US3554889A - Color cathode ray tube screens - Google Patents

Color cathode ray tube screens Download PDF

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Publication number
US3554889A
US3554889A US778167A US3554889DA US3554889A US 3554889 A US3554889 A US 3554889A US 778167 A US778167 A US 778167A US 3554889D A US3554889D A US 3554889DA US 3554889 A US3554889 A US 3554889A
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Prior art keywords
phosphor
layer
coating
thickness
screen
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Expired - Lifetime
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US778167A
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English (en)
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Clifton E Hyman
George M Krembs
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International Business Machines Corp
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International Business Machines Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/20—Manufacture of screens on or from which an image or pattern is formed, picked up, converted or stored; Applying coatings to the vessel
    • H01J9/22—Applying luminescent coatings
    • H01J9/221—Applying luminescent coatings in continuous layers
    • H01J9/225—Applying luminescent coatings in continuous layers by electrostatic or electrophoretic processes
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture

Definitions

  • This invention relates generally to the production of luminescent screens which are useful, for example, in producing cathode ray tubes (CRT) for the production of color images. More'specifically, the invention relates to improved methods for producing multiple phosphor layers on CRT screens.
  • color CRT displays may be most effectively produced by the use of multiple phosphor layers on a substrate or screen.
  • the multiple layer color screen approach has several important advantages over the previous stripe phosphor screen or shadow mask or dot screens. For example, multiple layer color screens have better resolution, contrast and brightness, and enable the use of single electron gun systems.
  • a thin transparent conductive coating of a material such as tin oxide is applied to a transparent glass screen that has been previously cleaned.
  • the tin oxide is preferably applied by chemical deposition onto a heated screen from a solution of tin chloride and antimony-trichloride in a methanol base, and in a water vapor atmosphere.
  • This conductive coating provides an electrode for cataphoretic deposition.
  • a first phosphor layer, having a thickness of approximately four microns is cataphoretically deposited over the thin transparent conductive coating, with the thickness of the first phosphor layer beingcontrolled to within one micron.
  • This second thin transparent conductive coating provides the electrode for an other cataphoretically deposited layer of phosphor, having a thickness of approximately two microns, and permits the thickness of the phosphor deposit to be controlled to within one-half micron. Subsequently, an additional thin transparent coating or coatings and cataphoretically deposited layer or layers of phosphor may be applied if desired.
  • the above invention is extremely useful in producing high quality multiple layer phosphor CRT- screens, which are especially useful, for example, in high density graphic display applications. Further, the preferred method enables the production of such screens in large sizes, and the method is relatively simple and inexpensive to practice.
  • FIG. 1' shows the steps comprising the preferred method of the present invention
  • FIG. 2 is an enlarged partial cross section through a CRT screen produced in accordance with the method illustrated in FIG. 1;
  • FIG. 3 is a chart showing the variables that may be controlled to employ the method of this invention.
  • FIG. 1 The preferred embodiment of the present invention is shown in FIG. 1.
  • a transparent glass base or substrate 10 (FIG. 2) is initially provided with a so-called electronically clean surface.
  • a standard CRT soft-lead glass faceplate was used.
  • the screen surface is initially washed with detergent and soaked in chromic acid, flushed with water, soaked in ammonium bifiuoride, and rinsed with pure water. The screen is then dried in a clean atmosphere.
  • the method of applying multiple layers of phosphors on the electronically clean glass substrate 10 initially involves coating the screen with a thin transparent conductive coating which, in the preferred embodiment, is tin oxide.
  • the thin transparent conductive coating 12 (FIG. 2) is applied to the screen in the following manner. Initially, a solution of tin chloride and methanol, mixed with 5 percent antimony-trichloride (by weight) is prepared. The solution is chemicall deposited on the substrate by heating the substrate, in any convenient way, to approximately 425 C., and spraying the solution thereon in the presence of a water-vapor atmosphere. A chemical deposition of tin oxide is achieved by the chemical interaction of the vapors as explained, for example, in U.S. Pat. No. 2,732,313.
  • the resulting transparent conductive coating 12 comprises tin oxide, which is doped with antimony.
  • the antimony doping serves the purpose of shifting the light transmissivity of the coating from near-infrared to the visible spectrum, and of enhancing the conductivity of the coating.
  • the preferred thickness of coating 12 is approximately 5,000 A., and this thickness is controlled by measuring the resistance during the chemical deposition, in a manner well known to those skilled in the art.
  • the tin oxide coating 12 has a surface resistance of approximately 30 to 40 ohms per square, and an optical transmissivity of approximately eighty percent.
  • a zinc cadmium sulfide (silver-activated) phosphor layer (commonly known as P-20) having a thickness of fourione micron is applied by cataphoretic deposition.
  • the following suspension is prepared. Elutriated fine particles of the preferred phosphor, approximately one to two microns in diameter are suspended in ethyl alcohol containing five percent water (by weight) and 10- moles per liter of thorium nitrate. Preferably, 3.5 mg. of phosphor per ml. of vehicle is used. The suspension is formed by addition of these ingredients, and agitation for approximately 30 minutes by milling, stirring, or vibration. It is important that the dielectric constant of the vehicle be approximately 30 since this will insure a relatively high mobility of the charged phosphor particles through the vehicle and will permit a low field strength to promote cataphoretic movement of the particles.
  • a phosphor layer 14, having a green color when activated, is cataphoretically deposited on the screen over the conductive coating 14 by initially placing the above-described suspension in a suitable container (not illustrated) having an electrode placed therein.
  • the coated substrate 10 is connected to the negative terminal of a DC. power supply and a platinum electrode is connected to the positive terminal of that supply in order to practice cataphoresis.
  • the platinum electrode is preferably located two centimeters from the tin oxide coating 12, and a field of approximately fifty volts per centimeter is applied across the electrodes.
  • the thickness of the phosphor layer 14 is extremely important to the successful production of a multi-phosphor layer CRT screen. Accordingly, reference should be made to FIG. 3 wherein a curve is presented that illustrates the relationship of the three parameters that effect the control of the thickness of phosphor layer 14 by cataphoretic deposition; i.e., time, field strength and concentration of deposition suspension. It will be observed that for the suspension 4 noted above, and at a field strength of fifty volts per centimeter, it takes approximately 1.5 minutes to deposit a four micron thick phosphor layer 14 on the coated substrate. For reasons to be explained hereinafter, that the thickness of phosphor layer 14 is preferably between three and five microns.
  • a second transparent conductive coating 16 having a thickness ranging from 400 A. to 500 A. is applied.
  • the coating 16 is indium oxide, and is applied by vacuum deposition.
  • the substrate 10 carrying coating 12 and layer 14 thereon is located in a vacuum chamber and heated to approximately 350 C.
  • Located in the chamber is an indium filament. In order to provide the necessary water vapor and oxygen for the formation of indium oxide, oxygen and water vapor is gradually bled into the chamber, and simultaneously the indium is evaporated from the filament.
  • the various vapors react in a manner well known to those skilled in the art to form an indium oxide coating or film 16 over the first phosphor layer 14.
  • the process is controlled to deposit a coating or film 16 on the order of 400 A. to 500 A. in thickness, for a reason to be related hereinafter.
  • a second phosphor layer 18 can now be deposited onto the substrate 10 over transparent conductive coating 16 at a thickness that may be very carefully controlled by using the coating 16 as an electrode for cataphoretic deposition.
  • a zinc sulfide silver activated layer 18 (a blue phosphor, commonly known as P-ll is deposited by cataphoresis as follows.
  • the screen 10, carrying the tin oxide coating 12, green phosphor layer 14 and indium oxide coating 16 is again placed in a container along with a zinc sulfide silver activated phosphor suspension that is prepared in the same manner and has the same concentration as explained above.
  • the phosphor layer 18 is cataphoretically deposited over the second thin conductive coating 16 using an electrode spacing of approximately two centimeters and a field strength of approximately 50 volts per centimeter.
  • the thickness of the blue phosphor layer 18 is carefully controlled to be Within the range of one and one-half to two and one-half (or twoione-half) microns.
  • another indium oxide coating 20 is applied over the blue phosphor layer 18 in the same manner as described above in regard to the application of indium oxide coating 16.
  • This coating 20 is also preferably 400 A. to 500 A. in thickness, and provides an electrode for cataphoretic deposition.
  • a third phosphor layer 22 of yttrium vanadate europiurn activated (or rare earth red phosphor) is cataphoretically deposited in the same manner as the phosphor layers 14 and 18.
  • the thickness of this third phosphor layer '22 is carefully controlled to within the range of one and one-half to two and one-half (or twoione-half) microns.
  • an ion-burn resistant layer of aluminium may be applied over the third phosphor layer 22, to form a multi-layer color CRT screen 30.
  • the overall thickness of the three phosphor layers applied by cataphoretic deposition in accordance with the present invention is six to ten microns. This thickness is very important since electron penetration is proportional to the square of the applied voltage, and to permit the application of voltage in a useful range (i.e., eighteen kv. or less) the total thickness of the phosphor layers 14, 18 and 22 must be held to ten microns or less. Eighteen kv. is considered the maximum useful voltage in CRT graphic applications due to safety considerations since operators are present, and due also to increased tube life and ease of beam deflection. It was found that the only satisfactory the screen.
  • This screen is extremely'u seful in the display of highdensity numerics or graphics 'sincethe' phosphor layers, besides being held to precisegthickness tolerance by virtue of the intervening conductive layers acting-as electrodes for cataphoretic-deposition, are characterized by fine uniform particle size, which leads. to high resolution, good contrast and generally good image quality. Furthermore,- it is anticipated that a screen 30 produced in this'i'nanner willexperience infrequent electronic breakdowns dueto the relativelylow voltage that is required to effectively excite the interveningphosphor. layers. Also,
  • the first thin conductive coating 12 may alternatively be indium oxide, sprayed upon the screen as described above.
  • the solution in such case would consist of indium chloride, methanol and antimony-trichloride.
  • the surface resistance of an indium oxide coating is approximately 150 to 200 ohms per square, and it would therefore not be as conductive as the tin oxide coating 12.
  • Certain other alternatives to the formation or application of the first conductive coating 12 include using titanium chloride to form a titanium oxide layer that is thereafter rendered conductive by reduction with zinc sulfide in accordance with the method suggested in US. Pat. No. 2,928,975. Still other alternatives to the formation of coating 12 that may occur to those skilled in the art include the vacuum evaporation of indium metal at partial pressure to form a transparent conductive coating of indium oxide; the vacuum evaporation of silver or aluminium metals and the subsequent glow discharge thereof in air. to render it transparent; and, the vacuum evaporation of aluminium onto the substrate 10 to a thickness of approxiamtely 1,000 A.
  • the aluminiurn would not be transparent initially, and after the first phosphor layer 14 is cataphoretically deposited, the aluminium must be rendered transparent by oxidation in air or in aqueous ammonium persulphate, or anodization by citric acid.
  • the premature oxidation or anodization of the aluminium, i.e., before deposition of layer 14 would render it non-conducting, and useless for the cataphoretic depositon of layer 14.
  • methol-isobutyl ketone may be used as the vehicle rather than ethyl alcohol.
  • nitric or acetic acid rather than provide 10" moles per liter of thorium nitrate, which incidentally provides an ionizable metal in suspension, it would be possible to utilize nitric or acetic acid to provide an ionizable salt.
  • the thorium nitrate gives better adhesion than those acids, possibly due to a hydroxide occlusion at the interface between the conductive coating and phosphor layer, and therefore thorium nitrate is preferred.
  • a method of producing a cathode ray tube screen having multiple layers of phosphor excitable by a single electron gun comprising;
  • step of applying to a glass substrate a thin transparent conductive coating includes depositing on the glass substrate a coating selected from the group consisting of tin oxide, inldium oxide, conductive titanium oxide, and transparent s1 ver.
  • a method of producing a cathode ray tube screen having three discrete phosphor layers comprising:
  • a second phosphor layer having a thickness ranging from one and one-half to two and one-half microns;
  • a third phosphor layer having a thickness ranging one and one-half to two and onehalf microns.
  • a transparent color image screen comprising:
  • a first cataphoretically deposited phosphor layer having a preselected color when excited and having a thickness ranging from three to five microns, the first cataphoretically deposited phosphor layer being adjacent the first conductive layer;
  • a second cataphoretically deposited phosphor layer having another preselected color when excited and having a thickness ranging from one and one-half to two and one-half microns, the second cataphoretically deposited phosphor layer being adjacent the second conductive transparent layer.
  • the transparent color image screen of claim 7 ineluding a third transparent conductive layer adjacent the second cataphoretically deposited phoisphor layer;
  • a third cataphoretically deposited phosphor layer adjacent the third conductive transparent layer said third cataphoretically deposited phosphor layer having a thickness ranging from one and one-half to two and one-half microns.
  • the first conductive transparent layer is approximately 5,000 A. in thickness
  • the second conductive transparent layer ranges from 400 A. to 500 A. in thickness
  • the third conductive transparent layer ranges from 400 A. to 500 A. in thickness.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Formation Of Various Coating Films On Cathode Ray Tubes And Lamps (AREA)
  • Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)
  • Luminescent Compositions (AREA)
US778167A 1968-11-22 1968-11-22 Color cathode ray tube screens Expired - Lifetime US3554889A (en)

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US77816768A 1968-11-22 1968-11-22

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US (1) US3554889A (enrdf_load_stackoverflow)
JP (1) JPS4812667B1 (enrdf_load_stackoverflow)
FR (1) FR2023844A1 (enrdf_load_stackoverflow)
GB (1) GB1252787A (enrdf_load_stackoverflow)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3663396A (en) * 1970-02-02 1972-05-16 Xerox Corp Kinescope photoelectrophoretic imaging method and systems
US3714011A (en) * 1970-07-17 1973-01-30 Columbia Broadcasting Sys Inc Method of electrophoretic deposition of cathodoluminescent materials
JPS49121473A (enrdf_load_stackoverflow) * 1973-03-05 1974-11-20
US3863086A (en) * 1972-11-30 1975-01-28 Gte Sylvania Inc Coated pattern mask for use in forming a color CRT screen structure and method for coating the mask
WO1989011158A1 (en) * 1988-05-03 1989-11-16 Zenith Electronics Corporation Cataphoretic process for screening color ray tubes
US4891110A (en) * 1986-11-10 1990-01-02 Zenith Electronics Corporation Cataphoretic process for screening color cathode ray tubes
US5600200A (en) * 1992-03-16 1997-02-04 Microelectronics And Computer Technology Corporation Wire-mesh cathode
US5601966A (en) * 1993-11-04 1997-02-11 Microelectronics And Computer Technology Corporation Methods for fabricating flat panel display systems and components
US5612712A (en) * 1992-03-16 1997-03-18 Microelectronics And Computer Technology Corporation Diode structure flat panel display
US5667655A (en) * 1996-04-15 1997-09-16 Zenith Electronics Corporation Method of making color screens for FED and other cathodoluminscent displays
US5675216A (en) * 1992-03-16 1997-10-07 Microelectronics And Computer Technololgy Corp. Amorphic diamond film flat field emission cathode
US5679043A (en) * 1992-03-16 1997-10-21 Microelectronics And Computer Technology Corporation Method of making a field emitter
US5697824A (en) * 1994-09-13 1997-12-16 Microelectronics And Computer Technology Corp. Method for producing thin uniform powder phosphor for display screens
US5763997A (en) * 1992-03-16 1998-06-09 Si Diamond Technology, Inc. Field emission display device
US5853554A (en) * 1995-02-01 1998-12-29 Si Diamond Technology, Inc. Composition and method for preparing phosphor films exhibiting decreased coulombic aging
US5861707A (en) * 1991-11-07 1999-01-19 Si Diamond Technology, Inc. Field emitter with wide band gap emission areas and method of using
US6127773A (en) * 1992-03-16 2000-10-03 Si Diamond Technology, Inc. Amorphic diamond film flat field emission cathode
US6629869B1 (en) 1992-03-16 2003-10-07 Si Diamond Technology, Inc. Method of making flat panel displays having diamond thin film cathode

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3663396A (en) * 1970-02-02 1972-05-16 Xerox Corp Kinescope photoelectrophoretic imaging method and systems
US3714011A (en) * 1970-07-17 1973-01-30 Columbia Broadcasting Sys Inc Method of electrophoretic deposition of cathodoluminescent materials
US3863086A (en) * 1972-11-30 1975-01-28 Gte Sylvania Inc Coated pattern mask for use in forming a color CRT screen structure and method for coating the mask
JPS49121473A (enrdf_load_stackoverflow) * 1973-03-05 1974-11-20
US3904502A (en) * 1973-03-05 1975-09-09 Westinghouse Electric Corp Method of fabricating a color display screen employing a plurality of layers of phosphors
US4891110A (en) * 1986-11-10 1990-01-02 Zenith Electronics Corporation Cataphoretic process for screening color cathode ray tubes
WO1989011158A1 (en) * 1988-05-03 1989-11-16 Zenith Electronics Corporation Cataphoretic process for screening color ray tubes
US5861707A (en) * 1991-11-07 1999-01-19 Si Diamond Technology, Inc. Field emitter with wide band gap emission areas and method of using
US5763997A (en) * 1992-03-16 1998-06-09 Si Diamond Technology, Inc. Field emission display device
US5703435A (en) * 1992-03-16 1997-12-30 Microelectronics & Computer Technology Corp. Diamond film flat field emission cathode
US6629869B1 (en) 1992-03-16 2003-10-07 Si Diamond Technology, Inc. Method of making flat panel displays having diamond thin film cathode
US6127773A (en) * 1992-03-16 2000-10-03 Si Diamond Technology, Inc. Amorphic diamond film flat field emission cathode
US5600200A (en) * 1992-03-16 1997-02-04 Microelectronics And Computer Technology Corporation Wire-mesh cathode
US5675216A (en) * 1992-03-16 1997-10-07 Microelectronics And Computer Technololgy Corp. Amorphic diamond film flat field emission cathode
US5679043A (en) * 1992-03-16 1997-10-21 Microelectronics And Computer Technology Corporation Method of making a field emitter
US5686791A (en) * 1992-03-16 1997-11-11 Microelectronics And Computer Technology Corp. Amorphic diamond film flat field emission cathode
US5612712A (en) * 1992-03-16 1997-03-18 Microelectronics And Computer Technology Corporation Diode structure flat panel display
US5601966A (en) * 1993-11-04 1997-02-11 Microelectronics And Computer Technology Corporation Methods for fabricating flat panel display systems and components
US5652083A (en) * 1993-11-04 1997-07-29 Microelectronics And Computer Technology Corporation Methods for fabricating flat panel display systems and components
US5614353A (en) * 1993-11-04 1997-03-25 Si Diamond Technology, Inc. Methods for fabricating flat panel display systems and components
US5697824A (en) * 1994-09-13 1997-12-16 Microelectronics And Computer Technology Corp. Method for producing thin uniform powder phosphor for display screens
US5853554A (en) * 1995-02-01 1998-12-29 Si Diamond Technology, Inc. Composition and method for preparing phosphor films exhibiting decreased coulombic aging
US5906721A (en) * 1995-02-01 1999-05-25 Si Diamond Technology, Inc. Composition and method for preparing phosphor films exhibiting decreased coulombic aging
US5667655A (en) * 1996-04-15 1997-09-16 Zenith Electronics Corporation Method of making color screens for FED and other cathodoluminscent displays

Also Published As

Publication number Publication date
DE1958486B2 (de) 1972-06-22
JPS4812667B1 (enrdf_load_stackoverflow) 1973-04-21
FR2023844A1 (enrdf_load_stackoverflow) 1970-08-21
DE1958486A1 (de) 1970-06-11
GB1252787A (enrdf_load_stackoverflow) 1971-11-10

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