KR20140081249A - Oxide Thin-Film Transistor Comprising Self-Assembly Monolayer and Method for Preparation thereof - Google Patents

Oxide Thin-Film Transistor Comprising Self-Assembly Monolayer and Method for Preparation thereof Download PDF

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KR20140081249A
KR20140081249A KR1020120150803A KR20120150803A KR20140081249A KR 20140081249 A KR20140081249 A KR 20140081249A KR 1020120150803 A KR1020120150803 A KR 1020120150803A KR 20120150803 A KR20120150803 A KR 20120150803A KR 20140081249 A KR20140081249 A KR 20140081249A
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self
gate insulating
assembled monolayer
thin film
film transistor
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이태권
김상복
박은유
문용식
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삼성정밀화학 주식회사
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
    • H01L29/66409—Unipolar field-effect transistors
    • H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
    • H01L29/66742—Thin film unipolar transistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate

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Abstract

The present invention relates to an oxide thin film transistor to which a self-assembled monolayer film is applied and a manufacturing method thereof. A thin film transistor according to the present invention is a thin film transistor including a gate electrode, a gate insulating film, a semiconductor film, and a source / drain electrode on a substrate. The oxide thin film transistor includes a self-assembled monolayer on the gate insulating film, The voltage can be lowered.

Description

TECHNICAL FIELD [0001] The present invention relates to an oxide thin film transistor using a self-assembled monolayer, and a manufacturing method thereof.

The present invention relates to an oxide thin film transistor to which a self-assembled monolayer film is applied and a manufacturing method thereof. To an oxide thin film transistor capable of improving mobility and lowering a threshold voltage by treating a self-assembled monolayer film on an insulating surface of a gate insulating film, and a method for manufacturing the same.

Oxide thin film transistor (Oxide TFT) not only enables realization of large-area and high-resolution display, but also can be applied to non-glasses 3D TV. Oxide material can be processed at low temperature and is suitable material for flexible display using plastic substrate . In addition, since the energy band gap is usually larger than 3 eV, it is attracting much attention as a next generation transistor applicable to a transparent display.

Oxide TFT is a backplane driving device for various display panels, and its potential and technological practicality are fully appreciated. Major display panel companies such as Korea and Japan are investing in research and development with mass production in mind. Oxide TFT is expected to emerge in the LCD, AMOLED, and electronic paper panel markets.

On the other hand, as a requirement for commercialization of such a product, the oxide TFT has to have a high mobility, the threshold voltage (V th ) must be lowered, the threshold voltage shift due to bias stress is reduced, Characteristics are required. However, in the case of an oxide TFT close to such a demand, it is still difficult to secure stable driving and reproducibility of the device.

The present inventors have found that when a self-assembled monolayer film is applied to an insulating surface of a gate insulating film in order to improve the mobility of the oxide thin film transistor and lower the threshold voltage, The interface characteristics can be improved, and thus the mobility can be improved and the threshold voltage can be lowered. Thus, the present invention has been completed.

SUMMARY OF THE INVENTION An object of the present invention is to provide an oxide thin film transistor using a self-assembled monolayer.

Another object of the present invention is to provide a method of manufacturing an oxide thin film transistor using a self-assembled monolayer.

According to an aspect of the present invention, there is provided an oxide thin film transistor including a gate electrode, a gate insulating film, a semiconductor film, and a source-drain electrode on a substrate, wherein the oxide thin film transistor further includes a self-assembled monolayer on the gate insulating film Oxide thin film transistor.

In the oxide thin film transistor according to the present invention, the monomolecular molecules forming the self-assembled monolayer may be selected from the group consisting of chlorosilanes, alkylsiloxanes having 8 to 18 carbon atoms, hexamethyldisilazane, carboxylic acid derivatives and phosphoric acid derivatives Is preferably selected.

In the oxide thin film transistor according to the present invention, it is preferable that the thickness of the gate insulating film is 100 to 1,000 nm, and the thickness of the self-assembled monolayer is within a range of 0.2 to 2.0 nm.

The interfacial characteristics can be controlled by introducing a hydrophobic group or a hydrophilic group into the terminal group of the monomolecules forming the self-assembled monolayer.

In the oxide thin film transistor according to the present invention, the oxide thin film transistor includes a substrate / a gate electrode / a gate insulating film / a self-assembled monolayer / a semiconductor film / a source / drain electrode structure and a substrate / a gate electrode / a gate insulating film / Drain electrode / semiconductor film structure, and the like.

According to another aspect of the present invention, there is provided a method of manufacturing an oxide thin film transistor including a gate electrode, a gate insulating film, a semiconductor film, and a source-drain electrode on a substrate, And forming the oxide thin film transistor.

The step of forming a self-assembled monolayer on the gate insulating layer may include forming an -OH functional group on the gate insulating layer and then supporting the substrate in an organic solution containing monomolecular monomolecular film forming monolayer The chamber is vacuumed using a vacuum pump, and a monomolecular liquid for forming a self-assembled monolayer is injected. The substrate is subjected to a heat treatment at a temperature ranging from room temperature to 100 ° C according to the characteristics of the material, Can be formed.

The oxide thin film transistor according to the present invention lowers the threshold voltage as well as improving the mobility of the thin film transistor by applying a self-assembled monolayer film to prevent charge trapping due to the -OH functional group on the insulating surface of the gate insulating film.

1 is a cross-sectional view illustrating a structure of an oxide thin film transistor according to an embodiment of the present invention.
2 is a cross-sectional view illustrating a structure of an oxide thin film transistor according to another embodiment of the present invention.
3 is a schematic view showing a structure in which a self-assembled monolayer film is formed using octadecyltrichlorosilane on a SiO 2 gate insulating film.
4 is an output (Id-Vd) curve obtained by increasing the gate voltage from 0 V to 60 V by 10 V and sweeping the drain voltage from 0 to 60 V, respectively, according to the present invention.
5 to 6 are graphs showing transfer (Id-Vg) and transfer (Id-Vg) obtained by changing the gate voltage from -20 V to 80 V while keeping the drain voltage at 40 V, 1/2 -Vg) curve.

Hereinafter, the present invention will be described in more detail with reference to the drawings.

FIG. 1 is a cross-sectional view of an oxide thin film transistor manufactured according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view of an oxide thin film transistor manufactured according to another embodiment of the present invention.

1 to 2, an oxide thin film transistor according to the present invention includes a substrate 100, a gate electrode 102, a gate insulating film 104, a self-assembled monolayer 106, an oxide semiconductor film 108, Drain electrode 110 or the substrate 100, the gate electrode 102, the gate insulating film 104, the self-assembling monolayer 106, the source-drain electrode 110 and the oxide semiconductor film 108.

Meanwhile, the structure of the oxide thin film transistor according to the above-described FIG. 1 and FIG. 2 may be changed to improve the characteristics of the transistor, and is not limited to the structure of the two devices.

In particular, with reference to FIG. 1, each layer of an oxide thin film transistor according to the present invention will be described.

In the oxide thin film transistor according to the present invention, the substrate 100 may be a substrate commonly used in this field, preferably a silicon wafer, a glass substrate, or a plastic substrate.

The gate electrode 102 formed on the substrate 100 may be formed to a thickness of 100 to 1,000 nm using a metal thin film layer or an oxide conductive thin film layer having high conductivity. As the metal, silver, aluminum, aluminum alloy, tungsten, copper, nickel, chromium, molybdenum, molybdenum, tungsten alloy, titanium, platinum and tantalum may be used. In particular, an oxide thin film transistor Indium-tin oxide (ITO), indium-zinc oxide (IZO), or the like may be used.

The gate electrode 102 may be formed by a method commonly used in this field and may be patterned by a suitable patterning method, for example, an etching process.

A gate insulating layer 104 is formed on the gate electrode 102 to a thickness of 100 to 1,000 nm. The gate insulating film 104 is an electrically insulating film and is located between the gate electrode 102 and the semiconductor film 108 to be formed in a subsequent process.

Typical materials constituting the gate insulating film 104 include a silicon-based insulating film such as a silicon oxide film (SiO 2 ), a silicon nitride film (SiN), a silicon oxynitride film (SiON), an aluminum oxide film (Al 2 O 3 ), a hafnium oxide film 2 ), a zirconium oxide film (ZrO 2 ), and various organic insulating film materials having good insulating film characteristics.

The gate insulating layer 104 may be formed using various methods such as atomic layer deposition (ALD), chemical vapor deposition (CVD), plasma Chemical vapor deposition (PECVD), reactive sputtering, and the like. Various methods can be used in combination or modification of these methods.

Then, a self-assembled monolayer 106 is formed on the gate insulating layer 104 to prevent charge trapping by the -OH functional group on the surface of the gate insulating layer 104.

As the monolayer forming the self-assembled monolayer 106, monomolecules generally used in this field can be used, but in particular, chlorosilanes such as octadecyltrichlorosilane, octadecyltrimethoxysilane and octadecyltrimethoxysilane such as octadecyltrichlorosilane, Hexamethyldisilazane, carboxylic acid derivatives, and phosphoric acid derivatives represented by decyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, and the like.

More preferably, when the gate insulating film is a silicon-based insulating film, an alkylsiloxane such as chlorosilane-based, octadecyltrimethoxysilane, or octadecyltriethoxysilane such as octadecyltrichlorosilane or hexamethyldisilazane is preferable And when the gate insulating film is a metal oxide based insulating film, a carboxylic acid derivative or a phosphoric acid derivative is preferable.

A method of forming the self-assembled monolayer 106 on the gate insulating film 104 can be either a liquid phase method or a vapor phase method, and any method can be adopted as long as reproducibility can be ensured. In the case of the liquid phase method, a substrate having a gate insulating film formed thereon is supported on a piranha solution, or a? H functional group is formed on the gate insulating film through UV-ozone treatment, and then the substrate is immersed in an organic And the chamber is vacuumed by using a vacuum pump. Then, a monomolecular liquid for forming a self-assembled monolayer is injected, and heat treatment is performed from room temperature to about 100 ° C according to the characteristics of the material The self-assembled monolayer film can be formed on the substrate having the gate insulating film formed thereon.

The formation of the alkylsiloxane self-assembled monolayer on the gate insulating film is performed as shown in the following reaction scheme 1.

[Reaction scheme 1]

Figure pat00001

As shown in Reaction Scheme 1, a thin film of water and -OH is present on the surface of the SiO 2 gate insulating film, and the alkyl siloxane is physically adsorbed on the film. The alkyl chains that are physically adsorbed in this way become fluid and become close to each other. Subsequently, the Si-X bonds are formed into Si-OH bonds through hydrolysis, and the alkyl siloxane is adsorbed. At this time, the generated OH functional group reacts with OH functional groups on the oxidized surface, and Si-O-Si bond is formed on the substrate through the condensation reaction. Si-O-Si bonds are generated while adjacent head groups cross-react.

In addition, formation of HMDS (hexamethyldisilazane) self-assembled monolayer on the gate insulating film is formed in accordance with the following reaction scheme.

[Reaction Scheme 2]

Figure pat00002

As shown in Reaction Scheme 2, the electron-rich oxygen of the -OH functional group formed on the surface of the SiO 2 gate insulating film causes a nucleophilic substitution reaction with the silicon atom of the HMDS, and the Si-O-Si (CH 3 ) 3 bond is formed. The Si-O-Si bonds are also formed by adjacent head groups in close proximity to each other.

The self-assembled monolayer film is treated on the gate insulating film using octadecyltrichlorosilane, which is one of the alkylsiloxanes, and is shown in FIG. The roughness of the surface of the gate insulating film can be alleviated through the self-assembled monolayer film processing of the long chain, and the charge mobility in the thin film transistor can be increased because the surface roughness is related to the surface roughness.

The self-assembled monolayer 106 is preferably formed to a thickness of 0.2 to 2.0 nm. When the thickness is less than 0.2 nm, the self-assembled monolayer 106 is not self-assembled due to van der Waals attraction due to intermolecular overlap, The roughness of the self-assembled film surface is lowered due to the random folding of the long alkyl chains, and the mobility is deteriorated.

In addition, the self-assembled monolayer 106 is a hydrophobic group in the terminal groups of a single molecule to form a (e.g., -CH 3), or a hydrophilic group (e.g., -OH, or -COOH) to control the interface properties by introducing a have. That is, since the hydrophilic group and the hydrophobic group can be freely introduced at the end of the monomolecular film forming the self-assembled monolayer, the characteristics according to the composition of the semiconductor film and the interface property of the gate insulating film can be easily controlled, and the adsorption and electric characteristics at the interface can be optimized.

In addition, fine patterning may be possible in the fabrication of an oxide thin film transistor by a solution process using the hydrophilic group and the hydrophobic group.

The oxide semiconductor film 108 may be formed to a thickness of 10 to 50 nm on the gate insulating film 104 surface-treated with the self-assembled monolayer film 106.

The oxide semiconductor film 108 may be a variety of oxide materials that are both oxides and electrically semiconducting. In particular, a transparent oxide semiconductor layer, for example, IGZO, ZnO, ZTO or the like is preferably used to fabricate an oxide thin film transistor which is manufactured on a glass substrate and has a transparent property.

The oxide semiconductor film 108 may be formed by various methods such as spin coating, slit coating, inkjet printing, reverse off-jet coating, And vacuum deposition processes such as atomic layer deposition (ALD), chemical vapor deposition (CVD), and reactive sputtering, but the present invention is not limited to these processes.

After the oxide semiconductor film 108 is formed, patterning of the oxide semiconductor thin film layer 108 can be performed by a general patterning method in this field, for example, a wet etching method or a dry etching method.

A source / drain electrode 110 is formed on the oxide semiconductor film 108 to a thickness of 50 to 100 nm. Like the gate electrode 102, the source / drain electrode 110 may use a metal thin film layer or an oxide conductive thin film layer having high conductivity. In particular, in order to fabricate an oxide thin film transistor having transparency formed on a glass substrate, it is preferable that the source / drain electrode 110 also use a transparent oxide conductive thin film layer.

Since the source / drain electrode 110 is electrically in direct contact with the semiconductor portion, unlike the gate electrode 102, an ohmic contact is formed at the contact portion with the semiconductor layer, . For example, aluminum zinc oxide (ZnO: Al) doped with Al at an appropriate concentration may be used for ITO or ZnO which is typically used. The source / drain electrode 110 is patterned at a predetermined position by using a suitable patterning method, for example, an etching process.

2, the gate electrode 102, the gate insulating film 104, and the self-assembled monolayer 106 are formed on the substrate 100 in the same manner as in FIG. 1, / Drain electrode 110 is first formed and patterned, and then an oxide semiconductor film 108 is formed thereon and etched.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

Example 1

Fabrication of self-assembled monolayer TFT using octadecyltrimethoxysilane

A gate electrode was deposited by sputtering to a thickness of 100 nm on the silicon substrate using molybdenum (Mo), and a 100 nm thick SiO 2 insulating film was formed by a PECVD process on the gate electrode. Then, fresh Si-OH was formed by immersing the substrate on which the insulating film was formed in a sulfuric acid (Hydrogenperoxide = 4: 1) solution for 30 minutes, and then ultrasonic waves were applied in the order of DI water and isopropyl alcohol Washed and dried in an oven for 30 minutes to remove moisture. Subsequently, the substrate was immersed in a toluene solution containing 0.25 wt% of OTS (octadecyltrimethoxysilane) monomer for 30 minutes, and ultrasonically cleaned in the order of toluene and IPA to form an OTS self-assembled monolayer. Then, an oxide semiconductor (IGZO) sol-gel solution was spin-coated on the SAM-treated gate insulating film at 500 rpm for 5 seconds and at 3000 rpm for 30 seconds to form a thin film. Treated in an oven at 150 캜 for 10 minutes and at 350 캜 for 30 minutes in an air atmosphere. Aluminum was deposited to a thickness of 50 nm by using a shadow mask to fabricate a TFT device composed of a source / drain electrode having a pattern of W / L = 1000 nm / 100 nm .

Example 2

Fabrication of self-assembled monolayer TFT using HMDS

A TFT device was fabricated in the same manner as in Example 1, except that HMDS was used instead of the OTS (octyltrimethoxysilane) monomer.

Comparative Example 1

Fabrication of a TFT device was completed in the same manner as in Example 1, except that the OTS self-assembled monolayer film was not formed on the SiO 2 insulating film.

Evaluation example 1

After the probe was probed to the gate and source / drain electrodes of the TFT manufactured according to Example 1 of the present invention, the gate voltage was increased from 0 V to 60 V by 10 V and the drain voltage was swept from 0 to 60 V, (output, Id-Vd) curve, which is shown in FIG.

While the drain voltage of each of the TFT manufactured in accordance with the first embodiment of the present invention was fixed to 40 V, varying the gate voltage of 80V to - 20 to transfer (transfer, Id-Vg) and mobility extract (Id 1 / 2 -Vg) curves are shown in FIGS. 5 and 6, and the mobility, threshold voltage and current blink ratio in the saturation region are extracted by the following formula, and the results are shown in Table 1 below .

The mobility, threshold voltage, and current flicker ratio of the TFT fabricated in Example 2 and Comparative Example 1 were also extracted in the same manner and the results are shown in Table 1 below.

Equation 1

Figure pat00003

Example 1 Example 2 Comparative Example 1 Mobility (unit) 1.4 cm 2 / V · s 1.2 cm 2 / V · s 0.4 cm 2 / V · s Threshold Voltage (Unit) 15 V 17 V 24 V Current flashing ratio (unit) 2 x 10 7 8 x 10 6 1 x 10 6

It can be seen from Table 1 that the mobility of the oxide thin film transistor according to the present invention is improved as compared with the conventional mobility, and that the threshold voltage is much lower than the conventional threshold voltage.

Claims (8)

1. An oxide thin film transistor comprising a gate electrode, a gate insulating film, a semiconductor film, and a source-drain electrode on a substrate,
And a self-assembled monolayer formed on the gate insulating layer. The method according to claim 1,
The monolayer forming the self-assembled monolayer may be selected from the group consisting of chlorosilanes, alkylsiloxanes having 8 to 18 carbon atoms, hexamethyldisilazane, carboxylic acid derivatives and phosphoric acid derivatives. The method according to claim 1,
Wherein the thickness of the gate insulating layer is 100 to 1,000 nm, and the thickness of the self-assembled monolayer is within a range of 0.2 to 2.0 nm. The method according to claim 1,
Wherein the interfacial characteristics are controlled by introducing a hydrophobic group or a hydrophilic group into the end group of the monomolecule forming the self-assembled monolayer. The method according to claim 1,
The oxide thin film transistor
Substrate / gate electrode / gate insulating film / self-assembled monolayer / semiconductor film / source-drain electrode structure; And
And a structure selected from the group consisting of a substrate, a gate electrode, a gate insulating film, a self-assembled monolayer film, a source-drain electrode, and a semiconductor film structure. A method of manufacturing an oxide thin film transistor including a gate electrode, a gate insulating film, a semiconductor film, and a source-drain electrode on a substrate,
And forming a self-assembled monolayer on the gate insulating layer. The method according to claim 6,
The step of forming the self-assembled monolayer on the gate insulating layer includes forming a -OH functional group on the surface of the gate insulating layer and then supporting the gate insulating layer in an organic solution containing monomolecular monomolecular film- A method of manufacturing a transistor. The method according to claim 6,
The step of forming the self-assembled monolayer on the gate insulating layer may include forming a chamber in a vacuum state by using a vacuum pump, injecting a monomolecular liquid for forming the self-assembled monolayer, and annealing the self-assembled monolayer Wherein the oxide thin film transistor is formed on the substrate.

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KR20160055334A (en) * 2014-11-07 2016-05-18 서울시립대학교 산학협력단 Organic field-effect transistors, and method for preparing thereof
US10991894B2 (en) 2015-03-19 2021-04-27 Foundation Of Soongsil University-Industry Cooperation Compound of organic semiconductor and organic semiconductor device using the same
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KR20190069946A (en) * 2017-12-12 2019-06-20 재단법인 나노기반소프트일렉트로닉스연구단 Method for preparing surface modified polymer thin film and method for fabricating organic electronic device comprising the same
WO2019190463A1 (en) * 2018-03-26 2019-10-03 Intel Corporation Multifunctional molecules for selective polymer formation on conductive surfaces and structures resulting therefrom
US11398428B2 (en) 2018-03-26 2022-07-26 Intel Corporation Multifunctional molecules for selective polymer formation on conductive surfaces and structures resulting therefrom
CN117276350A (en) * 2023-09-19 2023-12-22 华南理工大学 Zinc oxide-based double-gate thin film transistor and preparation method and application thereof

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