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CN107903712A - Metal oxide semiconductor ink and application method in a kind of inkjet printing technology - Google Patents

Metal oxide semiconductor ink and application method in a kind of inkjet printing technology Download PDF

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Publication number
CN107903712A
CN107903712A CN201711142406.3A CN201711142406A CN107903712A CN 107903712 A CN107903712 A CN 107903712A CN 201711142406 A CN201711142406 A CN 201711142406A CN 107903712 A CN107903712 A CN 107903712A
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Prior art keywords
metal oxide
ink
inkjet printing
semiconductor metal
organic polymer
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CN201711142406.3A
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Chinese (zh)
Inventor
陈惠鹏
郭太良
孙大卫
张国成
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Fuzhou University
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Fuzhou University
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Priority to CN201711142406.3A priority Critical patent/CN107903712A/en
Publication of CN107903712A publication Critical patent/CN107903712A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/38Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/36Inkjet printing inks based on non-aqueous solvents
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00Field-effect transistors [FET]
    • H10D30/60Insulated-gate field-effect transistors [IGFET]
    • H10D30/67Thin-film transistors [TFT]
    • H10D30/674Thin-film transistors [TFT] characterised by the active materials
    • H10D30/6755Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Thin Film Transistor (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

本发明公开一种喷墨打印技术中的半导体金属氧化物墨水的优化工艺,属于氧化物半导体技术和印刷电子技术领域,该工艺通过掺杂的方式改善薄膜性能,且掺杂比例可调,掺杂效果显著。该溶液以半导体氧化物前驱体及其对应溶剂作为基础溶液,通过加入第二溶剂及相应的有机聚合物制备成复合溶液完成墨水掺杂。本发明制作的有源层采用喷墨打印的方式制作,与基础溶液相比,该有源层在溶液中通过复合溶剂实现金属氧化物前驱体与有机聚合物的均匀共混,在成膜的过程中有机聚合物明显改善了溶剂挥发后图案的不均匀形貌,在后续的热处理工艺中,有机聚合物的掺杂影响了前驱体转变为金属氧化物的过程,通过促进了导电沟道的形成提高了其电子的迁移率。

The invention discloses an optimization process of semiconductor metal oxide ink in inkjet printing technology, which belongs to the field of oxide semiconductor technology and printed electronics technology. The process improves the film performance by doping, and the doping ratio is adjustable. The miscellaneous effect is remarkable. The solution uses the semiconductor oxide precursor and its corresponding solvent as a base solution, and prepares a composite solution by adding a second solvent and a corresponding organic polymer to complete ink doping. The active layer produced by the present invention is produced by inkjet printing. Compared with the base solution, the active layer realizes the uniform blending of the metal oxide precursor and the organic polymer through the composite solvent in the solution. During the process, the organic polymer significantly improved the uneven morphology of the pattern after the solvent volatilized. In the subsequent heat treatment process, the doping of the organic polymer affected the process of transforming the precursor into a metal oxide, and promoted the formation of the conductive channel. Formation increases the mobility of its electrons.

Description

Metal oxide semiconductor ink and application method in a kind of inkjet printing technology
Technical field
The present invention relates to semiconductor materials and devices and inkjet printing technology, belongs to printed electronics field, specifically relates to And metal oxide semiconductor ink and application method in a kind of inkjet printing technology.
Background technology
With the arrival of information age, Display Technique is just accelerating to large scale, and flexible, printable direction is developed, had In the array driving display device of source, the thin-film transistor technologies of its core technology have attracted a large amount of enterprises and the attention of researcher. Thin film transistor (TFT) is a kind of field-effect semiconductor device, including substrate, insulating layer, active layer, grid and source-drain electrode etc. are several Important component.Wherein active layer has vital influence for device performance and preparation process.In the nearly more than ten years In time, transistor active layer material is based on silicon materials, and TFT-LCD display devices are developed rapidly on this basis, and Become mainstream display terminal.In recent years, metal oxide is due to its high grade of transparency and mobility and relatively low is prepared into This and the characteristic prepared suitable for large area have attracted the exploitation and use of a large number of researchers and enterprise to the technology.However, But current silica-base material and metal oxide semiconductor material is required for the film-forming process by sputtering, chemical deposition to prepare Corresponding film is, it is necessary to which high vacuum environment and a large amount of mask plates, there is extremely complex technique and high cost of labor.
Present thin film transistor (TFT) mainstream technology is more more using being prepared on glass substrate by modes such as sputtering, chemical depositions Crystal silicon or metal-oxide semiconductor (MOS), for mode of printing prepares transistor, this preparation method has higher Manufacturing cost and complex technological process.It is right for mode of printing prepares inorganic, metal oxide thin film transistor (TFT) There is higher compatibility in substrate selection, it is the most frequently used now, most hot without the advantages that mask plate inkjet printing to be become A kind of preparation method of door.But the solution of inorganic, metal oxide material as marking ink when, its prepare MOTFT it is past Toward having, electron mobility and on-off ratio be not high, the performance shortcomings such as performance degradation caused by film uniformity is bad and be unfavorable for reality Border is applied and mass production.
The content of the invention
The object of the present invention is to provide the metal oxide semiconductor ink and application method in a kind of inkjet printing technology, By realizing the blending of double solvents, metal oxide precursor and organic polymer in the solution before forming thin film, into Organic polymer improves the uneven pattern of pattern after solvent volatilization during film, while have impact on presoma and be changed into gold Belong to the process of oxide, the formation by promoting conducting channel improves the mobility of its electronics.
The present invention is realized using following methods:
A kind of metal oxide semiconductor ink in inkjet printing technology, the ink are molten with metal oxide semiconductor presoma Solution based on liquid, completes to be blended and adulterates and be prepared into composite solution by adding the second solvent and organic polymer.It is described Metal oxide semiconductor persursor material be made of the metallic salt of organic or inorganic, include acetylacetone,2,4-pentanedione radical ion, second One or more anion in acid ion, nitrate ion, chlorion.The organic polymer is in the second solvent Dissolubility is good, and with stable chemical property and does not have directly with the metal oxide semiconductor presoma in water oxygen and ink The chemical reaction connect;
Second solvent includes esters and ketone.
The metal oxide semiconductor persursor material includes one kind in Indium Tris acetylacetonate and indium nitrate.
The molecular weight of the organic polymer is a certain molecular weight between 2000 to 1,000 ten thousand, including polystyrene and poly- One kind in methyl methacrylate.
The good solvent of the metal oxide semiconductor presoma includes alcohols and ethers, has excellent mix with the second solvent Dissolubility.
In the composite solution, the molar concentration of metal oxide semiconductor presoma between the M of 0.02 M ~ 0.8, and The mass fraction ratio of organic polymer solute and metal oxide precursor solute is 0.1:100 to 5:Between 100.
The application method of metal oxide semiconductor ink:Composite solution is prepared smooth one by way of inkjet printing On substrate, the contact angle of the substrate and composite solution is at 0 ~ 90 °, and the temperature of substrate is maintained at 30 ~ 50 DEG C during printing.This is compound Solution is printed upon on substrate afterwards, it is necessary to by thermal anneal process, and annealing temperature is at 200 ~ 300 DEG C.
Compared with prior art, remarkable advantage of the invention and have the beneficial effect that:The metal oxide that the present invention makes is thin Film transistor device, its active layer are prepared by the way of inkjet printing, its technique is simple, and operation is quick and precisely;And ink-jet is beaten The used active layer of print is then the blending that metal oxide precursor and organic polymer are realized by using double solvents, Organic polymer improves the uneven pattern of pattern after solvent volatilization during film forming, while have impact on presoma and be changed into The process of metal oxide, the formation by promoting conducting channel improve the mobility of its electronics.
Brief description of the drawings
Fig. 1 is the structure diagram of metal oxide thin-film transistor device in the present invention.
Fig. 2 is the transfer characteristic curve figure and corresponding deposited picture that the embodiment of the present invention 1,2 is tested out.
Fig. 3 is the corresponding longitudinal sagittal height figure of the pattern prepared by this discovery embodiment 1,2.
The corresponding X-ray electronic energy spectrum of active layer film prepared by this discovery of Fig. 4 embodiment 1,2.
【Label declaration】Wherein 100 be p-type doped silicon wafer, and 110 be insulating layer, and 120 be active layer, and 130 be source-drain electrode.
Embodiment
The present invention will be described in further detail by specific embodiment below.
Embodiment 1
1) silicon chip with 100 nm thick silicon dioxide insulating layers is distinguished in acetone, isopropanol, chloroform, deionized water Ultrasonic 10min, and dry up surface, vacuum drying using clean nitrogen.
2) silicon chip is subjected to oxygen plasma processing, specific method is:By the silicon chip insulating layer be placed in upwardly etc. from In daughter cleaning machine cavity, plasma potential is set as 630 V, handles 5min, face up taking-up after being disposed.
3) metal-oxide semiconductor (MOS) presoma solute Indium Tris acetylacetonate is dissolved in 3ml's with 120 mg/ml of final concentration Ethylene glycol monomethyl ether:Ethyl acetate (volume ratio 7:3) in double solvents, the polymethyl of 9mg is added on the basis of this solution Sour methyl esters(Molecular weight 120000), 60 DEG C stirring 2h after be stored at room temperature it is overnight.The syringe filters mistake that the solution passes through 0.22um Printed on after filter by type piezoelectric ink jet printer on demand on the insulating layer on silicon chip.The temperature of inkjet printing substrate is 40 DEG C, after the completion of printing, the silicon chip is in 80 °C of Heat preservation 30min, 225 °C of heating 1h afterwards.
4) the Au electrodes of 50 nm are formed on active layer using mask plate using the mode of physical vapour deposition (PVD).
Embodiment 2
1) silicon chip with 100 nm thick silicon dioxide insulating layers is divided in acetone, isopropanol, chloroform, deionized water Not ultrasound 10min, and dry up surface, vacuum drying using clean nitrogen.
2) silicon chip is subjected to oxygen plasma processing, specific method is:By the silicon chip insulating layer be placed in upwardly etc. from In daughter cleaning machine cavity, plasma potential is set as 630 V, handles 5min, face up taking-up after being disposed.
3) by metal-oxide semiconductor (MOS) presoma solute indium nitrate with the second for being dissolved in 3ml of 120 mg/ml of final concentration Alcohol:Ethyl acetate (volume ratio 7:3) in double solvents, it is stored at room temperature after 60 DEG C of stirring 2h overnight.Add on the basis of this solution Enter the polystyrene of 3mg(Molecular weight 200000), stirring at normal temperature 2h dissolvings are completely.The syringe filters that the solution passes through 0.22um Printed on after filtering by type piezoelectric ink jet printer on demand on the insulating layer on silicon chip.The temperature of inkjet printing substrate is 40 °C, after the completion of printing, the silicon chip is in 80 °C of Heat preservation 30min, 225 °C of heating 1h afterwards.
4) the Au electrodes of 50 nm are formed on active layer using mask plate using the mode of physical vapour deposition (PVD).
Device architecture prepared by the present invention is as shown in Figure 1.Embodiment 1 and inorganic, metal oxide prepared by embodiment 2 are thin The electricity transfer characteristic curve and corresponding deposited picture of film transistor are as shown in Fig. 2, the corresponding longitudinal direction of the pattern is cut at the same time Face is highly as shown in Figure 3.As shown in Figure 2, inorganic, metal oxide thin film transistor (TFT) is after polystyrene is added, mobility from 4.2 cm2V-1s-113.7 cm are brought up to2V-1s-1, Fig. 4 illustrates that the chemical constituent of the film is changed, this is property Can changed one of the main reasons.Meanwhile the uniformity of film is understood by Fig. 2 and Fig. 3, i.e. the whole height of film is poor, There is larger lifting.After adding polystyrene in solution, low pattern is improved between the senior middle school of both sides, and " coffee ring " phenomenon obtains To suppression.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, should all belong to the covering scope of the present invention.

Claims (8)

1.一种喷墨打印技术中的半导体金属氧化物墨水,其特征在于:该墨水以半导体金属氧化物前驱体溶液作为基础溶液,通过加入第二溶剂及有机聚合物完成共混掺杂并制备成复合溶液;1. A semiconductor metal oxide ink in inkjet printing technology, characterized in that: the ink uses a semiconductor metal oxide precursor solution as a base solution, and is prepared by adding a second solvent and an organic polymer to complete blending and doping into a complex solution; 所述的半导体金属氧化物前驱体材料由有机或无机的金属盐类组成,包含乙酰丙酮根离子、乙酸根离子、硝酸根离子、氯离子中的一种或多种阴离子;The semiconductor metal oxide precursor material is composed of organic or inorganic metal salts, including one or more anions in acetylacetonate ions, acetate ions, nitrate ions, and chloride ions; 所述的有机聚合物在第二溶剂中的溶解性好,并具有稳定的化学性质且不与水氧以及墨水中的半导体金属氧化物前驱体有直接的化学反应;The organic polymer has good solubility in the second solvent, has stable chemical properties and does not directly react with water, oxygen and the semiconductor metal oxide precursor in the ink; 所述的第二溶剂包括酯类和酮类。The second solvent includes esters and ketones. 2.根据权利要求1所述的一种喷墨打印技术中的半导体金属氧化物墨水,其特征在于:所述的半导体金属氧化物前驱体材料包括乙酰丙酮铟和硝酸铟中的一种。2. The semiconductor metal oxide ink in inkjet printing technology according to claim 1, characterized in that: the semiconductor metal oxide precursor material comprises one of indium acetylacetonate and indium nitrate. 3.根据权利要求1所述的一种喷墨打印技术中的半导体金属氧化物墨水,其特征在于:所述有机聚合物的分子量为2000到1000万之间的某一分子量。3. The semiconductor metal oxide ink in inkjet printing technology according to claim 1, characterized in that: the molecular weight of the organic polymer is a certain molecular weight between 20 million and 10 million. 4.根据权利要求3所述的一种喷墨打印技术中的半导体金属氧化物墨水,其特征在于:所述有机聚合物包括聚苯乙烯和聚甲基丙烯酸甲酯中的一种。4. The semiconductor metal oxide ink in inkjet printing technology according to claim 3, characterized in that: said organic polymer comprises one of polystyrene and polymethyl methacrylate. 5.根据权利要求1所述的一种喷墨打印技术中的半导体金属氧化物墨水,其特征在于:所述半导体金属氧化物前驱体的良溶剂包括醇类和醚类,与第二溶剂有优异的混溶性。5. the semiconductor metal oxide ink in a kind of inkjet printing technology according to claim 1, is characterized in that: the good solvent of described semiconductor metal oxide precursor comprises alcohols and ethers, and the second solvent has Excellent miscibility. 6. 根据权利要求1-5任一所述的一种喷墨打印技术中的半导体金属氧化物墨水,其特征在于:在复合溶液中,半导体金属氧化物前驱体的摩尔浓度在0.02 M ~0.8 M之间,且有机聚合物与半导体金属氧化物前驱体的质量分数比在0.1:100到5:100之间。6. The semiconducting metal oxide ink in any one of claims 1-5, wherein the molar concentration of the semiconducting metal oxide precursor is 0.02 M to 0.8 in the composite solution. M, and the mass fraction ratio of the organic polymer to the semiconductor metal oxide precursor is between 0.1:100 and 5:100. 7. 如权利要求1所述的半导体金属氧化物墨水的使用方法,其特征在于:所述的复合溶液通过喷墨打印的方式制备在一平整基板上,该基板与复合溶液的接触角在0 ~ 90°,且打印时基板的温度保持在30~50℃。7. The using method of semiconductor metal oxide ink as claimed in claim 1, characterized in that: the composite solution is prepared on a flat substrate by inkjet printing, and the contact angle between the substrate and the composite solution is between 0 ~ 90°, and the temperature of the substrate is kept at 30~50°C during printing. 8.根据权利要求7所述的半导体金属氧化物墨水的使用方法,其特征在于:该复合溶液打印在基板上后,需要经过热退火处理,退火温度在200~300℃。8. The method for using semiconductor metal oxide ink according to claim 7, characterized in that: after the composite solution is printed on the substrate, it needs to undergo thermal annealing treatment, and the annealing temperature is 200-300°C.
CN201711142406.3A 2017-11-17 2017-11-17 Metal oxide semiconductor ink and application method in a kind of inkjet printing technology Pending CN107903712A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109449245A (en) * 2018-10-22 2019-03-08 福州大学 A kind of metal oxide optotransistor and preparation method thereof
WO2023087353A1 (en) * 2021-11-19 2023-05-25 惠州华星光电显示有限公司 Transistor and method for manufacturing same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1400107A (en) * 2001-08-03 2003-03-05 中国科学院金属研究所 Ink jet printing method for preparing metal oxide functional film
CN102160182A (en) * 2008-09-17 2011-08-17 出光兴产株式会社 Thin film transistor having crystalline indium oxide semiconductor film
CN103779425A (en) * 2014-01-27 2014-05-07 上海交通大学 Preparing method for indium gallium zinc oxide semi-conductor film
CN104284952A (en) * 2012-02-29 2015-01-14 耶路撒冷希伯来大学伊森姆研究发展有限公司 Inks comprising metal precursor nanoparticles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1400107A (en) * 2001-08-03 2003-03-05 中国科学院金属研究所 Ink jet printing method for preparing metal oxide functional film
CN102160182A (en) * 2008-09-17 2011-08-17 出光兴产株式会社 Thin film transistor having crystalline indium oxide semiconductor film
CN104284952A (en) * 2012-02-29 2015-01-14 耶路撒冷希伯来大学伊森姆研究发展有限公司 Inks comprising metal precursor nanoparticles
CN103779425A (en) * 2014-01-27 2014-05-07 上海交通大学 Preparing method for indium gallium zinc oxide semi-conductor film

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109449245A (en) * 2018-10-22 2019-03-08 福州大学 A kind of metal oxide optotransistor and preparation method thereof
WO2023087353A1 (en) * 2021-11-19 2023-05-25 惠州华星光电显示有限公司 Transistor and method for manufacturing same
US12349583B2 (en) 2021-11-19 2025-07-01 Huizhou China Star Optoelectronics Display Co., Ltd. Transistor and manufacturing method thereof

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Application publication date: 20180413