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WO2018125015A1 - Technique pour la production d'une couche d'oxyde conducteur transparent par une technique d'enduction au rouleau - Google Patents

Technique pour la production d'une couche d'oxyde conducteur transparent par une technique d'enduction au rouleau Download PDF

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Publication number
WO2018125015A1
WO2018125015A1 PCT/TR2017/050704 TR2017050704W WO2018125015A1 WO 2018125015 A1 WO2018125015 A1 WO 2018125015A1 TR 2017050704 W TR2017050704 W TR 2017050704W WO 2018125015 A1 WO2018125015 A1 WO 2018125015A1
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WO
WIPO (PCT)
Prior art keywords
technique
roller
coating
solution
glass substrate
Prior art date
Application number
PCT/TR2017/050704
Other languages
English (en)
Inventor
Refika BUDAKOGLU
Ferhat ASLAN
Ibrahim BOZ
Original Assignee
Turkiye Sise Ve Cam Fabrikalari Anonim Sirketi
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Turkiye Sise Ve Cam Fabrikalari Anonim Sirketi filed Critical Turkiye Sise Ve Cam Fabrikalari Anonim Sirketi
Publication of WO2018125015A1 publication Critical patent/WO2018125015A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C03C2217/231—In2O3/SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/118—Deposition methods from solutions or suspensions by roller-coating

Definitions

  • This invention relates to the production of transparent conductive oxide thin films that form the basis of electronic device technology by a roller coating technique which allows them to deposit on glass surfaces with large areas having high transparency and electric conductivity under atmospheric pressure, without requiring a vacuum environment.
  • Thin film is the name given to the materials of various layers with thicknesses ranging from a size of nanometres to micrometers. Thin films, gaining popularity among research-development studies carried out in recent years form the basis of electronic device technology.
  • transparent conductive oxide thin films include examples such as flat panel screen electrodes, polymer electronics, gas sensors, varistors, solar cells and low emission (low-E) surface coating applications which reduce the emission value of glass surfaces in heat thermal insulation, respectively.
  • films with high optical transparency are used on the front surface.
  • the transparent material used on the front surface must be as conductive as metal in order to collect current carriers. This is only possible with transparent conductive oxide films.
  • ITO indium tin oxide
  • FTO fluorescence tin oxide
  • AZO antimony doped zinc oxide
  • GZO gallium doped zinc oxide
  • PLD pulsed laser deposition
  • MBE molecular beam epitaxy
  • ITO which is the most commonly-used among transparent conductive oxide films, is a highly disordered n-type wideband gap semiconductor obtained by doping tin (Sn) to indium oxide (ImCb). ITO films with a commercial value need to have a visible range light transparency of over 80% and surface resistance below a value of 20 ohm/square; in other words, transparency and electric conductivity of a film is desired to be high.
  • the most commonly used technique for the production of ITO films in today's technology is magnetron sputtering technique. In this technique, large volume vacuum systems are required for large scale implementations. Moreover, more than one sputtering source is required for the coating to deposit homogeneously on the whole surface. Since, technique magnetron sputtering technique is based on high cost and complicated systems, it is of great importance that alternative techniques which do not require a vacuum environment be developed and be introduced into the field of technology.
  • U.S. document no US2016024640 (Al) in the state of the art discloses a transparent and conductive film and the production technique for this film.
  • the invention mentioned in the document relates to a transparent oxide film with high transparency in the visible light range and an organic polymer film base.
  • a transparent conductive oxide coating is applied on the substrate.
  • the invention which is a transparent conductive oxide film comprises a thin conductive coating which has low resistivity and surface tension.
  • the coating is indium tin oxide (ITO).
  • ITO indium tin oxide
  • the coating applied on the polymer substrate is applied by RF superimposed DC spraying.
  • glass is used as substrate and ITO is coated on the glass by roller coating technique.
  • the RF superimposed DC sputtering technique mentioned in the invention in the state of the art is a completely different process than the roller coating technique.
  • the object of the present invention is to realize a transparent conductive oxide film production method by means of a roll coating technique which enables coating on wide surface materials at atmospheric pressure.
  • Another object of this invention is to realize a technique for the production of a transparent conductive oxide film by a roller coating technique which allows high quality production with high optical transparency at room conditions.
  • Yet another object of this invention is to realize a technique for the production of a transparent conductive oxide film by a roller coating technique which allows the production of a film with high optical transparency at the visible range directly on the line by using suitable solvents.
  • a solution of the film which is to be formed on the glass is prepared firstly.
  • This solution is a solution which comprises tin and indium as starting materials, preferably at different proportions.
  • wet films are obtained by applying them on the glass surface by a roller coating technique.
  • a glass substrate whereon the coating is to be applied is cleaned by using chemicals in an ultrasonic bath.
  • the coating solution is poured into an application vessel of a roller device, and the glass substrate is coated after the solution passes through the rollers.
  • the coated glass is subjected to heat treatment to remove the organic components to produce a thin film.
  • the obtained film is annealed and oxide layers are formed.
  • Figure 1 is a schematic view of the steps of the technique for the production of a transparent conductive oxide film by roller coating technique.
  • Figure 2 is a schematic view of the technique for the production of a transparent conductive oxide film by roller coating technique.
  • Figure 3 is a graph of the optical transparency (%, y axis) - wavelength (nm, x axis) of a glass 5 times ITO coated by roller coating technique and an uncoated glass
  • a technique for the production (100) of a transparent oxide thin film (F), wherein transparent conductive oxide thin films which form the basis of electronic device technology are produced by a roller coating technique which allows them to deposit on glass surfaces with large areas with high transparency and electric conductivity without requiring vacuum systems, comprises the steps of:
  • an indium oxide solution (S) comprising indium (III) nitratehydrate and tin 2-ethyl ethanoate as starting materials and triethanolamine as a stabilizer at different ratios is produced (1011),
  • a q quality parameter is determined according to the field of utilization of the film (F) to be formed on the glass substrate (A) before starting the coating process, q quality parameter of the film (F) varies according to the field of the utilization of the product to be obtained at the end of the process.
  • Q, quality parameter can be the thickness, optical transparency, resistivity, mobility or carrier intensity of the film (F).
  • the glass substrate (A) is subjected to coating processes successively.
  • the solution (S) to be used is prepared (101) first.
  • the solution (S) is prepared by sol-gel technique.
  • a homogeneous mixture is obtained by dissolving suitable salts or alkoxides of the elements in the chemical composition of the film (F) in a suitable solvent.
  • suitable salts or alkoxides of the elements in the chemical composition of the film (F) in a suitable solvent.
  • S solution (S) (101)
  • it comprises starting materials of tin and indium preferably at different proportions.
  • Indium (III) nitratehydrate or indium acetate or tin (II) chloride or 2-ethyl ethanoate as starting materials is used in the step of producing (1011) an indium oxide solution (S) comprising tin.
  • indium (III) nitratehydrate and tin 2-ethyl ethanoate are chosen as starting materials.
  • Triethanolamine is preferably used as a stabilizer.
  • ethanol as a solvent and preferably acetic acid as a catalyst are used.
  • the amounts of indium (III) pentahydrate and acetic acid are determined first.
  • the solution (S) formed by indium (III) pentahydrate and glacial acetic acid and the solution (S) formed by tin 2-ethyl ethanoate and ethanol are stirred separately at room temperature for 1-2 hours. After the stirring is completed separately, the stirring process is repeated after combining the two solutions (S). While preparing (101) the coating solution (S), the molar ratio of Sn/In in the solution is adjusted so as to be in a range of % 10-20. The said Sn/In ratio is determined by indium and tin starting materials.
  • the stirring process of the two solutions (S) continues at room temperature for 12-24 hours.
  • the stirring process is preferably performed with a magnetic mixer.
  • a thin film (F) is obtained (102).
  • glass substrate whereon the coating is to be applied are cleaned (1021).
  • Glass substrate (A) are cleaned by using chemicals in an ultrasonic bath.
  • Glass substrate (A) used in a preferred embodiment of the invention preferably have a size of 200 mm x 300 mm.
  • a coating is applied (1022) on the glass substrate (A).
  • the prepared solution (S) is first poured into a solution vessel (V) of a roller (R). The coating process is started after the solution (S) and the glass substrate (A) are put in a roller (R) device.
  • the glass substrate (A) is coated with the solution (S) by means of a cylindrical roller (R) ( Figure 2, in the arrow direction).
  • a cylindrical roller (R) Figure 2, in the arrow direction.
  • the type of the roller (R) and the rotational speed of it thinner or thicker films (F) are obtained.
  • the glass substrate (A) is coated (1022)
  • the glass substrate (A) is heat treated (1023) at a low temperature.
  • organic components of the solution (S) used in coating are removed from the surface of the glass substrate (A).
  • the removing process is preferably performed in an incubator by carrying out a heat treatment.
  • a thin film (F) layer is formed on the glass substrate (A).
  • films (F) After the heat treatment, films (F) still have an amorphous form.
  • films (F) with an amorphous form are annealed (1024) at a high temperature, in open air or in an inert gas environment.
  • the film (F) obtained on the glass substrate (A) is measured for the pre-determined quality parameter q. If the value obtained as a result of the measurement is concordant with the pre-determined q value, the process is ended. If the quality parameter q of the film (F) obtained as a result of the measurement hasn't reached the pre-determined value, the process is repeated (1025) by returning to step (1022).
  • the processes of (1022), (1023) and (1024) are repeated (1025) successively until the pre-determined q quality parameter is achieved and transparent oxide layers are formed.
  • the quality parameter q of the film (F) which is desired to be obtained on the glass substrate (A) by the technique for production (100) of a transparent conductive oxide film is the thickness of the obtained film (F) and the targeted q value is determined as 400 nm.
  • the thickness of the coating formed on the glass substrate (A) as a result of the first cycle is measured as 100 nm.
  • a film (F) with a thickness of 400 nm on the glass substrate (A) is formed by performing three more cycles.
  • the thickness of ITO films (F) coated five times is measured about 350 nm.
  • the resistivity, mobility and carrier intensity of an ITO sample are measured respectively as 4.49xl0 "3 ⁇ , 5.73 cm 2 /Vs and 2.42 x 10 20 cm “3 .
  • a graph of the optical transparency of a 5 times ITO coated glass (I/G) with a roller (R) device and an uncoated glass is given.
  • the vertical axis (y axis) represents transparency (%) and the horizontal axis (x axis) represents wavelength.
  • the transparency of ITO films (F) in the visible range is over 84%.
  • Results of hall effect measurements and results of UV-VIS spectrometry shows that transparent conductive oxide films produced with a roller (R) technique can be used in optoelectronic applications.
  • a transparent conductive oxide film (F) is produced on a glass substrate (A) under atmospheric pressure without using high-cost and complex systems such as vacuum systems.
  • the technique of the invention allows operation under atmospheric pressure and the coating of glass substrate (A) with a large surface area. Therefore, the technique of the invention can be used in industrial applications.
  • the absence of any vacuum devices in the system reduces the cost of the system and coating.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention concerne une technique (100) pour la production de couches minces d'oxyde transparent (F), qui forme la base d'une technologie de dispositif électronique ayant des propriétés élevées de transparence et de conductivité électrique, sans nécessiter de systèmes sous vide, sous pression atmosphérique sur des surfaces ayant une grande superficie si nécessaire, avec des techniques d'enduction au rouleau (R).
PCT/TR2017/050704 2016-12-30 2017-12-27 Technique pour la production d'une couche d'oxyde conducteur transparent par une technique d'enduction au rouleau WO2018125015A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR201620296 2016-12-30
TR2016/20296 2016-12-30

Publications (1)

Publication Number Publication Date
WO2018125015A1 true WO2018125015A1 (fr) 2018-07-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110551976A (zh) * 2019-08-23 2019-12-10 陕西工业职业技术学院 一种真空玻璃镀膜设备

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303554A (en) * 1979-06-22 1981-12-01 Hitachi, Ltd. Composition and process for producing transparent conductive film
GB2308080A (en) * 1995-12-15 1997-06-18 Samsung Display Devices Co Ltd Method for forming a transparent conductive layer
EP1012635A2 (fr) * 1997-01-27 2000-06-28 Peter D. Haaland Revetements, procedes et appareil pour reduire la reflexion a partir de substrats optiques
US20160024640A1 (en) 2013-01-16 2016-01-28 Nitto Denko Corporation Transparent conductive film and production method therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303554A (en) * 1979-06-22 1981-12-01 Hitachi, Ltd. Composition and process for producing transparent conductive film
GB2308080A (en) * 1995-12-15 1997-06-18 Samsung Display Devices Co Ltd Method for forming a transparent conductive layer
EP1012635A2 (fr) * 1997-01-27 2000-06-28 Peter D. Haaland Revetements, procedes et appareil pour reduire la reflexion a partir de substrats optiques
US20160024640A1 (en) 2013-01-16 2016-01-28 Nitto Denko Corporation Transparent conductive film and production method therefor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIU J ET AL: "PREPARATION, NANOSTRUCTURE AND PROPERTIES OF INDIUM TIN OXIDE (ITO) FILMS ON GLASS SUBSTRATES. PART 1. PREPARATION AND NANOSTRUCTURE", PHYSICS AND CHEMISTRY OF GLASSES, SOCIETY OF GLASS TECHNOLOGY, SHEFFIELD, GB, vol. 40, no. 5, 1 October 1999 (1999-10-01), pages 277 - 281, XP000890624, ISSN: 0031-9090 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110551976A (zh) * 2019-08-23 2019-12-10 陕西工业职业技术学院 一种真空玻璃镀膜设备

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