US20020047520A1 - Plasma picture screen with terbium(III)-activated phosphor - Google Patents

Plasma picture screen with terbium(III)-activated phosphor Download PDF

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US20020047520A1
US20020047520A1 US09/860,313 US86031301A US2002047520A1 US 20020047520 A1 US20020047520 A1 US 20020047520A1 US 86031301 A US86031301 A US 86031301A US 2002047520 A1 US2002047520 A1 US 2002047520A1
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phosphor
picture screen
plasma
green
gas
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US6462473B1 (en
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Thomas Juestel
Gerhard Spekowius
Sybrandus VAN Heusden
Gerrit Oversluizen
Siebe De Zwart
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LG Electronics Inc
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Koninklijke Philips Electronics NV
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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
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J11/42—Fluorescent layers
    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/778—Borates
    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/55—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing beryllium, magnesium, alkali metals or alkaline earth metals
    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • 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
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/42—Fluorescent layers

Definitions

  • the invention relates to a plasma picture screen provided with a front plate, which comprises a glass plate on which a dielectric layer and a protective layer are provided, with a carrier plate provided with a phosphor layer comprising a red and a blue phosphor as well as a green, Tb 3+ -activated phosphor, with a ribbed structure which subdivides the space between the front plate and the carrier plate into plasma cells which are filled with a gas comprising xenon, and with one or several electrode arrays on the front plate and the carrier plate for generating corona discharges in the plasma cells.
  • a front plate which comprises a glass plate on which a dielectric layer and a protective layer are provided, with a carrier plate provided with a phosphor layer comprising a red and a blue phosphor as well as a green, Tb 3+ -activated phosphor, with a ribbed structure which subdivides the space between the front plate and the carrier plate into plasma cells which are filled with a gas comprising
  • Plasma picture screens render possible color pictures with high resolution and large screen diagonal and have a compact construction.
  • a plasma picture screen comprises a hermetically closed glass cell which is filled with a gas, with electrodes in a grid arrangement. The application of a voltage causes a gas discharge which generates light in the ultraviolet range (145 to 185 nm). This light can be converted into visible light by means of phosphors and be emitted through the front plate of the glass cell to the viewer.
  • Phosphors which are particularly efficient under vacuum UV excitation are used for plasma picture screens.
  • green-emitting phosphors are, for example, Zn 2 SiO 4 :Mn (ZSM) and BaAl 12 O 19 :Mn (BAL). Both materials show a saturated green emission color with a high y-value of y>0.7.
  • a disadvantage of both materials is their comparatively long decay time t ⁇ fraction (1/10) ⁇ , for example, 30 ms for Zn 2 SiO 4 with 25% Mn. The cause of this is that the transition 4 T 1 ⁇ 6 A 1 relevant for the emission of the light is spin-forbidden.
  • Tb 3+ -activated phosphors are temperature stable and photostable, because Tb 3+ does not readily oxidize to Tb 4+ .
  • a further advantage of these phosphors over Mn 2+ -activated phosphors is their shorter decay time t ⁇ fraction (1/10) ⁇ , which lies between 2 and 10 ms, depending on the host lattice.
  • U.S. Pat. No. 6,004,481 accordingly describes a green-emitting Tb 3+ -activated phosphor for use in plasma picture screens which has the composition (Y 1 ⁇ x ⁇ y ⁇ z Gd x Tb y Ce z )BO 3 , With 0.0 ⁇ x ⁇ 0.2,0.01 ⁇ y ⁇ 0.1, and 0.0 ⁇ z ⁇ 0.1.
  • Tb 3+ -activated phosphors have a low y-value of y ⁇ 0.62.
  • the invention has for its object to provide a plasma picture screen with a Tb 3+ -activated phosphor whose green pixels provide light with an improved color point.
  • a plasma picture screen provided with a front plate, which comprises a glass plate on which a dielectric layer and a protective layer are provided, with a carrier plate provided with a phosphor layer comprising a red and a blue phosphor as well as a green, Tb 3+ -activated phosphor, with a ribbed structure which subdivides the space between the front plate and the carrier plate into plasma cells which are filled with a gas comprising xenon, and with one or several electrode arrays on the front plate and the carrier plate for generating corona discharges in the plasma cells, wherein the gas comprises xenon in a proportion of between 5 and 30% by volume.
  • the proportion of xenon in the gas is 10% by volume.
  • the green Tb 3+ -activated phosphor is chosen from the group (In x Gd 1-x )BO 3 :Tb (0 ⁇ x ⁇ 1), Y 2 SiO 5 :Tb, CeMgAl 11 O 19 :Tb, (Y 1-x-y Gd x Pr y ) BO 3 :Tb (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.05), GdMgB 5 O 10 :Ce,Tb and LaPO 4 :Ce,Tb.
  • Tb 3+ -activated phosphors are particularly efficient green-emitting phosphors when excited by VUV light.
  • the green Tb 3+ -activated phosphor may comprise (Y 1 ⁇ x ⁇ y Gd x Pr y )BO 3 :Tb (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.05).
  • FIG. 1 showing the construction and operating principle of a single plasma cell in an AC plasma picture screen.
  • a plasma cell of an AC plasma picture screen with a coplanar arrangement of the electrodes comprises a front plate 1 and a carrier plate 2 .
  • the front plate 1 comprises a glass plate 3 on which a dielectric layer 4 and thereon a protective layer 5 are provided.
  • the protective layer 5 is preferably made of MgO, and the dielectric layer 4 , for example, of glass containing PbO.
  • Parallel, strip-shaped discharge electrodes 6 , 7 are provided on the glass plate 3 and are covered by the dielectric layer 4 .
  • the discharge electrodes 6 , 7 are made, for example, of metal or ITO.
  • the carrier plate 2 is made of glass, and parallel, strip-shaped address electrodes 10 , for example made of Ag, are provided on the carrier plate 2 so as to run perpendicularly to the discharge electrodes 6 , 7 . Said address electrodes are covered with respective phosphor layers 9 which each emit light in one of the three basic colors red, green, or blue.
  • the individual plasma cells are separated by a ribbed structure 12 with separating ribs which are preferably made of a dielectric material.
  • a gas preferably a rare gas mixture of, for example, He, Ne, or Kr, which contains xenon in a quantity of 5 to 30% by volume is present in the plasma cell, and also between the discharge electrodes 6 , 7 , which alternate as the cathode and the anode.
  • a plasma is formed in the discharge region 8 by which radiation 11 in the UV range, in particular in the VWV range, is generated, depending on the composition of the gas.
  • This radiation 11 excites the phosphor layer 9 into phosphorescence, thus emitting visible light 13 in one of the three basic colors, which light issues through the front plate 1 to the exterior and thus forms a luminous pixel on the picture screen.
  • the dielectric layer 4 lying over the transparent discharge electrodes 6 , 7 in an AC plasma picture screen serves to counteract a direct discharge between the discharge electrodes 6 , 7 made of a conductive material, and thus the formation of an arc during ignition of the discharge.
  • a Tb 3+ -activated phosphor such as, for example, (In x Gd 1 ⁇ x )BO 3 :Tb (0 ⁇ x ⁇ 1), Y 2 SiO 5 :Tb, CeMgAl 11 O 19 :Tb, (Y 1 ⁇ x ⁇ y Gd x Pr y )BO 3 :Tb (0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 0.05), GdMgB 5 O 10 :Ce,Tb or LaPO 4 :Ce,Tb is used as the green-emitting phosphor in the phosphor layer.
  • (Y 1 ⁇ x ⁇ y Gd x Pr y )BO 3 :Tb (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.05) is used.
  • the gas preferably comprises a binary or ternary rare gas mixture of He/Xe, Ne/Xe, or He/Ne/Xe with a xenon quantity in the gas which lies between 5 and 30% by volume. Particularly preferred is a relative quantity of xenon in the gas of 10% by volume.
  • the increase of the xenon quantity in the gas to more than 5% by volume increases the y-value of the Tb 3+ -activated phosphors. As a result, the green pixels have a sufficiently green appearance.
  • a further advantage of the plasma picture screens with a xenon quantity above 5% by volume is that the intensity of the emission bands of neon in the 580 nm and 750 nm ranges is reduced as the xenon quantity increases. This also enhances the color saturation of the blue phosphors, i.e. the blue pixels.
  • a suspension of the phosphor (Y,Gd)BO 3 :Tb was prepared, to which additives such as an organic binder and a dispersing agent were added.
  • the suspension was provided in a structured manner on a carrier plate 2 by means of silk-screen printing and dried. This process step was carried out consecutively for the other two phosphor types with the emission colors red and blue.
  • the carrier plate 2 was made of glass and had a ribbed structure 12 and address electrodes 10 of Ag. All organic additives remaining in the phosphor layers 9 were removed by a thermal treatment of the carrier plate 2 at 400 to 600° C. in an atmosphere containing oxygen.
  • the carrier plate 2 was used for assembling an AC plasma picture screen, together with a front plate 1 comprising a glass plate 3 , a dielectric layer 4 of glass containing PbO, a protective layer 5 of MgO, and discharge electrodes 6 , 7 of ITO, and a gas mixture having a composition of 10% Xe and 90% Ne by volume, which screen showed an improved color saturation and an improved color constancy.

Abstract

The invention relates to a plasma picture screen with an improved color saturation and an improved color constancy. This is achieved through the use of Tb3+-activated phosphors and a gas mixture with an increased xenon content.

Description

  • The invention relates to a plasma picture screen provided with a front plate, which comprises a glass plate on which a dielectric layer and a protective layer are provided, with a carrier plate provided with a phosphor layer comprising a red and a blue phosphor as well as a green, Tb[0001] 3+-activated phosphor, with a ribbed structure which subdivides the space between the front plate and the carrier plate into plasma cells which are filled with a gas comprising xenon, and with one or several electrode arrays on the front plate and the carrier plate for generating corona discharges in the plasma cells.
  • Plasma picture screens render possible color pictures with high resolution and large screen diagonal and have a compact construction. A plasma picture screen comprises a hermetically closed glass cell which is filled with a gas, with electrodes in a grid arrangement. The application of a voltage causes a gas discharge which generates light in the ultraviolet range (145 to 185 nm). This light can be converted into visible light by means of phosphors and be emitted through the front plate of the glass cell to the viewer. [0002]
  • Phosphors which are particularly efficient under vacuum UV excitation are used for plasma picture screens. Frequently used green-emitting phosphors are, for example, Zn[0003] 2SiO4:Mn (ZSM) and BaAl12O19:Mn (BAL). Both materials show a saturated green emission color with a high y-value of y>0.7. A disadvantage of both materials is their comparatively long decay time t{fraction (1/10)}, for example, 30 ms for Zn2SiO4 with 25% Mn. The cause of this is that the transition 4T1→6A1 relevant for the emission of the light is spin-forbidden. In addition, the decay time t{fraction (1/10)} and the color point of a Mn2+-activated phosphor are strongly dependent on the Mn2+ concentration. A further disadvantage is the sensitivity of Mn2+ to an oxidation to Mn3+ or Mn4+, which reduces the stability of the phosphors.
  • By contrast, Tb[0004] 3+-activated phosphors are temperature stable and photostable, because Tb3+ does not readily oxidize to Tb4+. A further advantage of these phosphors over Mn2+-activated phosphors is their shorter decay time t{fraction (1/10)}, which lies between 2 and 10 ms, depending on the host lattice.
  • U.S. Pat. No. 6,004,481 accordingly describes a green-emitting Tb[0005] 3+-activated phosphor for use in plasma picture screens which has the composition (Y1−x−y−zGdxTbyCez)BO3, With 0.0<x<0.2,0.01<y<0.1, and 0.0<z<0.1.
  • A major disadvantage of Tb[0006] 3+-activated phosphors is their yellowy-green color point, which has a low y-value of y<0.62.
  • The invention has for its object to provide a plasma picture screen with a Tb[0007] 3+-activated phosphor whose green pixels provide light with an improved color point.
  • This object is achieved by means of a plasma picture screen provided with a front plate, which comprises a glass plate on which a dielectric layer and a protective layer are provided, with a carrier plate provided with a phosphor layer comprising a red and a blue phosphor as well as a green, Tb[0008] 3+-activated phosphor, with a ribbed structure which subdivides the space between the front plate and the carrier plate into plasma cells which are filled with a gas comprising xenon, and with one or several electrode arrays on the front plate and the carrier plate for generating corona discharges in the plasma cells, wherein the gas comprises xenon in a proportion of between 5 and 30% by volume.
  • It is particularly highly preferred that the proportion of xenon in the gas is 10% by volume. [0009]
  • An increased proportional quantity of xenon in the gas surprisingly increases the y-value of the color point of Tb[0010] 3+-activated phosphors. The result is that the green pixels of a plasma picture screen with a Tb3+-activated phosphor show a sufficiently saturated green.
  • It is furthermore preferred that the green Tb[0011] 3+-activated phosphor is chosen from the group (InxGd1-x)BO3:Tb (0 ≦x≦1), Y2SiO5:Tb, CeMgAl11O19:Tb, (Y1-x-yGdxPry) BO3:Tb (0≦x≦1, 0≦y≦0.05), GdMgB5O10:Ce,Tb and LaPO4:Ce,Tb.
  • These Tb[0012] 3+-activated phosphors are particularly efficient green-emitting phosphors when excited by VUV light.
  • It may be particularly highly preferable for the green Tb[0013] 3+-activated phosphor to comprise (Y1−x−yGdxPry)BO3:Tb (0≦x≦1, 0<y≦0.05).
  • This phosphor has a short decay time t[0014] {fraction (1/10)}=8 ms and a high y-value>0.61 of its color point.
    •
  • The invention will be explained in more detail below with reference to a Figure and an embodiment, with [0015]
  • FIG. 1 showing the construction and operating principle of a single plasma cell in an AC plasma picture screen.[0016]
  • In FIG. 1, a plasma cell of an AC plasma picture screen with a coplanar arrangement of the electrodes comprises a [0017] front plate 1 and a carrier plate 2. The front plate 1 comprises a glass plate 3 on which a dielectric layer 4 and thereon a protective layer 5 are provided. The protective layer 5 is preferably made of MgO, and the dielectric layer 4, for example, of glass containing PbO. Parallel, strip- shaped discharge electrodes 6, 7 are provided on the glass plate 3 and are covered by the dielectric layer 4. The discharge electrodes 6, 7 are made, for example, of metal or ITO. The carrier plate 2 is made of glass, and parallel, strip-shaped address electrodes 10, for example made of Ag, are provided on the carrier plate 2 so as to run perpendicularly to the discharge electrodes 6, 7. Said address electrodes are covered with respective phosphor layers 9 which each emit light in one of the three basic colors red, green, or blue. The individual plasma cells are separated by a ribbed structure 12 with separating ribs which are preferably made of a dielectric material.
  • A gas, preferably a rare gas mixture of, for example, He, Ne, or Kr, which contains xenon in a quantity of 5 to 30% by volume is present in the plasma cell, and also between the [0018] discharge electrodes 6, 7, which alternate as the cathode and the anode. After ignition of the surface discharge, whereby charges can flow along a discharge path between the discharge electrodes 6, 7 in the discharge region 8, a plasma is formed in the discharge region 8 by which radiation 11 in the UV range, in particular in the VWV range, is generated, depending on the composition of the gas. This radiation 11 excites the phosphor layer 9 into phosphorescence, thus emitting visible light 13 in one of the three basic colors, which light issues through the front plate 1 to the exterior and thus forms a luminous pixel on the picture screen.
  • The [0019] dielectric layer 4 lying over the transparent discharge electrodes 6, 7 in an AC plasma picture screen serves to counteract a direct discharge between the discharge electrodes 6, 7 made of a conductive material, and thus the formation of an arc during ignition of the discharge.
  • A Tb[0020] 3+-activated phosphor such as, for example, (InxGd1−x)BO3:Tb (0≦x≦1), Y2SiO5:Tb, CeMgAl11O19:Tb, (Y1−x−yGdxPry)BO3:Tb (0≦x≦1,0≦y≦0.05), GdMgB5 O10:Ce,Tb or LaPO4:Ce,Tb is used as the green-emitting phosphor in the phosphor layer. Preferably, (Y1−x−yGdxPry)BO3:Tb (0≦x≦1, 0≦y≦0.05) is used.
  • The gas preferably comprises a binary or ternary rare gas mixture of He/Xe, Ne/Xe, or He/Ne/Xe with a xenon quantity in the gas which lies between 5 and 30% by volume. Particularly preferred is a relative quantity of xenon in the gas of 10% by volume. The increase of the xenon quantity in the gas to more than 5% by volume increases the y-value of the Tb[0021] 3+-activated phosphors. As a result, the green pixels have a sufficiently green appearance.
  • A further advantage of the plasma picture screens with a xenon quantity above 5% by volume is that the intensity of the emission bands of neon in the 580 nm and 750 nm ranges is reduced as the xenon quantity increases. This also enhances the color saturation of the blue phosphors, i.e. the blue pixels. [0022]
  • The use of a Tb[0023] 3+-activated phosphor in combination with a gas comprising an increased proportion of xenon not only enhances the y-value of the color point of the green pixels, but also their luminance.
  • As Table 1 shows, the luminance of a monochrome plasma picture screen with (Y,Gd)BO[0024] 3:Tb as a phosphor increases by almost 30% compared with a monochrome plasma picture screen with Zn2SiO4:Mn. For a xenon content of 10% by volume in the gas, the color point of (Y,Gd)BO3:Tb still lies within the range of ZnS:Cu (x=0.31, y=0.61), which is used as a green-emitting phosphor in color cathode ray tubes.
    TABLE 1
    CIE color points and luminance of monochrome plasma picture
    screens with Zn2SiO4:Tb or (Y, Gd)BO3:Tb for various gas mixtures
    Gas composition CIE color point Luminance
    [Vol.-%] Phosphor [x, y] [cd/m2]
    3.5 Xe, 96.5 Ne Zn2SiO4:Mn 0.25, 0.67 1390
    3.5 Xe, 96.5 Ne (Y, Gd)BO3:Tb 0.36, 0.53 1820
    10 Xe, 90 Ne Zn2SiO4:Mn 0.15, 0.74 2700
    10 Xe, 90 Ne (Y, Gd)BO3:Tb 0.31, 0.60 3700
  • An embodiment of the invention will now be explained in detail, representing an example of how the invention may be implemented in practice. [0025]
    • EMBODIMENT
  • First a suspension of the phosphor (Y,Gd)BO[0026] 3:Tb was prepared, to which additives such as an organic binder and a dispersing agent were added. The suspension was provided in a structured manner on a carrier plate 2 by means of silk-screen printing and dried. This process step was carried out consecutively for the other two phosphor types with the emission colors red and blue. The carrier plate 2 was made of glass and had a ribbed structure 12 and address electrodes 10 of Ag. All organic additives remaining in the phosphor layers 9 were removed by a thermal treatment of the carrier plate 2 at 400 to 600° C. in an atmosphere containing oxygen.
  • The [0027] carrier plate 2 was used for assembling an AC plasma picture screen, together with a front plate 1 comprising a glass plate 3, a dielectric layer 4 of glass containing PbO, a protective layer 5 of MgO, and discharge electrodes 6, 7 of ITO, and a gas mixture having a composition of 10% Xe and 90% Ne by volume, which screen showed an improved color saturation and an improved color constancy.

Claims (4)

1. A plasma picture screen provided with a front plate (1), which comprises a glass plate (3) on which a dielectric layer (4) and a protective layer (5) are provided, with a carrier plate (2) provided with a phosphor layer (9) comprising a red and a blue phosphor as well as a green, Tb3+-activated phosphor, with a ribbed structure (12) which subdivides the space between the front plate (1) and the carrier plate (2) into plasma cells which are filled with a gas comprising xenon, and with one or several electrode arrays (6, 7, 11) on the front plate (1) and the carrier plate (2) for generating corona discharges in the plasma cells, characterized in that the gas comprises xenon in a proportion of between 5 and 30% by volume.
2. A plasma picture screen as claimed in claim 1, characterized in that the proportion of xenon in the gas is 10% by volume.
3. A plasma picture screen as claimed in claim 1, characterized in that the green Tb3+-activated phosphor is chosen from the group (InxGd1-x)BO3:Tb (0≦x≦1), Y2SiO5 :Tb, CeMgAl11O19:Tb, (Y1-x-yGdxPry)BO3:Tb (0≦x≦1,0≦y≦0.05), GdMgB5O10:Ce,Tb and LaPO4:Ce,Tb.
4. A plasma picture screen as claimed in claim 3, characterized in that the green Tb3+-activated phosphor comprises (Y1-x-yGdxPry)BO3:Tb (0≦x≦1,0 ≦y≦0.05).
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KR100961130B1 (en) 2010-06-07
CN1325124A (en) 2001-12-05
US6462473B1 (en) 2002-10-08
CN1218356C (en) 2005-09-07
EP1158559A2 (en) 2001-11-28
EP1158559A3 (en) 2004-05-19
DE10024835A1 (en) 2001-11-22
KR20010105212A (en) 2001-11-28
TW507238B (en) 2002-10-21
KR20070120927A (en) 2007-12-26
JP2002015674A (en) 2002-01-18

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