EP1910240A1 - Agents de gravure pour des couches conductrices, oxydiques et transparentes - Google Patents

Agents de gravure pour des couches conductrices, oxydiques et transparentes

Info

Publication number
EP1910240A1
EP1910240A1 EP06762349A EP06762349A EP1910240A1 EP 1910240 A1 EP1910240 A1 EP 1910240A1 EP 06762349 A EP06762349 A EP 06762349A EP 06762349 A EP06762349 A EP 06762349A EP 1910240 A1 EP1910240 A1 EP 1910240A1
Authority
EP
European Patent Office
Prior art keywords
etching
transparent
phosphoric acid
conductive layers
etching medium
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP06762349A
Other languages
German (de)
English (en)
Inventor
Armin Kuebelbeck
Werner Stockum
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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 Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1910240A1 publication Critical patent/EP1910240A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8051—Anodes
    • H10K59/80517—Multilayers, e.g. transparent multilayers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a novel etching medium for patterning transparent conductive layers such as those used in the manufacture of liquid crystal displays (LCD) using flat panel displays or organic light emitting displays (OLEDs) or thin film solar cells.
  • LCD liquid crystal displays
  • OLED organic light emitting displays
  • novel liquid etching medium can advantageously be applied by means of printing processes to the oxidic, transparent, conductive layers to be structured. A subsequent temperature treatment accelerates or starts the etching process.
  • An LC display consists essentially of two glass plates, provided with oxidic, transparent, conductive layers, mostly of indium tin oxide (ITO), which change their light transmission by applying a voltage. In between is a liquid crystal layer. By using spacers, the touch of the ITO
  • Oxidative, transparent, conductive layers thus play an outstanding role in the production process of flat-panel displays and thin-film solar cells.
  • At Flat screens based on liquid crystal displays or organic light emitting diodes at least the electrode facing the viewer must have the highest possible transparency in order to make the visual effect visible to the viewer.
  • a-Si amorphous silicon
  • CIS copper indium selenide
  • cadmium telluride the side of the solar cell facing the sun consists of an oxidic, transparent, conductive material. This is necessary because the semiconductive layers have too low an electrical conductivity, as an economic transport of charge carriers would be possible.
  • CTO Q cadmium stannate CdSnO 3 (CTO) ⁇ indium doped zinc oxide ZnO: ln (IZO) ⁇ undoped tin (IV) oxide (TO) ⁇ undoped indium (IM) oxide (I0)
  • ITO indium tin oxide
  • the oxidic, transparent, conductive layers are usually deposited over the entire surface of the substrate.
  • flat glass machine-drawn soda lime glasses, borosilicate glasses or similar glasses
  • Other suitable carrier materials are polycarbonate (PC), polyethylene terephthalate 10 (PET) and similar transparent polymers.
  • the transparent conductive layer is structured. With flat screens, individual picture elements (pixels or segments) can be controlled. In thin-film solar cells to reach a serial
  • the transparent, conductive layer is coated through an applied mask.
  • Mask evaporation or mask sputtering is a fairly straightforward process.
  • the method is not suitable for mass production, especially for the production of larger substrates.
  • the masks warp in the process due to different expansion coefficients of substrate and mask.
  • the masks can be used only for a few coating steps, since material is continuously deposited thereon.
  • more complex structures, such as hole structures can not be made with an overlay mask.
  • the resolving power with regard to the formation of finest lines and structures in this method is very limited. The mask sputtering has therefore been able to establish only for small batches with low numbers.
  • LASER light in the near infrared region NIR
  • Nd near infrared region
  • the method is described on the website of Laserod.com, Inc. (http://www.laserod.com/laser direct write.htm).
  • a disadvantage of this method is the relatively high instrumental effort, the low throughput in more complex structures and the re-deposition of vaporized material on adjacent areas.
  • the LASER ablation is used essentially only in the area of the thin-film solar cells, for example for cadmium tellurium solar cells.
  • An example of LASER ablation on transparent conductive layers is described (C. Molpeceres et al., 2005 J. Micromech, Microeng., 15 1271-1278).
  • etchants i. Of chemically aggressive compounds it comes to the dissolution of the attack of the etchant exposed material. In most cases, the goal is to completely remove the layer to be etched. The end of the etching is achieved by the impact with respect to the etchant substantially 10 resistant layer.
  • ⁇ coating of the substrate surface (for example by
  • etching Immersion of the substrates in the etching bath, etching o spin-on or spraying:
  • the etching is applied to a rotating substrate, the etching can be done without / with energy input (eg IR or UV irradiation) oc o dry etching process such as plasma etching in complex vacuum systems or etching with reactive gases in flow reactors.
  • energy input eg IR or UV irradiation
  • oc o dry etching process such as plasma etching in complex vacuum systems or etching with reactive gases in flow reactors.
  • liquid etching media especially for the widespread in the field of flat screens fully oxidized indium tin oxide (ITO), are described in the literature: ⁇ iron (III) chloride + hydrochloric acid ⁇ hot about 30 wt.% Hydrochloric acid ⁇ hot hydrobromic acid 48 wt % ⁇ aqua regia (partly diluted)
  • the etching in the gas phase, possibly in the plasma, of ITO is known, but currently plays only a minor role.
  • hydrogen bromide gas or hydrogen iodide gas is used.
  • Corresponding methods are described by Mitsui Chemical on the Internet site http: //www.mitsui- chem.co.ip / ir / 010910.pdf p.23.
  • the doped tin oxide layers are transparent, conductive layers such as those used in the manufacture of liquid crystal displays (LCD) using flat panel displays or organic light emitting displays
  • OLED organic light-emitting diode
  • thin-film solar cells used in thin-film solar cells. It is also an object of the present invention to provide new etching media which, after etching, can be easily removed from the treated surfaces under the action of heat, without leaving any residues.
  • the present invention provides etching media for etching oxide, transparent, conductive layers comprising at least one etchant
  • etching media according to the invention are particularly suitable for etching doped tin oxide layers.
  • Etching media according to the invention comprise as active, etching component at least one acid selected from the group consisting of ortho, meta, pyro, oligo- and polyphosphoric acid and / or meta-phosphorus pentoxide or mixtures thereof.
  • etching component at least one acid selected from the group consisting of ortho, meta, pyro, oligo- and polyphosphoric acid and / or meta-phosphorus pentoxide or mixtures thereof.
  • the present invention also relates to corresponding etching media in paste form, which except at least one
  • Contain etchant, solvent, particulate and / or soluble inorganic and / or organic thickeners and optionally additives such as defoamers, thixotropic agents, leveling agents, deaerators and adhesion promoters.
  • the present invention likewise provides a method for etching oxidic, transparent, conductive layers, in particular corresponding doped tin oxide layers.
  • the etching medium is applied by spraying, spin-coating, dipping or by printing by screen, stencil, stamp, pad or ink jet printing.
  • Corresponding etching media for applying the method are preferably applied to the substrate to be etched by means of a printing method.
  • the applied etching medium can be activated by heating.
  • the heating can accordingly take place in different ways, namely on a hotplate, in a convection oven, by IR radiation, visible light, UV radiation, or with the aid of microwaves.
  • oxidic, transparent, conductive layers for the production of solar cells can also be structured in a corresponding manner.
  • oxidic, transparent, conductive layers for the production of flat screens can also be structured in a corresponding manner.
  • WO 03/040345 describes a combined etching and doping medium for etching silicon nitride.
  • the etchant contained is based on phosphoric acid, or its salts and / or corresponding
  • Phosphoric acid or their salts or suitable precursors from which a phosphoric acid is released under suitable conditions of use.
  • Phosphonic acid phosphorous acid
  • phosphinic acid hypophosphorous acid
  • phenylphosphinic acid and other organic phosphinic acids phenylphosphonic acid and other organic phosphonic acid.
  • Suitable salts of phosphoric acid are mono-, di-, tri-salts of the acids listed under phosphoric acids. In particular, these include the corresponding more ammonium salts to understand. From these salts, the corresponding phosphoric acids are released in the formulations of the etching media, if appropriate by heating.
  • phosphoric acid precursors compounds which form by chemical reaction and / or thermal decomposition of phosphoric acids and / or their salts.
  • Suitable for use in the etching media according to the invention are in particular corresponding mono-, di- or th-esters of said phosphoric acids, such as, for example, monomethyl phosphate, di-n-butyl phosphate (DBP) and tert-butyl phosphate (TBP).
  • Phosphoric acids are per se Lewis acids that are capable of forming adducts with Lewis bases. These phosphoric acid adducts may optionally decompose at higher temperatures back into the starting materials. Lighter volatile or decomposing Lewis bases release the phosphoric acids.
  • An example of a suitable Lewis base is 1-methyl-2-pyrrolidone (NMP), which is also used in exemplified compositions of the invention.
  • phosphoric acid-based etching media have considerable advantages: ⁇
  • the etching medium can be selectively applied in the form of a thickened paste to the substrate to be etched by means of a printing process. On the complex photolithography can be omitted.
  • ⁇ Due to the very low volatility of the etching medium, which assumes a vitreous state during the etching process ("Phosphorsalzperle"), the etch rate is constantly high, even for small amounts of etching medium, over a longer period of time Within a few minutes their etching power by evaporation of the solvent or etching medium almost completely.
  • the etching can be started by heat input. at
  • the etching rate in volloxidatorm is indium tin oxide ca.
  • the etching medium has a very low vapor pressure. As a result, it is not corrosive to the environment. Thus, for example, metallic components such as: printheads, printing screens, etc., which are in direct contact with the etching medium, can easily be used.
  • the now ready to use paste can be printed with a 260 mesh stainless steel mesh screen.
  • polyester or similar sieve materials can be used.
  • Polyester or similar sieve materials are used.
  • the now ready to use paste can be printed with a 260 mesh stainless steel mesh screen.
  • polyester or similar sieve materials can be used.
  • Substrate glass with 125nm ITO layer
  • the etched line had an average width of 50 ⁇ m.
  • Viscosity of etching medium 7-1 OmPas (with optimized etching paste)
  • Pixel Resolution 1440 dpi Printhead Distance: 1 mm
  • Substrate glass with 125nm ITO layer
  • the etched line had a width of ⁇ 35 ⁇ m.

Abstract

Nouvel agent de gravure pour la structuration de couches conductrices transparentes, telles qu'elles sont utilisées par exemple dans la fabrication d'afficheurs à cristaux liquides (LCD) pourvus d'écrans plats ou d'afficheurs à diodes électroluminescentes organiques (OLED) ou pour des cellules solaires à couche mince. Il s'agit spécialement de compositions exemptes de particules à l'aide desquelles des structures sélectivement fines peuvent être gravées dans des couches conductrices, oxydiques et transparente, sans endommager ou attaquer les surfaces adjacentes. Le nouvel agent de gravure liquide selon la présente invention peut être avantageusement déposé sur les couches conductrices, oxydiques et transparentes à structurer à l'aide de procédés d'impression. Un traitement thermique consécutif accélère ou fait démarrer le processus de gravure.
EP06762349A 2005-07-25 2006-07-03 Agents de gravure pour des couches conductrices, oxydiques et transparentes Withdrawn EP1910240A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005035255A DE102005035255A1 (de) 2005-07-25 2005-07-25 Ätzmedien für oxidische, transparente, leitfähige Schichten
PCT/EP2006/006444 WO2007012378A1 (fr) 2005-07-25 2006-07-03 Agents de gravure pour des couches conductrices, oxydiques et transparentes

Publications (1)

Publication Number Publication Date
EP1910240A1 true EP1910240A1 (fr) 2008-04-16

Family

ID=36939209

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06762349A Withdrawn EP1910240A1 (fr) 2005-07-25 2006-07-03 Agents de gravure pour des couches conductrices, oxydiques et transparentes

Country Status (9)

Country Link
US (1) US7824563B2 (fr)
EP (1) EP1910240A1 (fr)
JP (1) JP4901866B2 (fr)
KR (1) KR101325957B1 (fr)
CN (2) CN104496192A (fr)
DE (1) DE102005035255A1 (fr)
MY (1) MY145052A (fr)
TW (1) TWI391473B (fr)
WO (1) WO2007012378A1 (fr)

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Also Published As

Publication number Publication date
KR20080030681A (ko) 2008-04-04
CN104496192A (zh) 2015-04-08
DE102005035255A1 (de) 2007-02-01
US20080217576A1 (en) 2008-09-11
KR101325957B1 (ko) 2013-11-07
TW200712179A (en) 2007-04-01
CN101228097A (zh) 2008-07-23
TWI391473B (zh) 2013-04-01
JP4901866B2 (ja) 2012-03-21
US7824563B2 (en) 2010-11-02
JP2009503825A (ja) 2009-01-29
MY145052A (en) 2011-12-15
WO2007012378A1 (fr) 2007-02-01

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