WO2012043912A1 - Procédé de fabrication d'un transistor à couche mince et circuit électronique utilisant le procédé de pulvérisation - Google Patents

Procédé de fabrication d'un transistor à couche mince et circuit électronique utilisant le procédé de pulvérisation Download PDF

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WO2012043912A1
WO2012043912A1 PCT/KR2010/006879 KR2010006879W WO2012043912A1 WO 2012043912 A1 WO2012043912 A1 WO 2012043912A1 KR 2010006879 W KR2010006879 W KR 2010006879W WO 2012043912 A1 WO2012043912 A1 WO 2012043912A1
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substrate
derivatives
thin film
roll
manufacturing
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PCT/KR2010/006879
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English (en)
Korean (ko)
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노용영
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한밭대학교산학협력단
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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
    • H01L29/66—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
    • 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
    • H01L27/1222—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, shape or crystalline structure of the active layer
    • H01L27/1225—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, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
    • 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
    • H01L27/1259—Multistep manufacturing methods
    • H01L27/1292—Multistep manufacturing methods using liquid deposition, e.g. printing
    • 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
    • H01L29/66969—Multistep manufacturing processes of devices having semiconductor bodies not comprising group 14 or group 13/15 materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating

Definitions

  • the present invention relates to a method of manufacturing a thin film transistor and a method of manufacturing an electronic circuit including the same, and more particularly, forming a semiconductor layer, an insulator layer, a conductive electrode layer coated by a spray method, and stacking them to form a top gate or bottom.
  • TFTs thin film transistors
  • the biggest advantage of this manufacturing method is that the thin film can be manufactured at a relatively low manufacturing cost compared to the process of forming the electronic functional thin film based on the conventional vacuum apparatus.
  • Much research is being conducted to utilize the TFT manufactured by the solution process as a logic circuit of a low-cost RFID tag for recognizing an individual article unit that replaces a driving element or a barcode of a next-generation flexible display.
  • the TFT thus manufactured may be applied to various flexible electronic devices implemented on a polymer substrate.
  • the photolithographic method is mainly used in the process of forming an electrode or a wiring.
  • a conductive film is formed by a conventional film forming method, such as sputtering, plating, or CDD, after which a photosensitive material is applied onto a substrate, and is developed by irradiating with light, and then etching the conductive film in accordance with a resist pattern.
  • the step of forming the electrode or the wiring pattern of the functional thin film requires extensive equipment such as a vacuum apparatus and complicated processes in forming, patterning, film forming, and etching the thin film.
  • the material use efficiency is only a few percent, and when the process is terminated, it cannot be reused and disposed of, resulting in high manufacturing costs and a large amount of unnecessary chemical waste.
  • substrate is proposed using the liquid droplet discharge method (so-called inkjet method) which discharges a liquid material from a liquid discharge head in a liquid droplet state.
  • inkjet method liquid droplet discharge method
  • Japanese Patent Application Laid-Open No. 2003-317945 where a thin film pattern ink, which is a functional liquid obtained by dispersing conductive fine particles such as metal fine particles or a precursor thereof, is directly pattern-coated on a substrate. After that, heat treatment or laser irradiation is performed to convert the film into a conductive film pattern of a thin film.
  • the conventional complicated film forming process, photolithography, and etching process are unnecessary, and the process is greatly simplified, and the amount of raw materials used is small and productivity is improved.
  • the inkjet printing process is a method of producing a thin film by applying only a small amount of ink to a desired portion through a very small nozzle, so that the ink is applied only to a desired portion, so that the production and value of chemical waste and by-products are higher than those of other printing processes.
  • the inkjet process has a relatively slow printing speed and requires a relatively long time for accurate alignment of the inkjet head and the substrate in order to eject ink where desired, so that a high-speed roll-to-roll based continuous process is applied.
  • a high-speed roll-to-roll based continuous process is applied.
  • it is difficult to realize higher resolution patterning precision only with relatively expensive equipment.
  • the manufacturing cost per unit of the device must be maintained at 10 won or less, so the practical application is possible.
  • a photolithography or various vacuum deposition processes are required. Therefore, there is a disadvantage that too much manufacturing cost.
  • the present invention is to provide a method for manufacturing a thin film transistor and an electronic circuit through a spray printing method that can be applied to a large area at a very low cost.
  • the thin film can be patterned through various printing processes.
  • this process in a roll-to-roll, it is possible to manufacture the device at a high speed, so that the manufacturing cost can be drastically reduced and the device can be manufactured at a very low cost of less than 10 won.
  • a main object of the present invention is to provide a method for manufacturing a large area TFT and an electronic circuit by applying a large area of the electronic functional thin film that can be patterned through a spray printing method at a relatively low price.
  • the spray coating method is combined with a roll-to-roll based continuous process to apply a large-area electronic functional thin film to a plastic substrate proceeding at a high speed, thereby manufacturing a TFT and an electronic circuit. It is another purpose to provide a way to do it.
  • the heat treatment may be performed to prepare a TFT by evaporating the remaining solvent.
  • the present invention has the effect of applying a large area TFT through a very inexpensive process.
  • FIG. 1 is a schematic diagram of manufacturing a TFT by applying a semiconductor ink on a substrate provided through a spray printing method.
  • FIG. 2 is a schematic diagram illustrating a method of forming a pattern by applying a solution only to an open part by applying spray printing on a shadow mask in which a pattern is formed in advance.
  • FIG. 3 is a schematic diagram of a bottom gate type TFT.
  • FIG. 4 is a schematic diagram of a top gate type TFT.
  • 5 is an optical microscope image of various organic semiconductor thin films applied by spray coating on source / drain electrodes formed through spray coating.
  • FIG. 6 shows a transition curve of a P-Channel tip pentacene organic thin film transistor manufactured by spray printing.
  • Figure 7 shows the transition curve of N-Channel dicyano phenylene dicarboxyl imide prepared by spray printing.
  • FIG. 8 is a schematic diagram of a CMOS type inverter in which P-Channel and N-channel are respectively patterned through a spray printing method.
  • FIG. 9 shows an output curve of a CMOS input inverter made of P-Channel tip pentacene and N-channel dicyano phenylene dicarboxyl imide through a spray printing method.
  • FIG. 10 shows a gain curve according to a CMOS input voltage made of P-Channel tips pentacene and N-channel dicyano phenylene dicarboxyl imide through a spray printing method.
  • FIG. 11 shows a schematic view of a thin film transistor manufacturing process through a roll-to-roll spray printing method.
  • FIG. 1 is a schematic diagram of manufacturing a TFT by applying a semiconductor ink on a substrate provided through a spray printing method.
  • FIG. 2 is a schematic diagram illustrating a method of forming a pattern by applying a solution only to an open part by applying spray printing on a shadow mask in which a pattern is formed in advance.
  • the present invention relates to a method of manufacturing a TFT by spraying a solution from a spray coating onto a substrate.
  • the spray coating method is also applicable to the roll-to-roll continuous process.
  • FIG. 3 is a schematic diagram of a bottom gate type TFT.
  • FIG. 4 is a schematic diagram of a top gate type TFT.
  • 5 is an optical microscope image of various organic semiconductor thin films applied by spray coating on source / drain electrodes formed through spray coating.
  • a substrate on which a TFT is to be manufactured must be prepared.
  • Usable substrates include n-type or p-type doped silicon wafers, glass substrates, polyethersulphones, polyacrylates, polyetherimides, polyimides, polyethylene Terephthalate (polyethyeleneterepthalate), polyethylene naphthalate (polyethylene naphthalate) includes a plastic film and an indium tin oxide coated glass substrate and a plastic film, but is not limited thereto.
  • After dissolving the desired material in a suitable concentration in a solvent it is applied to the substrate through a spray apparatus, and the solvent is evaporated through heat treatment to prepare a thin film in a solid state.
  • a shadow mask with a desired pattern is placed on a substrate where a pattern is needed, such as a source / drain electrode of a thin film transistor, and a solution is sprayed through a spray device to produce a thin film having a desired pattern through heat treatment.
  • the organic semiconductor coating liquid used in the present invention may be polythiophene and its derivatives, polythiothiothiophene and its derivatives, TIPS pentacene and its derivatives, and pentacene precursors.
  • the metal oxide coating used in the present invention is selected from oxite oxide mixed with zinc, indium, gallium, tin and the like. More specifically, zinc oxide, indium tin oxide, tin oxide, zinc tin oxide, indium gallium zinc oxide oxide, etc. may be mentioned. However, it is not necessarily limited thereto.
  • the metal oxide ink is formed through a spray method and a thin film is heat-treated at 100 to 600 ° C. to obtain desired semiconductor properties.
  • a polymer insulating solution is prepared by completely dissolving a material used as an insulating layer in a solvent to form a gate insulating film.
  • the gate insulating film is composed of a single film or a multilayer film of an organic insulating film or an inorganic insulating film capable of a solution process, or an organic-inorganic hybrid film.
  • the inorganic insulating film a solution in which nanoparticles such as Al 2 O 3, Ta 2 O 5, BST, and PZT, which can be formed by a solution process, is dispersed, is used, and any one or more selected from among them is used.
  • the organic insulating film may include polymethacrylate (PMMA, polymethylmethacrylate), polystyrene (PS, polystyrene), phenolic polymer, acrylic polymer, imide polymer such as polyimide, arylether polymer, amide polymer, fluorine polymer, p -Use any one or more selected from xyrene-based polymer, vinyl alcohol-based polymer, parylene (parylene).
  • PMMA polymethacrylate
  • PS polystyrene
  • phenolic polymer acrylic polymer
  • imide polymer such as polyimide, arylether polymer, amide polymer, fluorine polymer
  • p -Use any one or more selected from xyrene-based polymer, vinyl alcohol-based polymer, parylene (parylene).
  • a polymer electrolyte-based gel material is used as a gate insulating film through spray coating.
  • the gate insulating film is present in a gel state and may serve as both the gate insulating film and the gate electrode without forming the gate electrode.
  • the gate electrode is formed by spray printing using the conductive ink used to form the source / drain electrodes described above to form the gate electrode. Patterning is attempted using the shadow mask method described above to selectively form a gate electrode only on the active layer of the transistor.
  • CMOS inverter In order to form an electronic circuit such as a CMOS inverter or a ring oscillator through the spray coating method, hole-transfer and electron-transfer semiconductor inks for forming P-Channel and N-Channel are patterned through a shadow mask as shown in FIG. Connect to 1: to manufacture CMOS inverter.
  • the ring oscillator is manufactured by connecting the gate and the drain of the CMOS inverter through a via hole and connected in series.
  • FIG. 6 shows a transition curve of a P-Channel tip-pentacene organic thin film transistor manufactured by spray printing.
  • Tips pentacene is dissolved in a solvent such as toluene, xylene or chlorobenzene at a concentration of 10 mg / ml and sprayed in the spray coating for about 1-10 seconds to obtain a thin film, preferably about 30-200 nm thick.
  • a solvent such as toluene, xylene or chlorobenzene
  • the present invention is not necessarily limited thereto, and a person skilled in the art can adjust the injection time and thickness as necessary. Maintain a spacing of 10 – 30 cm between the substrate and the spray jet nozzle.
  • the fabricated TIP pentacene thin film transistor showed the characteristics of a typical hole-transfer transistor and its device performance showed 0.1 cm2 / Vs mobility and 15 V threshold voltage.
  • the method for preparing disaano phenylene dicarboxyl imide solution for spray printing is very similar to the method for preparing tip's pentacene solution described above, and the solvent used is also the same.
  • the prepared dicyano phenylene dicarboxyl imide thin film transistor showed the characteristics of a typical electron transfer thin film transistor.
  • the measured device characteristics showed a mobility of 0.1 cm2 / Vs and a threshold voltage of -8 V.
  • FIG. 8 is a schematic diagram of a CMOS-type inverter in which the P-Channel and the N-channel are respectively patterned through a spray printing method.
  • a pattern in which the source electrode of the P-channel transistor and the drain electrode of the N-channel transistor are combined on the substrate is formed by a photolithography process or inkjet printing process using gold. Place a shadow mask on the formed pattern where only portions of the P-type or N-type transistors are open, respectively, apply only tippentacene on the active layer of the P-Channel transistor, and dicyano phenylene dicarboxylic acid on the active layer of the N-Channel transistor. Demann is applied selectively.
  • FIG. 9 shows an output curve of a CMOS input inverter made of P-Channel tip pentacene and N-channel dicyano phenylene dicarboxyl imide through a spray printing method.
  • the fabricated CMOS inverter showed stable inverter output curve even at low voltage of 20 volts.
  • FIG. 10 shows a gain curve according to a CMOS input voltage made of P-Channel tip pentacene and N-channel dicyano phenylene dicarboxylic imide through a spray printing method.
  • the fabricated CMOS inverter showed very high voltage gain of about 20 degrees.
  • the roll-to-roll spray printing apparatus includes: a substrate on which a substrate is positioned; A take-up roll and a take-up roll for continuously moving the substrate; A roller for maintaining a constant tension and speed of the substrate;
  • a spray coating unit for spraying a coating liquid on the substrate.
  • the roll-to-roll spray printing of the present invention places a substrate on an upper portion of a substrate and connects both ends of the substrate to a winding roll and an unrolling roll, and then uses the roller to wind the winding.
  • a continuous printing operation is possible in which the coating liquid is sprayed from the spray coating portion onto a substrate located on the upper portion of the substrate portion while continuously moving while maintaining a constant tension and speed of the substrate portion connected to the roll and the unwinding roll.
  • Example 1 Manufacture of organic thin film transistor through spray coating method
  • Glass substrates (Corning Glass, Eagle 2000) were washed in acetone, IP, and distilled water for 10 minutes each by an ultrasonic cleaner and dried by spraying with nitrogen gas to remove impurities on the substrate.
  • the prepared substrate was placed 15 cm under the spray nozzle of the spray coating part, and then dissolves tip pentacene (sigma-aldrich) in toluene in 1% by weight in order to manufacture an organic thin film transistor, and 0.2 microns in order to remove impurities or residues in the solution.
  • the Teflon filter of the meter was used to remove impurities such as undissolved residues and dust.
  • the tip pentacene solution thus prepared is transferred to a reservoir of a spray coater. It was sprayed for 10 seconds in the prepared spray coating.
  • the substrate was heat-treated at 120 ° C. for 10 minutes through a hot plate.
  • the prepared insulator thin film is heated by heating tungsten filament or boat to aluminum in a high vacuum chamber maintained at a vacuum of 10 -6 Torr or lower to vaporize the aluminum, and then vaporize the aluminum through the shadow mask on which the active layer of the transistor is located. Only a thin film was formed thereon, and the thickness of the deposited gate electrode was found to be 15 nm.
  • Glass substrates (Corning Glass, Eagle 2000) were washed in acetone, IP, and distilled water for 10 minutes each by an ultrasonic cleaner and dried by spraying with nitrogen gas to remove impurities on the substrate.
  • the prepared substrate was placed 15 cm under the spray nozzle of the spray coating part, and then zinc oxide (ZnO) nanoparticles (nano new material) were dissolved in isopropyl alcohol at a concentration of 5.5% by weight, followed by stirring for about 1 hour at a stirring speed of 300 RPM. It was left for 24 hours to completely dissolve.
  • ZnO zinc oxide
  • impurities such as undissolved residues and dust were removed by using a 0.2 micron Teflon filter.
  • the zinc oxide solution thus prepared was transferred to a reservoir for spray coating and sprayed for 20 seconds on the prepared spray coating. After spraying the coating solution, the substrate was heat treated at 400 ° C. for 1 hour using a vacuum oven.
  • a substrate was prepared as in Example 1 to form N-type and P-type source / drain patterns for an inverter in a CMOS type on the substrate.
  • the shape of the specific pattern is the same as the schematic diagram of FIG.
  • a shadow mask in which only the active layer of the P-type transistor was opened was first placed, and a tip pentacene solution was prepared as in Example 1 above, and then it was applied by spray printing. Thereafter, heat treatment was performed as in Example 1 to remove the remaining solvent. Then, place a shadow mask in which only the active layer of the N-type transistor is opened, prepare a solution of dicyano phenylene dicarboxyl imide as in Example 1, apply it by spray printing, and heat-treat the remaining solvent. It was completely removed.
  • Glass substrates (Corning Glass, Eagle 2000) were washed in acetone, IP, and distilled water for 10 minutes each by an ultrasonic cleaner and dried by spraying with nitrogen gas to remove impurities on the substrate.
  • the prepared substrate was placed 15 cm under the spray nozzle of the spray coating part, and then dissolves tip pentacene (sigma-aldrich) in toluene in 1% by weight in order to manufacture an organic thin film transistor, and 0.2 microns in order to remove impurities or residues in the solution.
  • the Teflon filter of the meter was used to remove impurities such as undissolved residues and dust.
  • the tip pentacene solution thus prepared is transferred to a reservoir of a spray coater. It was sprayed for 10 seconds in the prepared spray coating.
  • the substrate was heat-treated at 120 ° C. for 10 minutes through a hot plate.

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  • 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)
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  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thin Film Transistor (AREA)

Abstract

La présente invention concerne un procédé servant à fabriquer un transistor à couche mince et un procédé servant à fabriquer un circuit électronique le comportant, le procédé servant à fabriquer un transistor à couche mince par un procédé d'impression par pulvérisation comprenant : une étape consistant à préparer un substrat ; une étape consistant à préparer une solution à appliquer sur le substrat ; une étape de revêtement du substrat avec la solution préparée en utilisant un dispositif de pulvérisation ; et une étape servant à vaporiser le solvant restant en exécutant un traitement thermique après la réalisation de l'étape de revêtement. La présente invention permet le revêtement d'un transistor à couche mince d'aire importante au moyen d'un processus très économique et simple.
PCT/KR2010/006879 2010-09-27 2010-10-08 Procédé de fabrication d'un transistor à couche mince et circuit électronique utilisant le procédé de pulvérisation WO2012043912A1 (fr)

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KR10-2010-0093038 2010-09-27
KR1020100093038A KR101172187B1 (ko) 2010-09-27 2010-09-27 스프레이 방식을 이용한 박막트랜지스터 및 전자회로를 제조하는 방법

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