EP1301937B1 - Dalle en verre munie d'electrodes en un materiau conducteur - Google Patents

Dalle en verre munie d'electrodes en un materiau conducteur Download PDF

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Publication number
EP1301937B1
EP1301937B1 EP01945408A EP01945408A EP1301937B1 EP 1301937 B1 EP1301937 B1 EP 1301937B1 EP 01945408 A EP01945408 A EP 01945408A EP 01945408 A EP01945408 A EP 01945408A EP 1301937 B1 EP1301937 B1 EP 1301937B1
Authority
EP
European Patent Office
Prior art keywords
alloy
electrodes
plate according
dielectric layer
dopant
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.)
Expired - Lifetime
Application number
EP01945408A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1301937A1 (fr
Inventor
Agide Moi
Luc Berthier
Jean-Pierre Creusot
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.)
Thomson Plasma SAS
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Thomson Plasma SAS
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Filing date
Publication date
Application filed by Thomson Plasma SAS filed Critical Thomson Plasma SAS
Publication of EP1301937A1 publication Critical patent/EP1301937A1/fr
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Publication of EP1301937B1 publication Critical patent/EP1301937B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/10—AC-PDPs with at least one main electrode being out of contact with the plasma
    • H01J11/12—AC-PDPs with at least one main electrode being out of contact with the plasma with main electrodes provided on both sides of the discharge space
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/22—Electrodes, e.g. special shape, material or configuration
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J11/38—Dielectric or insulating layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/22—Electrodes
    • H01J2211/225—Material of electrodes

Definitions

  • the present invention relates to a slab comprising a glass substrate on which at least one electrode is made of a conductive material. It relates more particularly to the material for producing the electrodes, especially when the slab is used in the manufacture of display panels such as plasma panels.
  • the present invention will be described with reference to the manufacture of plasma panels.
  • the present invention is not limited to the plasma panel manufacturing method, but may be used in all types of processes requiring materials of the same type under similar conditions.
  • PDP Plasma panels generally called PDP for "Plasma Display Panel” in English are flat screen type of display screens.
  • PDPs There are several types of PDPs that all operate on the same principle of an electric discharge in a gas, accompanied by a light emission.
  • the PDPs consist of two insulating glass slabs, typically glass soda-lime type, each supporting at least one network of conductive electrodes and delimiting between them a gas space.
  • the slabs are joined to each other so that the electrode arrays are orthogonal, each electrode intersection defining an elementary luminous cell to which a gaseous space corresponds.
  • the electrodes of a plasma panel must have a number of features. Thus, they must have a low electrical resistivity. Indeed, the electrodes feeding several thousand cells, it circulates a high current inside the electrode which can go up to 500 mA at 1 A instantaneous. On the other hand, plasma panels having a large size up to 60 "diagonal, the length of the electrodes is large. cause a significant loss of light output due to the voltage drop associated with the current flow in the electrodes.
  • the electrode array is covered with a thick layer of a dielectric material, usually a borosilicate glass.
  • a dielectric material usually a borosilicate glass.
  • the electrodes must have a high resistance to corrosion, in particular during the baking of the dielectric layer; indeed, during this phase of the process, the reactions between the dielectric layer and the electrode, or even between the glass of the slab and the electrode, cause an increase in the electrical resistance of the electrode and the products of this reaction lead to degradation of the optical transmission, the dielectric constant and the breakdown voltage of the dielectric layer.
  • a first technique consists in depositing a paste or ink based on silver, gold or a similar material.
  • This conductive paste is deposited in a thickness generally greater than or equal to 5 microns, by means of screen printing, vaporization, various coating.
  • the electrodes are obtained directly during the deposition or by a photogravure process.
  • this technique requires a specific annealing at a temperature above 500 ° C to obtain the conduction and the use of several specific dielectric layers to minimize the diffusion of the electrode materials in the dielectric, this diffusion is likely to degrade the electrical and optical characteristics of the panel.
  • the second technique consists of thin-layer metal deposition.
  • the thickness of the layers is from a few hundred angstrom to a few microns.
  • the electrodes are obtained generally by photolithography or "lift-off" of a thin layer of copper or aluminum deposited by evaporation under vacuum or by sputtering.
  • the document EP1220267 published after the filing of the present application, describes the use of aluminum alloys, such as Al-Mn alloy, for this type of electrodes.
  • the document JP56-121254 describes the use of aluminum and copper. This thin film technology does not require annealing to obtain the conduction of the electrodes.
  • electrode resistances R ⁇ 5 to 12 m ⁇ ⁇ according to the materials used for electrodes having a thickness of 2 to 5 ⁇ m.
  • the materials used in this case although having high conductivity, react with the glass substrate and the dielectric layer when it is fired, which leads to an increase in the resistance of the electrodes and to an impairment of the performance of the layer dielectric due to diffusion in the dielectric of the reaction products between the material of the electrode and the dielectric layer. Formation of bubble strings is observed which degrades the transparency of the dielectric layer, its dielectric constant and its breakdown voltage.
  • multilayer deposits consisting of, for example, stacks of Al-Cr, Cr-Al-Cr, Cr-Cu-Cr layers have been proposed.
  • the present invention therefore aims to overcome the aforementioned drawbacks of the thin film deposition technique by providing a new material for producing an array of electrodes on a glass substrate.
  • the subject of the present invention is a slab comprising a glass substrate on which at least one electrode made of a conducting material is formed, characterized in that, at least at the interface between said electrodes and the glass and / or at least at the interface between said electrodes and the dielectric layer, the conductive material of the electrodes is constituted by a metal alloy based on aluminum and / or zinc having a melting point greater than 700 ° C.
  • the metal alloy based on aluminum and / or zinc comprises at least 0.01% by weight of at least one dopant whose nature and proportions in the alloy are adapted to obtain a point melting said higher alloy at 700 ° C; preferably, the nature of the dopant is adapted so that the corresponding alloy does not comprise a eutectic point; preferably, this dopant is selected from the group consisting of titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron (zinc alloy) and antimony.
  • the dopant is preferably chosen to obtain an alloy having an electrical resistivity as close as possible to that of the pure conductive material.
  • a substrate 10 which may be constituted for example by a glass called FLOAT GLASS.
  • the glass substrate may be optionally annealed or shaped.
  • Other types of flat glass may be used, in particular glasses of the borosilicate or alumino-silicate type.
  • a thin layer 20 of a conductive material is deposited on the substrate 10.
  • This layer 20 typically has a thickness of between 0.01 ⁇ m and 10 ⁇ m.
  • this layer is constituted by a metal alloy based on aluminum or zinc, which has a melting point greater than that of aluminum or pure zinc, in this case greater than 700 ° C. .
  • This metal alloy comprises between 0.01% and 49% by weight of at least one dopant; the nature and proportions of the dopants are adapted in a manner known per se to obtain a melting point of the alloy greater than 700 ° C .; preferably, these dopants are chosen so as to form alloys without eutectic point; preferably, these dopants are chosen so as to have expansion coefficients that are much smaller than those of the conductive material in order to reduce the coefficient of expansion of the alloy and to bring it closer to that of the substrate and also of the dielectric, as explained hereafter ; preferably, this dopant is chosen from the group comprising manganese, vanadium, titanium, zirconium, chromium, molybdenum, tungsten, iron (zinc-based alloy) and antimony; preferably, the proportions of dopant are of the order of 2% by weight in the alloy.
  • a conventional method of the prior art is used; a vacuum deposition method such as vacuum sputtering is preferably used, vacuum evaporation, vacuum CVD deposition for "Chemical Vapor Deposition" in English.
  • a variant of the present invention it is possible to perform vacuum deposition in the form of a multilayer, for example using several targets in the case of vacuum spraying.
  • a first layer of alloy will be deposited for the part in contact with the substrate and then a conductive layer of the base metal without doping aluminum or zinc, then again an alloy layer intended for be in contact with the dielectric layer, which may be of different composition than the first alloy layer.
  • FIG. 1b and 1c schematically shows the realization of the electrode array following the deposition of a metal layer 20, which in this case is an aluminum-based alloy having a melting point greater than 700 ° C.
  • the electrode patterns 21 are made using known methods of "lift off” or photoengraving type. As shown on the figure 1b the layer 20 is covered with a resin 30 and is etched. The pattern of the electrodes 21 is determined using a UV-illuminated mask, depending on the type of resin used, namely a positive or negative resin. Then, the electrodes themselves are etched with a single etching bath having a composition identical or similar to that used for pure aluminum.
  • the method of manufacturing the electrode array which has just been described makes it possible to obtain, for the different layers of the electrode, identical widths; a geometry of electrodes comparable to that obtained by producing pure aluminum electrodes is then obtained; much more regular flanks are obtained more precisely than in the case of multilayers such as the Al-Cr or Cr-Al-Cu or Cr-Cu multilayers known and previously mentioned; we only use a single etching bath, which is more economical.
  • the electrodes 21 are then covered by a thick layer 22 of a dielectric material in using a conventional method such as screen printing, roller coating or spraying a suspension or a dry powder.
  • the dielectric layer consists of a glass or enamel based on lead oxide, silica and boron, based on bismuth oxide, silica and lead-free boron, based on oxide of bismuth, lead, silica and boron as a mixture.
  • an aluminum-based metal alloy having a melting point greater than 700 ° C. and comprising, as dopant, an element chosen from titanium, zirconium, vanadium, chromium, molybdenum, Tungsten, manganese and antimony have a number of advantages. Titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese and antimony are alloys without eutectic point.
  • An aluminum alloy comprising 2% by weight of vanadium or titanium has a melting point of about 900 ° C., compared with 660 ° C. for pure aluminum.
  • the melting point of an aluminum alloy with 2% manganese is 700 C and it has a resistivity of about 4 ⁇ Cm against 2.67 ⁇ Cm for pure aluminum.
  • the above materials have expansion coefficients much lower than that of aluminum, which allows to reduce the coefficient of expansion of the alloy and bring it closer to that of the substrate and the dielectric layer. Thus, it reduces the risk of occurrence of cracks in the dielectric layer as well as in the magnesia layer during the various stages of cooking.
  • electrodes of aluminum alloy containing 2% titanium have a R ⁇ of 25 m ⁇ ⁇ after firing the dielectric layer at 585 ° C for 1 hour, a value close to that obtained before firing.
  • the electrode / glass interface has a uniform metallic appearance and the electrode / dielectric layer interface does not present a rosary of bubbles.
  • electrodes with a thickness of 3 ⁇ m in pure aluminum have an R ⁇ which goes from 10m ⁇ ⁇ before firing of the dielectric layer to 25 ⁇ ⁇ after firing of the dielectric layer at a temperature above 550 ° C for 1 hour.
  • the appearance of the metal / glass interface is greyish and nonuniform and many strings of bubbles are present at the electrode / dielectric layer interface.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Gas-Filled Discharge Tubes (AREA)
EP01945408A 2000-07-21 2001-06-13 Dalle en verre munie d'electrodes en un materiau conducteur Expired - Lifetime EP1301937B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0009570A FR2812125A1 (fr) 2000-07-21 2000-07-21 Dalle en verre munie d'electrodes en un materiau conducteur
FR0009570 2000-07-21
PCT/FR2001/001822 WO2002009137A1 (fr) 2000-07-21 2001-06-13 Dalle en verre munie d'electrodes en un materiau conducteur

Publications (2)

Publication Number Publication Date
EP1301937A1 EP1301937A1 (fr) 2003-04-16
EP1301937B1 true EP1301937B1 (fr) 2010-08-18

Family

ID=8852766

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01945408A Expired - Lifetime EP1301937B1 (fr) 2000-07-21 2001-06-13 Dalle en verre munie d'electrodes en un materiau conducteur

Country Status (10)

Country Link
US (1) US6784618B2 (ja)
EP (1) EP1301937B1 (ja)
JP (1) JP4915890B2 (ja)
KR (1) KR100755331B1 (ja)
CN (1) CN1257522C (ja)
AU (1) AU2001267635A1 (ja)
DE (1) DE60142835D1 (ja)
FR (1) FR2812125A1 (ja)
TW (1) TWI239937B (ja)
WO (1) WO2002009137A1 (ja)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW586336B (en) * 2003-06-30 2004-05-01 Ritdisplay Corp Electrode substrate of flat panel display
KR101254411B1 (ko) * 2008-07-28 2013-04-15 엑손모빌 케미칼 패턴츠 인코포레이티드 Ｅｍｍ-12를 이용하여 알킬방향족을 제조하는 방법
CN102560368A (zh) * 2010-12-28 2012-07-11 鸿富锦精密工业（深圳）有限公司 壳体及其制造方法
CN110192285A (zh) * 2017-01-23 2019-08-30 东洋铝株式会社 太阳能电池用膏状组合物

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1220267A2 (en) * 1998-12-28 2002-07-03 Pioneer Corporation Plasma display panel

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6023457B2 (ja) * 1980-02-29 1985-06-07 富士通株式会社 表示パネル用電極の製造方法
JPS60101839A (ja) * 1983-11-07 1985-06-05 Nec Corp プラズマデイスプレイパネル
JPH0644892A (ja) * 1992-07-22 1994-02-18 Hitachi Ltd 熱陰極構体
US5793158A (en) * 1992-08-21 1998-08-11 Wedding, Sr.; Donald K. Gas discharge (plasma) displays
JPH06139923A (ja) * 1992-10-23 1994-05-20 Pioneer Electron Corp プラズマディスプレイパネルの製造方法
US6150027A (en) * 1995-06-16 2000-11-21 Hitachi, Ltd Glass composition, structure, and apparatus using the same
JP3339554B2 (ja) * 1995-12-15 2002-10-28 松下電器産業株式会社 プラズマディスプレイパネル及びその製造方法
JPH09245652A (ja) * 1996-03-13 1997-09-19 Dainippon Printing Co Ltd プラズマディスプレイパネルの電極及びその形成方法
JPH10188818A (ja) * 1996-12-27 1998-07-21 Pioneer Electron Corp プラズマディスプレイパネル
KR100268725B1 (ko) * 1997-10-22 2000-10-16 김순택 플라즈마디스플레이장치의격벽제조방법및그에의한플라즈마디스플레이장치
JPH11242935A (ja) * 1997-12-03 1999-09-07 Sharp Corp プラズマ情報表示素子
JPH11329254A (ja) * 1998-05-12 1999-11-30 Matsushita Electric Ind Co Ltd プラズマディスプレイパネル
JP2000260329A (ja) * 1999-03-05 2000-09-22 Matsushita Electric Ind Co Ltd プラズマディスプレイパネルとその製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1220267A2 (en) * 1998-12-28 2002-07-03 Pioneer Corporation Plasma display panel

Also Published As

Publication number Publication date
US6784618B2 (en) 2004-08-31
CN1443361A (zh) 2003-09-17
FR2812125A1 (fr) 2002-01-25
KR20030015396A (ko) 2003-02-20
EP1301937A1 (fr) 2003-04-16
JP4915890B2 (ja) 2012-04-11
WO2002009137A1 (fr) 2002-01-31
US20030151365A1 (en) 2003-08-14
KR100755331B1 (ko) 2007-09-05
AU2001267635A1 (en) 2002-02-05
JP2004505411A (ja) 2004-02-19
CN1257522C (zh) 2006-05-24
TWI239937B (en) 2005-09-21
DE60142835D1 (de) 2010-09-30

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