KR20130102148A - Bio sensor using solution-processed oxide thin film transistor and manufacturing method thereof - Google Patents

Bio sensor using solution-processed oxide thin film transistor and manufacturing method thereof Download PDF

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KR20130102148A
KR20130102148A KR1020120023122A KR20120023122A KR20130102148A KR 20130102148 A KR20130102148 A KR 20130102148A KR 1020120023122 A KR1020120023122 A KR 1020120023122A KR 20120023122 A KR20120023122 A KR 20120023122A KR 20130102148 A KR20130102148 A KR 20130102148A
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oxide semiconductor
semiconductor layer
znsno
thin film
dna
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김현재
김시준
정주혜
윤두현
박성하
김병훈
이준의
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연세대학교 산학협력단
성균관대학교산학협력단
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12QMEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
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    • C12Q1/6825Nucleic acid detection involving sensors
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    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/414Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4145Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS specially adapted for biomolecules, e.g. gate electrode with immobilised receptors

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Abstract

The present invention relates to a biomaterial detection sensor such as DNA using a solution process oxide thin film transistor.
In other conventional thin film transistor biosensor manufacturing, in order to overcome both the cost burden of performing the vacuum deposition process and the environmental and thermal vulnerability associated with the organic thin film transistor biosensor, the present invention provides an oxide based solution solution. By providing a thin film transistor biosensor, a high-sensitivity biosensor with reliability, reproducibility, environmental / heat excellence, and high electrical characteristics can be mass-produced at low cost.
Immobilization of DNA or the like in the exposed channel region of the oxide thin film transistor of the present invention reduces mobility, thereby reducing the current flowing in the channel. It is possible to detect the presence of DNA or the like.

Description

Oxide thin film transistor biosensor based on solution process and its manufacturing method {BIO SENSOR USING SOLUTION-PROCESSED OXIDE THIN FILM TRANSISTOR AND MANUFACTURING METHOD THEREOF}

The present invention relates to a biosensor using a field effect transistor and a method of manufacturing the same, and more particularly, to a biomaterial detection sensor such as DNA using a solution process oxide thin film transistor (Oxide Thin Film Transistor) and a manufacturing method thereof. will be.

Recently, as interest in human health and safety increases, studies on biosensors, particularly DNA detection methods, are being actively conducted. Conventional DNA detection methods utilize a fluorescence detection method of a labeled probe or target, but there is a limitation in that an expensive optical system is required and sensitivity is limited. Therefore, label-free methods such as electrochemical detection, microcantilever, and various field effect transistors have been proposed. In particular, the DNA detection method using organic thin film transistors among various field effect transistors has high sensitivity, and can be directly converted (Direct Transduction) detection, and the low cost of manufacturing can be noted recently. I am getting it. However, in the case of an organic thin film transistor, due to the inherent reactivity of the organic material, a relatively high sensitivity sensor can be manufactured, but on the other hand, it is easily modified due to the reactivity of the organic material, which leads to reliability and reliability. Reproducibility issues, environmental / heat vulnerability issues, and low electrical properties still remain to be improved.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-described problems, and an object of the present invention is to maintain advantages such as high sensitivity of organic thin film transistors, direct conversion detection, and low cost manufacturing. At the same time, it seeks to overcome disadvantages such as reliability, reproducibility, environmental / heat vulnerability, and low electrical properties.

Therefore, the present invention is to solve the above problems by applying an oxide thin film transistor (Oxide Thin Film Transistor) excellent in reliability and reproducibility compared to the organic thin film transistor in addition to the advantages, such as high sensitivity, low cost manufacturing.

According to the present invention,

Board;

A gate electrode formed on the substrate;

A gate insulating film formed on the gate electrode;

An oxide semiconductor layer formed on the gate insulating film; and

A source effect transistor comprising: a source and drain electrode formed on the oxide semiconductor layer, the oxide semiconductor layer being exposed;

A biomaterial is bonded to a portion of the oxide semiconductor layer exposed between the source and drain electrodes to detect a component of the biomaterial from a current-voltage characteristic of the field effect transistor. Can be.

In addition, the present invention, the oxide semiconductor is nGaZnO, ZnO, ZrInZnO, InZnO, AlInZnO, ZnO, InGaZnO 4 , ZnInO, ZnSnO, In 2 O 3 , Ga 2 O 3 , HfInZnO, GaInZnO, HfO 2 , SnO 2 , WO 3 , TiO 2 , Ta 2 O 5 , In 2 O 3 SnO 2 , MgZnO, ZnSnO 3 , ZnSnO 4 , CdZnO, CuAlO 2 , CuGaO 2 , Nb 2 O 5, or any one of TiSrO 3 or a compound thereof A field effect transistor biosensor can be provided.

In addition, the present invention, the bio-material to be detected, single-strained DNA (ssDNA), double-stranded DNA (double-strained DNA: dsDNA), nanostructured DNA (nanostructure DNA), antigen (antigen), It is possible to provide a field effect transistor biosensor comprising an antibody.

Further, according to the present invention,

Applying an oxide semiconductor solution onto a substrate including a gate electrode and a gate insulating film covering the gate electrode;

Heat treating the oxide semiconductor solution to form an oxide semiconductor layer;

Forming a source and a drain electrode on the oxide semiconductor layer, wherein the oxide semiconductor layer is exposed;

A biosensor manufacturing method may be provided by bonding a biodetector to the exposed oxide semiconductor layer to detect a biomaterial from current-voltage characteristics of a field effect transistor.

In addition, the present invention, the oxide semiconductor layer is nGaZnO, ZnO, ZrInZnO, InZnO, AlInZnO, ZnO, InGaZnO 4 , ZnInO, ZnSnO, In 2 O 3 , Ga 2 O 3 , HfInZnO, GaInZnO, HfO 2 , SnO 2 , Any one selected from WO 3 , TiO 2 , Ta 2 O 5 , In 2 O 3 SnO 2 , MgZnO, ZnSnO 3 , ZnSnO 4 , CdZnO, CuAlO 2 , CuGaO 2 , Nb 2 O 5, or TiSrO 3 , or a compound of these materials It can provide a biosensor manufacturing method characterized in that it is included.

In addition, the solvent of the solution forming the oxide semiconductor layer is acetic acid, ammonia, water, methanol, methanol, ethanol, 2-methoxyethanol ( Polar group consisting of 2-methoxyethanol), formamide, or acetone, benzene, chloroform, chloroform, dimethylsulfoxide, dioxane, dioformane, dimethylformamide, Selected from tetrahydrofuran,

The solution is prepared by using a sol-gel method,

As a method of forming an oxide semiconductor layer on the substrate, screen printing, spin coating, dip coating, spray method, roll-to-roll process Alternatively, a method of manufacturing a biosensor using any one method selected from ink-jet methods may be provided.

In addition, the present invention, the method of immobilizing the bio-detector to the exposed oxide semiconductor layer (immobilization), characterized in that any one selected from pipetting or ink-jet (Ink-jet) method A biosensor manufacturing method can be provided.

Further, according to the present invention,

The channel layer of the field effect transistor is formed of an oxide semiconductor layer based on a solution process,

The biomaterial detection method may be provided by exposing the formed oxide channel region to immobilize the biomaterial to detect the presence of the biomaterial from current-voltage characteristics.

In addition, the present invention, the oxide semiconductor is nGaZnO, ZnO, ZrInZnO, InZnO, AlInZnO, ZnO, InGaZnO 4 , ZnInO, ZnSnO, In 2 O 3 , Ga 2 O 3 , HfInZnO, GaInZnO, HfO 2 , SnO 2 , WO 3 , TiO 2 , Ta 2 O 5 , In 2 O 3 SnO 2 , MgZnO, ZnSnO 3 , ZnSnO 4 , CdZnO, CuAlO 2 , CuGaO 2 , Nb 2 O 5, or any one of TiSrO 3 or a compound thereof It is possible to provide a bio-material detection method, characterized in that made.

Forming an oxide semiconductor aqueous solution by a liquid phase manufacturing process on a substrate; And forming an oxide semiconductor thin film by heat treatment on the oxide semiconductor.

In the above, preferably, the method of forming an aqueous solution of the oxide semiconductor on the substrate is screen printing, spin coating, dip coating, spray method, roll-to-roll process Any one method selected from a (Roll-to-Roll) or ink-jet (Ink-Jet) method may be used.

According to the present method, reliability, reproducibility, and environment are achieved by using field effect transistors, one of the label-free methods, in particular, oxide thin film transistors. It is possible to manufacture high-sensitivity biosensor with excellent thermal and electrical characteristics. In addition, by using a solution process it is possible to manufacture a biosensor with a simple manufacturing process and low cost.

1 to 3 are cross-sectional views illustrating a method of manufacturing a solution process oxide thin film transistor according to an embodiment of the present invention and DNA detection using the same.
4 and 5 are atomic force microscopy (AFM) photographs obtained by immobilizing DNA nanostructures on oxide semiconductor thin films and analysis results for confirming the presence of DNA nanostructures.
6 is a result of current-voltage measurement of a solution process oxide thin film transistor after immobilization of a DNA nanostructure.
7 to 10 are current-voltage measurement results of a solution process oxide thin film transistor showing various solvent effects for transferring DNA onto an oxide semiconductor thin film.
11 to 12 are schematic views showing various processing forms of biomaterials that can be detected through the oxide thin film transistor biosensor of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, embodiments of the present invention illustrated below may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. Embodiment of the present invention is provided to more completely describe the present invention to those skilled in the art.

1 to 3 are cross-sectional views illustrating a method of manufacturing a solution process oxide thin film transistor according to an embodiment of the present invention and DNA detection using the same.

First, the solution process oxide thin film transistor is fabricated with a bottom gate structure, or inverted staggered structure, which is a commonly used structure in AMLCDs. In particular, there is an advantage that can reduce the cost, especially during mass production.

An oxide semiconductor layer 230 is formed on the substrate 200 by a liquid phase manufacturing process. Specifically, for example, InGaZnO, ZnO, ZrInZnO, InZnO, AlInZnO, ZnO, InGaZnO 4 , ZnInO, ZnSnO, In 2 O 3 , Ga 2 O 3 , HfInZnO, GaInZnO, HfO 2 , SnO 2 , WO 3 , TiO 2 , Ta 2 O 5 , In 2 O 3 SnO 2, MgZnO, ZnSnO 3, ZnSnO 4 , CdZnO, CuAlO 2 , CuGaO 2 , Nb 2 O 5, or an oxide semiconductor including a compound of the above, or an oxide semiconductor including a compound of the above materials, for example, a sol-gel (Sol-gel) It is manufactured in a liquid state, such as a gel) method and applied onto the substrate 200.

Here, the substrate 200 may be formed of an insulating material such as, for example, glass, plastic, silicon, or synthetic resin, and includes a gate electrode 210 and a gate insulating film 220.

Here, any solvent used for forming the oxide semiconductor layer 230 may be used without limitation as long as it can dissolve the metal compound. Specifically, a polar group consisting of acetic acid, ammonia, water, methanol, ethanol, 2-methoxyethanol, and formamide Or may be selected from acetone, benzene, chloroform, dimethyl sulfoxide, dithythyformamide, dioxane, dioxane, dimethylformamide, and tetrahydrofuran.

As a method of applying a solution for forming the oxide semiconductor layer 230 on the substrate 200, for example, a screen printing method, a spin coating method or an ink-jet method, etc. It is possible to use, but not limited to.

The oxide semiconductor layer 230 coated in the liquid phase is heat treated. In this case, as the heat treatment method, it is possible to use a furnace, a hot plate, a laser, and the like, but is not limited thereto.

The source 240 and the drain 250 electrodes are placed on the heat-treated oxide semiconductor layer 230 thin film. In this case, the source and drain electrodes 240 and 250 may be patterned by using a mask or a lithography process. Accordingly, the channel region of the oxide semiconductor layer 230 may be exposed.

An biomaterial 260 such as DNA is immobilized to the exposed oxide semiconductor channel region. In this case, a pipetting or ink-jet method may be used as the method of immobilization, but is not limited thereto. At this time, the biomaterial 260 such as DNA may be selected from among single-strained DNA (ssDNA), double-strained DNA (dsDNA) and DNA nanostructure.

Example

Into: Ga: Zn = 3: 1: 2 ratio was added to 2-methoxyethanol solvent to prepare a 0.5 M solution.

In, Ga, Zn was used as the precursor (precursor) as follows.

indium nitrate hydrate [In (NO 3 ) 3 H 2 O]

gallium nitrate hydrate [Ga (NO 3 ) 3 H 2 O]

zinc acetate dihydrate [Zn (CH 3 COO) 2 H 2 O]

In addition, after the solution was applied to the substrate 200, the heat treatment process was pre-heat treatment at about 300 minutes at 300 ℃, after about 2 hours at 500 ℃.

However, in addition to the above specific values, it is possible to prepare a mol ratio solution of various oxide solutions, and the heat treatment temperature may be different, and in particular, a thin film may be sufficiently formed by controlling the heating time at a low temperature of 300 ° C or lower.

Reference is now made to the analysis of specimens obtained according to the examples.

FIG. 4 is an atomic force microscopy (AFM) photograph of an immobilized DNA nanostructure on an oxide semiconductor thin film. In the left side, the oxide semiconductor thin film itself is shown. On the right, a DNA nanostructure is bonded. to be. DNA can be spliced into various forms, for example, polygonal nanostructures, with large spots in the picture on the right indicating a bundle of DNA.

5 is a photograph showing an analysis result for confirming the presence of DNA nanostructures (nanostructure). The photo on the left shows the horizontal size, and the photo on the right shows the vertical size.

FIG. 6 shows current-voltage measurement results of a solution process oxide thin film transistor after immobilization of a DNA nanostructure. Compared to the graph without DNA nanostructures, when the DNA nanostructures are bonded, they show a significantly lower current curve, indicating that they can function as a sufficient detection sensor, and only solvents can be bonded for differentiation from solvent effects. One graph is also shown, in which case the current change is insignificant, indicating that it is sufficient to be used as a sensor for detecting DNA nanostructures.

7 to 10 illustrate the current-voltage measurement of a solution process oxide thin film transistor showing various solvent effects for transferring DNA onto an oxide semiconductor thin film. The solvent can be selected.

Fig. 11 schematically shows DNA structures detectable by a biosensor using an oxide thin film transistor of the present invention. Although they are intact, they can be processed into various other shapes, and the processed ones are detected with high sensitivity through the oxide thin film transistor of this embodiment. 12 also shows a DNA track structure that can be detected through the oxide thin film transistor of this embodiment.

According to the DNA detection method using the solution process oxide thin film transistor of the present invention as described above, the reliability and reproducibility problems of the existing organic thin film transistor It also has the advantage of improving the environmental / heat vulnerability, low electrical characteristics. In addition, with the high sensitivity of the organic thin film transistor (Organic Thin Film Transistor), it is possible to detect the direct conversion (Direct Transduction), and also maintain the advantage that it can be manufactured at low cost.

Although a preferred embodiment of the DNA detection method using the solution process oxide thin film transistor according to the present invention described above has been described, the present invention is not limited thereto, but the claims and the detailed description of the invention and the accompanying It is possible to carry out various modifications within the scope of one drawing and this also belongs to the present invention.

200: substrate
210: gate
220: gate insulating film
230: oxide semiconductor layer
240: source
250: drain
260: biomaterial

Claims (9)

Board;
A gate electrode formed on the substrate;
A gate insulating film formed on the gate electrode;
An oxide semiconductor layer formed on the gate insulating film; and
A source effect transistor comprising: a source and drain electrode formed on the oxide semiconductor layer, the oxide semiconductor layer being exposed;
And bonding a biomaterial to a portion of the oxide semiconductor layer exposed between the source and drain electrodes to detect a component of the biomaterial from the current-voltage characteristics of the field effect transistor.
The method of claim 1, wherein the oxide semiconductor is nGaZnO, ZnO, ZrInZnO, InZnO, AlInZnO, ZnO, InGaZnO 4 , ZnInO, ZnSnO, In 2 O 3 , Ga 2 O 3 , HfInZnO, GaInZnO, HfO 2 , SnO 2 , WO 3 , TiO 2 , Ta 2 O 5 , In 2 O 3 SnO 2 , MgZnO, ZnSnO 3 , ZnSnO 4 , CdZnO, CuAlO 2 , CuGaO 2 , Nb 2 O 5, or any one of TiSrO 3 or a compound thereof Field effect transistor biosensor, characterized in that is made. The biomaterial of claim 1, wherein the biomaterial to be detected is a single-strained DNA (ssDNA), a double-strained DNA (dsDNA), a nanostructured DNA (nanostructure DNA), or an antigen. (antigen), field effect transistor biosensor comprising an antibody (antibody). Applying an oxide semiconductor solution onto a substrate including a gate electrode and a gate insulating film covering the gate electrode;
Heat treating the oxide semiconductor solution to form an oxide semiconductor layer;
Forming a source and a drain electrode on the oxide semiconductor layer, wherein the oxide semiconductor layer is exposed;
And attaching a biodetector to the exposed oxide semiconductor layer to detect a biomaterial from current-voltage characteristics of a field effect transistor.
The method of claim 4, wherein the oxide semiconductor layer comprises nGaZnO, ZnO, ZrInZnO, InZnO, AlInZnO, ZnO, InGaZnO 4 , ZnInO, ZnSnO, In 2 O 3 , Ga 2 O 3 , HfInZnO, GaInZnO, HfO 2 , SnO 2 , Any one selected from WO 3 , TiO 2 , Ta 2 O 5 , In 2 O 3 SnO 2 , MgZnO, ZnSnO 3 , ZnSnO 4 , CdZnO, CuAlO 2 , CuGaO 2 , Nb 2 O 5, or TiSrO 3 , or a compound of these materials Biosensor manufacturing method comprising the. The method of claim 5, wherein the solvent of the solution forming the oxide semiconductor layer is acetic acid, ammonia, water, methanol, methanol, Ethanol, 2-methoxyethanol ( Polar group consisting of 2-methoxyethanol), formamide, or acetone, benzene, chloroform, chloroform, dimethylsulfoxide, dioxane, dioformane, dimethylformamide, Selected from tetrahydrofuran,
The solution is prepared by using a sol-gel method,
As a method of forming an oxide semiconductor layer on the substrate, screen printing, spin coating, dip coating, spray method, roll-to-roll process Or an ink-jet (Ink-Jet) method using any one selected from the method of manufacturing a biosensor.
The method of any one of claims 4 to 6, wherein a method of immobilizing the biodetector to the exposed oxide semiconductor layer is any one selected from pipetting or ink-jet. Biosensor manufacturing method characterized in that using the method. The channel layer of the field effect transistor is formed of an oxide semiconductor layer based on a solution process,
And detecting the presence of the biomaterial from the current-voltage characteristic by exposing the formed oxide channel region to immobilize the biomaterial.
The method of claim 8, wherein the oxide semiconductor is nGaZnO, ZnO, ZrInZnO, InZnO, AlInZnO, ZnO, InGaZnO 4 , ZnInO, ZnSnO, In 2 O 3 , Ga 2 O 3 , HfInZnO, GaInZnO, HfO 2 , SnO 2 , WO 3 , TiO 2 , Ta 2 O 5 , In 2 O 3 SnO 2 , MgZnO, ZnSnO 3 , ZnSnO 4 , CdZnO, CuAlO 2 , CuGaO 2 , Nb 2 O 5, or any one of TiSrO 3 or a compound thereof Bio-material detection method, characterized in that made.
KR1020120023122A 2012-03-07 2012-03-07 Bio sensor using solution-processed oxide thin film transistor and manufacturing method thereof KR20130102148A (en)

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Cited By (7)

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KR101446290B1 (en) * 2014-03-28 2014-10-07 연세대학교 산학협력단 Method for manufacturing flexible bio sensor using solution process
CN105506585A (en) * 2015-12-10 2016-04-20 上海电机学院 Preparation method for copper-gallium oxide infrared transparent conductive nano crystal membrane
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101446290B1 (en) * 2014-03-28 2014-10-07 연세대학교 산학협력단 Method for manufacturing flexible bio sensor using solution process
KR101638501B1 (en) 2015-03-24 2016-07-11 한국과학기술연구원 pH sensor and method for fabricating the same
CN105506585A (en) * 2015-12-10 2016-04-20 上海电机学院 Preparation method for copper-gallium oxide infrared transparent conductive nano crystal membrane
KR20190054740A (en) * 2017-11-14 2019-05-22 주식회사 엘지화학 Method for manufacturing thin film transistor sensors
CN108709915A (en) * 2018-09-01 2018-10-26 罗杰雄 A kind of harmful gas in vehicle detection device
CN108709915B (en) * 2018-09-01 2021-11-19 山东多瑞电子科技有限公司 Harmful gas detection device in car
KR20210157147A (en) 2020-06-19 2021-12-28 성균관대학교산학협력단 Sensor for monitoring 3D-cultured cell or tissue and Method for fabricating the same based on roll-to-roll process
KR20220078168A (en) * 2020-12-03 2022-06-10 아주대학교산학협력단 Ultra-low voltage operated DNA sensor based on solution-processed metal oxide semiconductors and manufacturing method thereof

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