KR20150011936A - Substrate for Thin Film Transistor - Google Patents
Substrate for Thin Film Transistor Download PDFInfo
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- KR20150011936A KR20150011936A KR1020130087167A KR20130087167A KR20150011936A KR 20150011936 A KR20150011936 A KR 20150011936A KR 1020130087167 A KR1020130087167 A KR 1020130087167A KR 20130087167 A KR20130087167 A KR 20130087167A KR 20150011936 A KR20150011936 A KR 20150011936A
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- South Korea
- Prior art keywords
- barrier layer
- substrate
- thin film
- film transistor
- roll
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 70
- 239000010409 thin film Substances 0.000 title claims abstract description 40
- 230000004888 barrier function Effects 0.000 claims abstract description 94
- 229920001721 polyimide Polymers 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 33
- 239000010408 film Substances 0.000 claims description 28
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 26
- 238000002834 transmittance Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000010924 continuous production Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 87
- 230000000052 comparative effect Effects 0.000 description 28
- 230000035699 permeability Effects 0.000 description 13
- 229920001228 polyisocyanate Polymers 0.000 description 12
- 239000005056 polyisocyanate Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000002294 plasma sputter deposition Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- 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
- H01L29/78603—Thin film transistors, i.e. transistors with a channel being at least partly a thin film characterised by the insulating substrate or support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1218—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or structure of the substrate
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Ceramic Engineering (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Thin Film Transistor (AREA)
Abstract
The present invention relates to a substrate for a thin film transistor, and more particularly, to a substrate for a thin film transistor, and more particularly to a substrate for a thin film transistor having a barrier layer containing silicon oxide on at least one side of a polyimide film, The thin film transistor substrate for a flexible electronic device can be provided with a roll-to-roll process, which is advantageous for a large-area and continuous process, and it is possible to reduce the manufacturing cost and the manufacturing cost It is effective.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a substrate for a thin film transistor which is useful for flexible electronic devices.
Recently, a plasma display panel (PDP), a liquid crystal display (LCD), an organic light emitting diode (OLED), or the like, which is a flat panel display in a conventional CRT (Cathode Ray Tube) In particular, in the future, researches are being actively carried out in the world to realize such a flat panel display as a flexible display.
In such a flat panel display, a substrate is basically used as a glass substrate. In a typical flat panel display, a glass substrate is used as the most suitable material for a TFT substrate because a high temperature heat treatment is required to form the TFT.
However, since the glass substrate has basically too rigid properties, it has poor flexibility and is not suitable as a substrate for a flexible display.
In comparison with glass substrates, flexible display substrates are excellent in weight, formability, non-destructiveness, and design. In particular, they can be manufactured by a roll-to-roll production method, However, there has not been developed a flexible display substrate of a plastic material suitable for commercialization yet.
In order for such a plastic substrate to be a substrate of a flexible display, basically excellent light transmittance is required and a combination of properties such as thermal stability, chemical resistance and surface flatness are required in a complicated manner. In particular, .
In addition, in addition to deterioration due to internal factors such as deterioration of the light emitting layer due to oxygen from ITO used as an electrode and deterioration due to reaction between the light emitting layer and the interface, the flat panel display device, particularly the electroluminescence display device, , Ultraviolet rays, and manufacturing conditions of the device. Particularly, the packaging of the electroluminescence display device is very important because external oxygen and moisture have a serious effect on the lifetime of the device.
For this purpose, conventionally, display devices provided on the substrate are sealed with a metal cap or coated with a protective film. However, there has been a problem that moisture and the like from the outside can permeate through the substrate of the flat panel display device. Particularly, in the case of a substrate formed of an organic material as described above, there is a problem that penetration of moisture and the like from the outside is easier.
The main object of the present invention is to provide a thin film transistor of a flexible electronic device capable of applying a roll-to-roll process and having excellent thermal stability and flexibility while maintaining excellent optical characteristics, For example,
In order to achieve the above object, one embodiment of the present invention is a polyimide film comprising: a polyimide film; And a barrier layer containing silicon oxide on at least one side of the polyimide film.
In one preferred embodiment of the present invention, the polyimide film has an average transmittance of at least 85% at 350 to 700 nm measured with a UV spectrophotometer based on a film thickness of 10 to 100 mu m, a yellowness value of 15 or less, and TMA And an average linear expansion coefficient measured at 50 to 250 DEG C according to the Method is 50.0 ppm / DEG C or less.
In one preferred embodiment of the present invention, the silicon oxide may include a unit structure represented by the following formula (1).
≪ Formula 1 >
In Formula 1, m and n are each independently an integer of 0 to 10.
In one preferred embodiment of the present invention, the barrier layer may be characterized by a thickness of 0.3 to 3.0 mu m.
In a preferred embodiment of the present invention, the barrier layer is formed by roll-to-roll plasma enhanced chemical vapor deposition.
In a preferred embodiment of the present invention, the roll-to-roll plasma enhanced chemical vapor deposition may be performed under a process condition in which the plasma power is 1.0 to 3.0 KHz.
In a preferred embodiment of the present invention, the substrate for a thin film transistor may further include a wet organic gas barrier layer between the polyimide film and the barrier layer.
In one preferred embodiment of the present invention, the wet organic gas barrier layer may include a compound represented by the following formula (2).
(2)
Wherein X is
In a preferred embodiment of the present invention, the wet organic gas barrier layer may be characterized by a thickness of 1.0 to 20.0 mu m.
The present invention can provide a substrate for a thin film transistor of a flexible electronic apparatus having excellent optical characteristics and water permeability while having excellent bending property and thermal stability. Such a substrate for a thin film transistor can be subjected to a roll- It is possible to have a very advantageous advantage in the process, and to increase the productivity and reduce the manufacturing cost.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.
Throughout this specification, when an element is referred to as "comprising" or "containing" an element, it is to be understood that this does not exclude other elements, it means.
Throughout this specification, it is to be understood that when an element is referred to as being "on one side" of another element, it is to be understood that any element may be formed on one side of the other element, And means that, if located on the side of another element, it may include another element between any element and another element.
The present invention relates to a polyimide film; And a barrier layer containing silicon oxide on at least one side of the polyimide film.
Hereinafter, the present invention will be described in detail.
The substrate for a thin film transistor of the present invention includes a barrier layer on at least one side of the polyimide film.
The polyimide film is usually obtained by polymerizing a diamine and an acid dianhydride and then imidizing it. The polyimide film of the present invention is a colorless transparent film having inherent heat resistance of a polyimide resin and not yellowing And preferably has an average transmittance of at least 85% at 350 to 700 nm measured with a UV spectrophotometer on the basis of a film thickness of 10 to 100 탆, a yellowness of 15 or less, and a transmittance of 50 A polyimide film having an average coefficient of linear expansion (CTE) of 50.0 ppm / DEG C or less as measured at 250 DEG C can be used.
If the film has an average transmittance of less than 85% based on the film thickness of 10 to 100 탆, or a yellowness value of more than 15, transparency may be low and the film may not be applicable to displays or optical elements. If it exceeds the ppm / ° C, there is a fear that the thermal expansion coefficient difference with the plastic substrate becomes large and the device is overheated or a short circuit is generated when the temperature is high.
The barrier layer contained in at least one side of the polyimide film is for improving the low hygroscopicity of the substrate and contains a silicon oxide having a unit structure represented by the following formula (1).
≪ Formula 1 >
In the above formula (1), m and n are each independently an integer of 0 to 10, and when n or m is 0 in the above formula (1), it is possible to maximize the low hygroscopicity and high heat resistance as a pure inorganic layer, In order to improve the flexibility of the substrate for a thin film transistor, n or m in formula (1) may have an alkyl chain of suitable length as a natural number of 1 or more. In the above formula (1), when n or m is 10 or more, the coating solution tends to aggregate during coating due to the hydrophobic property, so that it is difficult to exhibit low hygroscopicity.
Here, the thickness of the barrier layer is preferably 0.3 to 3.0 占 퐉, and preferably 0.3 占 퐉 or more for ensuring adequate low hygroscopicity, and the thickness is preferably 3.0 占 퐉 or less in terms of flexibility of the substrate for a thin film transistor .
As described above, the substrate for a thin film transistor of the present invention including the barrier layer can be advantageous in that it can obtain properties of improved transmittance, lowered yellowness and lower water permeability, and particularly low moisture permeability, It is an essential element to protect.
Further, when the barrier layer is formed on the surface of the polyimide film of the present invention, the surface roughness of the surface of the polyimide film may be 2 nm or less, which brings about an advantage of planarization of the substrate. This planarization advantage can facilitate the movement of carriers when forming an electrode or a thin film transistor (TFT).
The barrier layer may be formed by a roll-to-roll plasma enhanced chemical vapor deposition (PECVD) process. In view of productivity, the barrier layer is preferably formed by two deposition rolls which act as an anode electrode. A roll-to-roll plasma enhanced chemical vapor deposition apparatus of KOBELCO Co., Ltd. can be used.
In the roll-to-roll plasma enhanced chemical vapor deposition, a discharge is generated between a cathode and an anode at the lower end to generate a plasma, and the source is evaporated by heat. At this time, in the roll-to-roll plasma-enhanced chemical vapor deposition, a plasma is formed between rolls by applying an electrode to each roll, and a carrier gas is flowed therebetween. Productivity can be expected when mass production.
In addition, the roll-to-roll plasma enhanced chemical vapor deposition can control the film component according to the source to be used, and it is possible to control the amount of the carrier gas such as oxygen and nitrogen and the content of the source to maintain the density of the film at an appropriate level, . In addition, the roll-to-roll plasma enhanced chemical vapor deposition has an advantage that it can form films of several nm to several 탆 without cracks.
The roll-to-roll plasma-enhanced chemical vapor deposition can regulate the density of the film by controlling the plasma power. However, there is a disadvantage in that the surface temperature increases to about 300 ° C. as the output increases. However, there is no optical loss and a dense film is formed .
Plastic films such as general polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polycarbonate (PC) film and polyethersulfone (PES) have low heat resistance and do not increase plasma power. it is difficult to form a film of density. However, in the case of the polyimide film, since it has a high heat resistance, it can increase the power and can deposit a high-density film without optical loss.
Specifically, when the plasma condition of the roll-to-roll plasma enhanced chemical vapor deposition is high, the deposition surface temperature reaches 300 ° C and the film is densely formed. However, as mentioned above, a plastic film having heat resistance of less than 200 占 폚 can not have a high barrier property because the film and the film are expanded and contracted during the deposition and rewinding process.
The plasma power of the roll-to-roll plasma enhanced chemical vapor deposition according to the present invention is in the range of 1.0 to 3.0 KHz. When the power is less than 1.0 KHz, the dense film can not be formed as described above. If the power exceeds 3.0 KHz, There is a problem that it is burned or the device can not be maintained.
In addition, as a conventional general deposition method for forming an inorganic material on a surface, plasma enhanced chemical vapor deposition or sputtering has a disadvantage in that the deposition area is limited due to limitations of vacuum equipment. However, in the roll-to-roll plasma enhanced chemical vapor deposition of the present invention, There is a very advantageous advantage in area and continuous process.
The substrate for a thin film transistor according to the present invention may further include a wet organic gas barrier layer between the polyimide film and the barrier layer to further improve the optical transparency and low hygroscopicity of the substrate.
The wet organic gas barrier layer may contain a polyisocyanate compound represented by the following formula (2).
(2)
Wherein X is
The polyisocyanate compound is an organic compound having a plurality of isocyanate groups in one molecule, and the number of isocyanate groups contained in one molecule of the polyisocyanate compound is preferably 5 or less.
Such a polyisocyanate compound may react with an acrylic resin having a hydroxyl group to form a polyisocyanate compound containing an acrylate group. The acrylate group-containing polyisocyanate compound can form a crosslinked structure capable of improving the physical properties of the coating film upon curing. In the polyisocyanate compound containing an acrylate group, if the number of the isocyanate groups is 5 or more, it is advantageous from the viewpoint of gas barrier, but the degree of crosslinking is high and the film is stiff, which may lower the bending property, which is an important physical property in the substrate for a flexible transistor.
Examples of the polyisocyanate compound having two isocyanate groups in the molecule include diisocyanate monomers such as tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, norbornene diisocyanate, and the like. These diisocyanate monomers include, It is possible to react with an acrylic resin having an actual group to form a diisocyanate compound containing an acrylate group.
The thickness of the wet organic gas barrier layer of the acrylate group-containing polyisocyanate is preferably 1.0 to 20.0 mu m. In order to ensure the barrier property of the substrate for a desired thin film transistor, the thickness of the wet organic gas barrier layer is preferably 1.0 mu m or more And it is preferable to set the thickness to 20.0 占 퐉 or less in order to exclude that the flexibility of the transparent polyimide substrate deteriorates.
The wet organic gas barrier layer can be obtained through a series of steps of coating, drying and curing a solution containing a polyisocyanate containing an acrylate group on a polyimide film. Here, the method of coating the solution containing the acrylate group-containing polyisocyanate on one surface or both surfaces of the polyimide film may be a spray coating, a bar coating, a spin coating, a dip coating And the like can be selected from among various methods.
The curing of the wet organic gas barrier layer is an ultraviolet curing method, and in view of this, a photoinitiator may be included in a solution containing an acrylate group. Examples of the photoinitiator include benzoin ether photoinitiators, benzophenone photoinitiators, and combinations thereof. The conditions for ultraviolet curing can be ultraviolet curing by irradiating ultraviolet rays having a wavelength of 312 and / or 365 nm at 500 to 10,000 J / m 2 .
The substrate for a thin film transistor according to the present invention can further improve the optical characteristics and barrier characteristics of the substrate by including the barrier layer and the wet organic gas barrier layer together on the polyimide film .
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.
< Manufacturing example 1>
1-1: Preparation of polyimide powder
832 g of N, N-dimethylacetamide (DMAc) was charged into a 1 L reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a condenser while nitrogen was passed through the reactor. 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was dissolved and the solution was maintained at 25 占 폚. Thereto were added 31.09 g (0.07 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanedioanhydride (6FDA) and 8.83 g (0.03 mol) of biphenyltetracarboxylic dianhydride (BPDA) ) Was added and stirred for a certain period of time to dissolve and react. The temperature of the solution was maintained at 25 占 폚. Then, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution having a solid content of 13 wt%. 25.6 g of pyridine and 33.1 g of acetic anhydride were added to the polyamic acid solution, stirred for 30 minutes, and further stirred at 70 ° C for 1 hour. The mixture was cooled to room temperature and precipitated with 20 L of methanol. The precipitated solid was filtered and pulverized And then dried at 100 DEG C under vacuum for 6 hours to obtain 111 g of a solid powdery polyimide.
1-2: Production of polyimide film
0.03 g (0.03 wt%) of amorphous silica particles having an OH group bonded to its surface was added to N, N-dimethylacetamide (DMAc) at a dispersion concentration of 0.1%, ultrasonic treatment was performed until the solvent became transparent, 100 g of the solid component powder of Example 1-1 was dissolved in 670 g of N, N-dimethylacetamide (DMAc) to obtain a 13 wt% solution. The thus obtained solution was coated on a stainless steel plate, The film was peeled off from the stainless steel plate and fixed to the frame with a pin. The frame with the film fixed therein was placed in a vacuum oven, slowly heated from 100 ° C to 300 ° C for 2 hours, cooled gradually and separated from the frame to obtain a polyimide film. Thereafter, the substrate was subjected to heat treatment at 300 ° C for 30 minutes as a final heat treatment process. The prepared polyimide film had a thickness of 50 탆, an average light transmittance of 89.5%, a yellowness of 2.4, and an average coefficient of linear thermal expansion (CTE) of 20 ppm / 캜 measured at 50 to 250 캜 according to the TMA- .
< Comparative Example 1>
The polyimide film prepared in Production Example 1 was prepared and used as Comparative Example 1.
< Comparative Example 2>
A solution obtained by dissolving 15 g of a polyisocyanate (Natoco, KLS-009 55 wt%) containing acrylate in which m and n are 1 and R 1 is a hexyl group and R 2 is a hexyl group in Formula 2 is dissolved in 15 ml of PGMEA, Coated on both sides of the polyimide film of Comparative Example 1 using a coater and dried at a temperature of 80 캜 to obtain a coating film having a thickness of 15 탆. Thereafter, a wet organic gas barrier layer having a thickness of 15 mu m was formed by irradiating two wavelengths simultaneously with energy of 100 mW / cm < 2 > for 10 seconds by using an ultraviolet curing machine of 312 nm and 365 nm to form a wet organic gas barrier layer, And a wet organic gas barrier layer were successively laminated on the substrate.
< Comparative Example 3>
A silicon oxide (silicon of Kobelco) having m and n of 0 in the formula (1) was vapor-deposited on the polyimide film of Comparative Example 2 to form a barrier layer having a thickness of 0.2 占 퐉 to form a wet organic coating layer, a polyimide film, A substrate for a thin film transistor in which a gas barrier layer and a barrier layer were sequentially laminated was produced. At this time, the deposition of the barrier layer was performed at a line speed of 1.2 m / min., A power of 1.5 KHz, and a vacuum degree of 0.7 pascal using roll-to-roll PECVD from Kobelco.
< Comparative Example 4>
The barrier layer, the wet organic gas barrier layer, the polyimide film, the wet organic gas barrier layer, and the barrier layer were sequentially formed by the same method as that of the substrate for a thin film transistor of Comparative Example 3, To fabricate a thin film transistor substrate.
< Comparative Example 5>
A barrier layer having a thickness of 3 占 퐉 was formed under the conditions of a line speed of 0.15 m / min. And a power of 0.6 kHz at the time of formation of a barrier layer to form a barrier layer, a wet organic gas A substrate for a thin film transistor in which a barrier layer, a polyimide film, a wet organic gas barrier layer and a barrier layer were sequentially laminated was produced.
< Comparative Example 6>
A substrate for a thin film transistor was manufactured in the same manner as in Comparative Example 5 except that a barrier layer, a wet organic gas barrier layer, a PET film, a wet organic gas A substrate for a thin film transistor in which a barrier layer and a barrier layer were sequentially laminated was produced.
< Comparative Example 7>
A barrier layer having a thickness of 5 占 퐉 was formed under the conditions of a line speed of 0.15 m / min when a barrier layer was formed through roll-to-roll PECVD to form a wet organic gas barrier layer , A polyimide film, a wet organic gas barrier layer, and a barrier layer were successively laminated on the substrate.
< Comparative Example 8>
The barrier layer, the wet organic gas barrier layer, the polyimide film, the wet organic gas barrier layer, and the barrier layer, which are sequentially stacked, are formed by the same method as that of the polyimide substrate of Comparative Example 7, Substrate for a transistor was manufactured.
< Example 1>
A silicon oxide (Kobelco Silicone) having m and n of 0 in the formula (1) was vapor-deposited on the polyimide film prepared in Preparation Example 1 to form a barrier layer having a thickness of 0.3 占 퐉 so that the polyimide film and the barrier layer were sequentially Thereby producing a laminated thin film transistor substrate. At this time, the deposition of the barrier layer was performed at a line speed of 1.0 m / min., A power of 1.2 KHz, and a vacuum degree of 0.7 pascal using roll-to-roll PECVD from Kobelco.
< Example 2>
A substrate for a thin film transistor in which a barrier layer, a polyimide film, and a barrier layer were sequentially stacked was prepared by forming a barrier layer on both sides by roll-to-roll PECVD in the same manner as the substrate for a thin film transistor of Example 1.
< Example 3>
A barrier layer having a thickness of 5 占 퐉 was formed under the conditions of a line speed of 0.45 m / min when a barrier layer was formed through roll-to-roll PECVD in the same manner as that of the substrate for a thin film transistor of Example 1 to form a polyimide film and barrier Layer was successively laminated on the substrate.
< Example 4>
A substrate for a thin film transistor in which a barrier layer, a polyimide film and a barrier layer were sequentially laminated was produced by forming a barrier layer on both sides by roll-to-roll PECVD in the same manner as the substrate for a thin film transistor of Example 3.
< Example 5>
A barrier layer having a thickness of 3 占 퐉 was formed under the conditions of a line speed of 0.15 m / min and a power of 1.5 KHz when the barrier layer was formed by roll-to-roll PECVD, Layer, a polyimide film, and a barrier layer were successively laminated on the substrate.
< Example 6>
A barrier layer having a thickness of 3 탆 was formed under the conditions of a line speed of 0.15 m / min and a power of 1.5 KHz when the barrier layer was formed by roll-to-roll PECVD, Layer, a wet organic gas barrier layer, a polyimide film, a wet organic gas barrier layer, and a barrier layer were sequentially stacked on a substrate.
< Example 7>
A substrate for a thin film transistor in which a wet organic gas barrier layer, a polyimide film, a wet organic gas barrier layer and a barrier layer were sequentially laminated was formed by forming the barrier layer only through roll-to-roll PECVD in the same manner as in Example 6 .
≪ Property evaluation method &
The properties were measured by the following methods, and the results are shown in Table 1.
(1) Average light transmittance (%) measurement
Optical transmittance at 350 to 700 nm was measured using a spectrophotometer (CU-3700D, KONICA MINOLTA).
(2) Measurement of yellowness
The yellowness was measured using a spectrophotometer (CU-3700D, KONICA MINOLTA).
(3) Water permeability (g / m 2 / day) measurement
Water permeability (WVTR) was measured using a water-in-oil transient (MOCON / US / Aquatran-model-1).
(4) Coefficient of thermal expansion (CTE)
TMA (Perkin Elmer, Diamond TMA) was used to measure the thermal expansion coefficient at 50 ~ 250 ° C twice in accordance with the TMA-Method. The temperature rise rate was 10 ° C / min and a load of 100mN was applied, Respectively.
(%)
(g / m 2 / day)
(Radius of curvature mm)
(ppm / DEG C)
As shown in Table 1, in the case of Comparative Example 1, when the polyimide film was used alone, the moisture permeability could not protect the device from moisture. In Comparative Example 2, the wet organic gas barrier layer was formed on both sides However, the moisture permeability was also found to be inadequate to protect the device from moisture.
In the case of Comparative Examples 3 to 4, it was found that although the barrier layer was formed, the barrier layer was thin, and the moisture permeability was high, so that it was not suitable for protecting the device from moisture. In the case of Comparative Example 5 The low power of the roll-to-roll PECVD system showed that the film had a low density and a high water permeability. In the case of Comparative Example 6 using a PET film as a substrate, the water permeability was also high or the coefficient of thermal expansion It is not suitable for a high-temperature process for forming a device or the like in a process subsequent to a cursor.
In the case of Comparative Examples 7 to 8, it was confirmed that the flexural characteristics were too low to be used as a flexible electronic device substrate.
On the other hand, Examples 1 to 7 were found to be suitable for use as a substrate for a thin film transistor of a flexible electronic device by satisfying both optical transmittance, yellowing degree, water permeability, flexural characteristic and thermal expansion coefficient.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
And a barrier layer containing silicon oxide on at least one side of the polyimide film.
≪ Formula 1 >
M and n are each independently an integer of 0 to 10;
(2)
Wherein X is
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080055531A (en) * | 2006-12-15 | 2008-06-19 | 주식회사 코오롱 | Colorless polyimide film |
| KR20110094049A (en) * | 2008-12-12 | 2011-08-19 | 린텍 가부시키가이샤 | Laminate, method for producing same, electronic device member, and electronic device |
| KR20120078514A (en) * | 2010-12-31 | 2012-07-10 | 코오롱인더스트리 주식회사 | The transparent polyimide substrate and the method for producing it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080055531A (en) * | 2006-12-15 | 2008-06-19 | 주식회사 코오롱 | Colorless polyimide film |
| KR20110094049A (en) * | 2008-12-12 | 2011-08-19 | 린텍 가부시키가이샤 | Laminate, method for producing same, electronic device member, and electronic device |
| KR20120078514A (en) * | 2010-12-31 | 2012-07-10 | 코오롱인더스트리 주식회사 | The transparent polyimide substrate and the method for producing it |
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