nanocomposite was observed to vary from 0 nm to 15 μm.

As described above, although the embodiments have been described with limited examples and drawings, various modifications and variations can be made by those skilled in the art from the above description. For example, even if the described techniques are performed in a different order than the described method, and/or the described components are combined or combined in a different form than the described method, or are replaced or substituted by other components or equivalents. Adequate results can be achieved. Therefore, other implementations, other embodiments, and equivalents of the claims also fall within the scope of the claims described below.

10: High tensile substrate
20: electrode layer
30: Conductive polymer nanostructure

Claims (12)

High tensile substrate with a tensile strength of 50% or more;
A patterned electrode layer formed on the high tensile substrate; and
Comprising polyaniline (PANI) nanostructures formed on the patterned electrode layer.
Multi-functional sensor. According to paragraph 1,
A multi-functional sensor, wherein the high-tensile substrate is a high-tensile polymer substrate selected from the group consisting of polydimethylsiloxane (PDMS), polyurethane (PU), and Ecoflex. According to paragraph 1,
The electrode layer is a metal selected from titanium (Ti), gold (Au), platinum (Pt), and silver (Ag); or polyfluorene, polyphenylene, polypyrene, polyazulene, polynaphthalene, polyacetylene (PAC), poly(p-phenylene vinylene) (PPV), polypyrrole (PPY), polycarbazole, polyindole, polya. A polyconductive polymer selected from zepine, polyaniline (PANI), polythiophene (PT), poly(3,4-ethylenedioxythiophene) (PEDOT), and poly(p-phenylene sulfide) (PPS). Features a multi-functional sensor. According to paragraph 1,
The electrode layer is a multifunctional sensor characterized in that it has a pattern of a horizontal interdigitated electrode (IDE) structure including a plurality of finger electrodes with a predetermined spacing on a plane. According to paragraph 1,
The multi-function sensor is characterized in that it further includes an adhesive layer between the high-tensile substrate and the electrode layer. delete delete According to paragraph 1,
The polyaniline (PANI) nanostructure is a multifunctional sensor characterized in that an inter-bridge is formed between the polyaniline (PANI) nanostructures when grown. According to paragraph 1,
The multi-functional sensor is a multi-functional sensor characterized in that it detects tensile or deformation strain through changes in electrical conductivity flowing in an inter-bridge between polyaniline (PANI) nanostructures formed on an electrode layer in a high-tensile substrate. Forming a high-tensile strength substrate with a tensile strength of 50% or more on an auxiliary substrate (S10);
Forming a patterned electrode layer on the high tensile substrate (S20);
Forming polyaniline (PANI) nanostructures on the patterned electrode layer (S30); and
Including the step (S40) of removing the auxiliary substrate.
Manufacturing method of multifunctional sensor. According to clause 10,
The step (S20) of forming a patterned electrode layer on the high tensile substrate is
Forming a photoresist layer on a high-tensile substrate (S21);
Performing patterning on the photoresist layer (S22);
Forming an electrode layer on the patterned portion (S23); and
A method of manufacturing a multi-functional sensor, comprising the step of removing the photoresist layer to form a patterned electrode layer (S24). According to clause 10,
The step (S30) of forming polyaniline (PANI) nanostructures on the patterned electrode layer is
Forming a photoresist layer except for the plurality of finger electrode regions of the electrode layer (S31);
Forming polyaniline (PANI) nanostructures in a plurality of finger electrode regions (S32); and
A method of manufacturing a multi-functional sensor, comprising the step of removing the photoresist layer (S33).