CA2059135A1 - Color display system using thin film color control - Google Patents
Color display system using thin film color controlInfo
- Publication number
- CA2059135A1 CA2059135A1 CA 2059135 CA2059135A CA2059135A1 CA 2059135 A1 CA2059135 A1 CA 2059135A1 CA 2059135 CA2059135 CA 2059135 CA 2059135 A CA2059135 A CA 2059135A CA 2059135 A1 CA2059135 A1 CA 2059135A1
- Authority
- CA
- Canada
- Prior art keywords
- light
- display system
- accordance
- valve metal
- color
- 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.)
- Abandoned
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
- G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
A high resolution, full color, thin film display system is formed of (1) discrete areas of an anodic oxide coated valve metal film (40) of graded thickness, coupled with silicon dioxide over-layer for protection and a transparent conductor underlayer, to provide high intensity selectable color display at said areas with high resolution pixel monochromatic and/or multi-color selection and (2) a high resolution back-light activator which comprises x-, y- rows of thin electrodes (22, 24) spanning a thin layer of photovoltaic material (26) and constructed to act as a light filter matrix or directly as a light source matrix, with the option of one set of said electrodes (25) being coincident with the said areas.
Description
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Ih~ po~tion~ o~ tho ~leld o~ display systems and o~othRr ~iel~ addr~s~6~ by the p~ese~ in~ention include consumer and indu~trial video, pr~ction ~ideo, military and scienti~ic display panel5, Golor ~ilter control5, and light sources. Ihe term "dlsplay" as used herein includes displays and display-like systems, unless o*herwise ;n~cated.
Ihe state of the art of display systems includes gelatin or dyed polymide filter mat~rials associated with matrix light source means with intensities of d~ play-transmission (as a px~x~nt of saurce light) of ab3ut sixty for bluergreen spec*rzl ranges and m nety for red. For a gcod review, see, e.g., Iatham et al., ~Color Filters From Dyed Polymides~ Solid State Tedhnolo~y pMay 1988). The state o~ the art also inClUdes active ~.,, Y; ~ ~
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Ih~ po~tion~ o~ tho ~leld o~ display systems and o~othRr ~iel~ addr~s~6~ by the p~ese~ in~ention include consumer and indu~trial video, pr~ction ~ideo, military and scienti~ic display panel5, Golor ~ilter control5, and light sources. Ihe term "dlsplay" as used herein includes displays and display-like systems, unless o*herwise ;n~cated.
Ihe state of the art of display systems includes gelatin or dyed polymide filter mat~rials associated with matrix light source means with intensities of d~ play-transmission (as a px~x~nt of saurce light) of ab3ut sixty for bluergreen spec*rzl ranges and m nety for red. For a gcod review, see, e.g., Iatham et al., ~Color Filters From Dyed Polymides~ Solid State Tedhnolo~y pMay 1988). The state o~ the art also inClUdes active ~.,, Y; ~ ~
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matrix liquid crystal display (ICD) means. See, e.g., Sakai et ali. (NTT), "A DefectJTolerant 5echnology ~or An Astive-Matrix LCD Integrated With Peripheral Circuits~ SID (Society for : Information Display) 88 Digest pp. 400 - 403. ~hin film diode or .. :. transis~or light emitter arrays can be provided in similar fashion. The foregoing publlcations are incorpo~ated herein by reference as thcugh s~t out at length herein. ~ The present i~ventlon prcvides ~ignl~icant bene~its compared to the s~ate of ', the art and camm~raial practice thereo~.
i, u It i5 an object o~ the present invention to pravide,~ displays o~ high resoluticn dot area (pixel) selection, with high intensity o~ color availability selectable avQr a large spectral ra~gQ in cus~m tailored de~ign and production-~, . It is A ~urth~r ck~ect 0~ the in~nt~n to pr~vid~
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:;~. ~si~r th~cug~u~ ~ v~iblo c~i~al ~pec~ ~alu~ ~d, blu~ een) ~nd ~rab~y al~o in t~ni~ ~pe~ rar~es " l~on~ visible ~e.g., near ~ ar ~, uV) .
It i~ a ~her c~ect o~ t~ invE3ntlon to pra~ride sudh ~-............... di~plays o~ canpact otn~ form.
,; It is a ~er ~bject of the irn~ention to prcnride such dis;plays wi~h lang life an~ lc~ failure vulnerab;l ity.
--: It is a ~urther cbject of the inv~nticn t~ prcvide such displays economically and simply.
It is a further cbjeck of the invenkion to provide such i displays with high ~peed o~ response to control signals and ~ si~nply ~c~ol ~ in c~inati~ t~itll.
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WO 90/~6057 2 0 5 ~ 1 3 a PCr/US90/03335 It is a f~art~r bb~ect oî the invention to pmvide such display free of parallax and/or anisotr~ lim~tations of its ~ptical characteris~ic.
It is a further ~bject of tha i2~ ion to provide such ~play wi~h a high degree of te~perature stability and/or chemical ~tability ~ all cor~litions of marmfacture and ~se.
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Wo 90/16057 2 ~ 5 91~ a PCT/US90/U333~ ~
lhe cbjects of the invention are re21iz~d in a system using thin f~lm technology to pr3vide a key color control section and also using such technology for light oontrol steps other than color ~;ltering.
me display system has a l~ght source and high r~olution light control ~ er p~oducing selected dots o~ light o~lglnation or passage at high resolution (or dots of light blockag~ in an amblent of essentially collimatad light).
In its light passage embodiments, the system is constructed ~nd arranged 80 ~hat a beam oP light impacts a ~hin ~i~m color c~ntrol parel and passes thxou~h it ~or is re~lected by it), and pxeP~rrably al~o pas~es th~ough a pr~t~ctive t3z~q>lrent ~ore~n, to a view~r. Ihe col~r cont~ol panel ccmprlsa~ ~ highly adhQr~nt color r~pon~ m~t~ri~l, p~a~rrabl~
an ~nodically oxi~iz~d ~hin ~ilm Or ~antalum or ~n~alum nitrides or other anodically oxldl~ible metal (valve me~al).
Pre~Qrrably, the color control and light ccntrol ~ilter portions are inte~rated to some extent as hereinafter described to a~ford automatic self-alignment of cross-hatched ~e.~., x-, y-) ele~*rodes to define an array of cross-cvers, automat~cally slaved in cor~ect array positions. Dcts of light are prcduceable at the cross-overs to yield controlled Ip;x~lsl as sm211 as a single dot or with a grcup of dcts ~a few or many) defining each P~.
In acccn~ance with the inventicn ~Plected areas of the tantalum cxide (preferr~bly adjacent stripes in a SQt, wi~h an array of repeatlng such sets o~ ~tripe8) æ e o~ different thicknesses to produce di~erent color responses to wo go/16057 2 ~ 5 913 ~ PCT/US90/03335 ~ ?;,~
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incident/transmitted light. AscGrding to a further ~ of the invention ~he tantalum oxide "layer" h~s internal sublay~rs of tantalum oxide and a tr~nsp~rent material, e.g., silicon dioxide.
Ihere can be multiples of such sublaye~s stacked over each other to enhance the brilliance of color response, according to a further asp2ct of the invention.
The color contr~l elements ar~ ~preferrably) side by ~lde in a sin~le thin ~ilm layer or in each of several such ~ublayers therQby a~Pording high intensity. The general illuminating light passin~ thrzugh color bands of the cantrol layer projects aver a wide angle space after passi~g through the color layer with ~nl~c*r~pic cptical resFonse, i.e. aver 90' (pre~errably aver 135') o~ vie ~ angle. ~he tantalum oxide ~ilm, or the like, is vary stable and resistant to savQre conditions o~ t~mp~ratur~ an~or acidia ar alkalin~ anvironme~.
It ~ ~ormed by ancdic oxidation u~ing an und~rlayer o~
t~n3prrcnt khln ~lm net~ coa~in~ o~ ~ha m~t~ a~ ~n ia el~ctrod~. rrh~ m4~al may b~ 1 layQr of e~ectrically eonduative, tran~parent material ~or ~ptimum resistivity ~n end use.
Where th0 anodic oxide separates x-, y- electrodes or the like ~a~ indiea~ed above for prcferred crhxxluDents~ then a very high dieleetric eonstant separati~n of such electrcde groups c2Ln be formed with high ele~t,ieal insulating value, but acoommcdating close spac ~ .
Other objects, features, a~d advan~ages will be apFarent frcm the follcwlng deta;~ed descriptic~ of preferred embodlments taken in c~njunction with the acccrç~vry m g drawing in which:
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WO 90/160~7 2 ~ 5 ~ ~ 3 ~ Pcr/US90/03335 E~ I~IaN OF q~ nRa~
~ IG. 1 is an i~ic sketc~h of an ~r~i~t of a di~play .syst~n of the inven~
~ I:GS. 2 and 3 are lateral ar~l transverse cmss-section sh3tches (tak~ ak the re~ective viewing dlrections II-II and III~I~ o~ EIG. 1) ~N ~n expand~d scale, o:~ a portion of the ~IG.
1 ~bod~nt;
~ IGS. 3A, 3C ar~ 3D are secticned sketctles, further expanded and hiqhly schematic illustratLng stepe of construction of a portion o~ th~ oolor control ~ection (and a part of the pixel s41ection s2cticn) o~ the FIG. 1 embodim:nt and FIG. 3B i9 a flow ch2rt outlln~ o~ those cc*~truction steps ~nnka that there i~ a chang~ ln ccnstrLction ~n FIGg. 3A--3D compnrod to FIG. 3 wh~ra~n th3 ~para~ oleotxodc~ o~ FIG. 3 ar~ o~itt~d and r~placed by y- ~lectr~de~ in~egrn~4d wi~h color ~trip~s in FIGS.
3A, 3D)~
FIG. 4 is an expanded ~ace vi~w o~ the glass substrate (screen) o~ the FIG. 1 embodiment indicating 0electi~ely established doks of light passage an~ blockage an~ a si~gle pixel arbitrarily established as a nine dot by nine dot square (althcugh a pixel could be established m~ch larger or as small as a single dot):
FIGS. 5 - 7 are sim~lar face ~iews for other embodime*ts of pix~l c~*l~mdnation on the di~rlay screen;
FIGS. aA an~ 8~ are dia ~ s of usage o~ the color fil~er of the display ~ystem withcut hi~h resolution areas segrega~ion, bNt rather as a broad area color control ~ilter ln ';' ` ~ ! ' , ~ , . . .
W V 9Q/~6057 2 a ~ 9 l 3 ~ PCT/US9~/0333s .~ .
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~ssi~e (8A) and reflective (8b) m~des;
FIG. g is a sectioned sketch (taXen laterally as in FIG.
2) of a variation of the FIGS. 1-8~ entxxLu~ents using kuss bars to reduce resistivity losses alon~ the elongated conductors; and FIG. 10 is a related cir~uit diagram.
FIG. 11 is a trace of decreasing sheat resistivity of an indium~tin-cxlde coakiny as enhanced thrcugh an aspect of the present invention.
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rEIaIlED DESC~I}TICN OF E513~3~RED ENE01TN~N75 Referr1ng now to FI~. 1, there is shown an embcdlment d the invention comprising a light source 10; a light passage section 20; and a display screen 30 with a color de~i ~ back coating 40 (at the interface-planar region between 20 and 30) hereinafter described. As variants frcm this embod~mcnt, (a) the light ~cuxce can be s~t back at a distance or (b) the light souxc~ and llght ~ilt~r can be in~egrated in vario~ ways as explained bel~w. The viewer's position is indica~ed at E. m e elements 10, 20, 30 are pr~ferrably of compact ~lab-like form and can each be made in thicknescPc mubet~ntlally below an inch.
FIG. 1 al~co ahcws that the section 20, which is electrically controlled has x-electrodes 22 and y-electrode~ 24 in the ~o~ms o~ arrays o~ linear conduc~o~s in spaced paxall~l planes (one plane for each array~. ~hen electrlcal curr~nt is supplied to ons x-el~c~r~d~ c~nduc~or a2 and ono y~el~c~xodc connection 2~, ~he ~ o~ ~iv~ ~m i5 controll~ (~g into aacount voltage drops along the lengths o~ such elongated conducto~s) so that a voltage iB supplied to an essen~ially tubular cro~ cve~ ~pct.
The light sourcc 10 pre~errably comprises a ~ull specbrum, level intensity source, but in specialized applications (or for economy) may be of narrow spec*ral range (wlthin or : :
outside the visible range) or with unusual intensity or attenuation at particular wavelengths. Ihe light scurce material chDices can be electrolu= m escent, ~nc~u~#R~ent, fluorescent, or - other thermal, phckovoltaic or dlsK~nge m2ans.
FIGS. 2 - 3 show the light pass element 20 expanded side and top view sections of the FIG. 1 ar~ul~3n~nt comprising wi~es (or striped coatings or other eguivalents) 22 and 24 ~or x- and ~- electrodÆs, re2pec~1vely. ~h~ ele~trcde wirQs o~ skrip~s ar~
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w o go/160~7 2 0 5 ~ 1 3 ~ PCT/US90~03335 .., g of fLne diam~r or span and ~andwich a phokovoltaic liquid ~stal mat~rial 26. When crossing x- and y- electrodes are active a~ a crossover material spanning point, the local material is activated to pass or block light (depending on the selected material) to produce a high resolution spot of light passaga (or blockage) of no higher than .005" x .005" or as lcw as .0001 inches x .0001 mches, preferrably about .0005 to .001 inches (.0125 to .025 mm: l/2 to 1 mil) x .0005 to .001 inches, or circular equivzlents. Generzlly, for uni~orm spacing of x- and y~ electrode arrays the sp~t will be in-between ideal circular and squar~ configuration (an approximate square wlth rcunded corners). But essentially per~ect squares or circles of light passage (or bloc~age) can be pro~uced with specialize~d elec-trode/light-con~rol-material combinations, or elongated spots can be E~xxh~3ed, using ~rti~ac~s well kncwn to those ~killed in the art o~ hlgh resolution displa~s, ~; ;
FlGS~ 2 ~ 3 and 3A ~l~a ahow ~h~ gl~s~ di~play ~reen 30 and ~k~ oolor de~ining back coating 40 a~or~ln~ ~ protec~ed, high re501ution color de~inln~ ~ys~m. Ihe screen can be made o~
varicus ~orm~ o~ glass or glass equivalents suited to various aE~llcations, including tra~p~rent or translucen~ plastla and c~ramic plate ~or mRsh) materlals. Ih~ coating 40 can comprlse (e.g., as in the ~IG. 2 - 3 embcdiment) a base 42 o~ tantalum and an overlayer 44 of anodic lly formed tantalum pentoxide, in turn overlaid with a protective coat 46 of silicon dioxide. The coating 40 preferrably ccmprises (e.g., as in the FIG. 2 - 3 &mh~;mP~t takÆn together with FIGS. 3A--3D) a tranrp rc~t bass portion 25 of, preferrably, about 3,000 Angstroms thick indium/t m oxide which ' ccntrollably coated on the screen 30 (or onto a tempor~ry substrate and then transferred to the screen). Ihe coatlng method is pref~rrably sputtar~ng (under pref d conditlons o~ 1 X 10-5 Torr F~ re (with a partial E4~isure oP ~iK microns o~ oxygen ~n a bac ~ d ~nert :~:' - ' ' ':! , " . . , '` : . . ~ . . . ' ~ .'.'`. . . . . .
WO 90/16057 2 ~ t~ ~ 1 3 a PCT/US90/0333~ ~
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ambient gas), one t ~ volts, 1.5 anps discharge, spu~kermg an indium/tm ~ e ca ~ target with deposition conditions adjusted to give akout five ohms per square sheet resistivity indium/tin oxide. Such indium/tin Gxide systems per se are well Xnown and characterized in the display arts. They are transparont in the full visible spectrum and have oon~ul}able electrical resistivlty/conductivity further conditions. The lndium/tin oxide is overcoated with a thin layer 42 o~ tantalum nitride, pre~errably on the order o~ 1,000 Angstroms and applied by vacuum deFcsition, sputtering or electrolytic molecular beam epitaxy (M~E). ~he tantalum nitride ls then anodically oxidized to form a layer 46 of tantalum pentoxide at a thicXness effective as a blue filter. Interval stripes 26I are etched in the coating ~0 dcwn to the glass level. Ih~ remain~ng isolatRd metal/metal oxide stripes ~6G and 46R are th0n ~ ized to di~ering oxide thickne~ses o~ adJacent such skripc~, ~n a x~p~at~n~ s~ries o~
~t~ o~ grad~d tantalum oxide thickne~s ~ yleld~ng di~xent color re~pon9q~ aorre~pon~ng to ~an~al~ oxida ~hiaknc~e ~ndicated ~9 cxi~ atripes 4~, 46G ~nd 46~ (typically wi~h combined tan~alum and tantalum cxide thicknesse~ d about 1,600, 1,400 and 1,200 Asgst~rms ~ ti~ely, based on an original 1,000 Ar~strom tan~alum ~ilm, to de~ins red, green and blue responsiva stripe~, r ~ ively). Ihe isolated strips 42/25 are available as ancdic e~ectrcde conductors to form stripes 46G and 46R to green and red. By "response" or "respo.nsive" to a giv~n color we mean that the stripe will pass that oolor spectral cc=ç=Dsnt of a light source. qhe three adjacent stripes 4~R, 46G, 46B de~ine a set 46S whlch ' one o~ a series of many such se~s spanning the ccating ~o define a full display area.
It will be ncked that in the FI~. 2 - 3 s~bcdim~nt separate y-electrcdes 24 (preferrably o~ optically tr~c~oun3nt, but electrically conductive ma~qr~al such a~ indium~tin oxide, I.q'.O.) ~or light passage elem2n~ 20 and ~an~al~lm str~pes ~6 are .` :: , . : ,:,. :.:: ., ,: . , , ": ,., .. ,.. ;. :.:: ,., ~ .", :, "
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provided (as anodic electrodes and, ultLmately, as color filters). Ih2re is a problem o~ aligning electrodes 2~ and 26 which can be overoome. It can also be avoided. As shown in FIG.
3A, I.T.O. stripes 25 (or a ~ull base layex before etching in the stripe intervals 26I) can be provided under the tantalum layer(s) 42 to enhance oonductivity thereo~ ~or service as y-electrodes of element 20 ~hareby resolving alignment problems, Th~ ~nodlzing (oxidation) conditions ccmprise a series of anodi~ing steps at dif~er~nt voltages applie~ to the sheet of indium/tin oxide overlaid with tantalum (acting as an anode) and a distant ccurtcr-electrode (cathode) to produce the respec*ive stripes, under anodization oonditions and oontrols, a~ ~ll as criteria, well kncwn in the electrnchc=ical art~, inoluding pre~errably, ~or present purpo6e~ ~ use o~ citric acid a~u~cu~
electrol~ta. Cbnventlonal high resolution n~ ng t~chniqu~ m~
~tcp. ~kX~ , ik i5 p~e~arr~d ~ when in~ n~l ~tr~pes break up the indium~tin oxld~ ~tripQ~ - to u~a the in~ium/tin oxlde base layers a~ select~vely activat0d electrodes tor simultanecusly acti~ated a~ diP~erent voltaga levels) to ~acilitate anodization.
qhe pre~erred normal process, as indlcated in FIG. 3B
(for ccrstsuc*ion o~ an i~ted y-electr2de color control stripe array), is to coa~ the glass with I.T.O.: then coat with Ta2N: then anodize to blue transmit: then to etch interval stripes (using conventional photo lithographic processing including a mE~k~ng step to create precise, reliable alignment and width cont m l of intervals and rl=eLsLing raised strires);
~hen anodizing g ~ trar ~ it arxl red trar ~ it s~ripes: then dÆpositing pbokoresist protection mask over the ~hree colors, leaving in~erval stripes between color i~tripes clear: and then deFositing cpaque material over ~he entire plate. Finall~, on~
li~ts o~ unwanted cpa~u~ ma~r~al and r~L~L~ng phLtor~sidue.
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wO 90~16057 ~ ~ 5 ~ ~ 3 ~. PCT/US9o/0333~
m us the adjacent stripes of a resultant set are separated by high resolutian cpaque interval segments. Alterna-tively, high resolution interval defining mask stripes can be applied to the coatm g a~ any other stage of development. Such intervals, when used, provide the cpportunity for sharper relief (contrast) to colors.
FIGS. 3 and 3A prcvide expandRd ~llustration o~ the above described s~riping usin~ intervals between color stripes of an RGB set and between sets. Ihe glass screen 30 is of twenty-~ive to forty m~l thickness depcnling on total size of display for rigidity and coated with repeating sets, each comprising three stripes 46R (red), 46G ~green), 46B (blue), ~ep æated by intexvals 46I. The latt~r may be bar~ or bac~illed with an opaque ma~erial. The interval~ pres~rve el~ctrical saparation o~
stripes ~6R, ~6B, 26G ~3 well a~ ual di~tinctn~ o~ ~uch oolor ~tripe~ n3tcd ab~va, the ~tripe~ ar~ ~hln ~ilnL~ wlth mwltipla l~y~r~ ~he wldth ~pan o~ ~ch o~ stripe~ 26R, 26G, 26B
i5 abaut .005", p~ rrably a~g., .OOlll ~or use at p~ ~ t ~ndustrial goal l~vel~ in the ocnsumer TV field prac*ice (being .0l5"); but, ~or okher applications, e.g. H~TV, the width can be set as low as .OOOl"-.0002"). This is rela~able ~o selected spot sizes of the light filt~r section ~0 and desired display screen color resolution andVor desired pixæl size, as a ~hole, for the end use display, all as dlsI1~;scd further, below. Ihe stripe width is preferrably uniform, but may be non-uniform for scme applications. ~he interval stripes are from twenty to one hL~x~n3d fifty Feroent of adjacent color stripe widths (taking an av~rage where adjaoe nt stripes are of different widths). of ccurse, the ~ s~ripe can be made sm2ller or omitted (i.e~, unber ten peroent o~ adjacent active stripe width).
~ IG. 3A alsD shows th~ associated light source lO pr~du-.,. . :. . , , . :. . .
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~ 2 ~ 3 ~ ~
cing a un1form, preferrably collimated light output Ll and electrically controlled filter section 20 (typically abou~ ten to forty ~ils, i.e., .010-.040 in. range) prc~ucing selectively Fx~3d large or small spots of li~ht I2. As note~ above, the reverse stra~egy can be us0d, i.e. selective blocXage. Large spots of light passage ~or blockage) are ccmposites o~ adjacent 3mall spcts of such passage ~or blockage).
Ag m~ntioned abov~, FIGS. 3A ~and FIGS. 3C-3D) also show a further emkodlment o~ the invention wherein light source and control are combined as shown at lO/20-EL using an electrolum1nsccnt material ~or other artifact, e.g., an array of semiconductive light emitting diodes or light emitting Fhw~phor~ he ~lectrode strips 22, 25 prcvide the cross~ng x-, y activi~ation matrix ~or ~lective li~ht emission.
Pra~r~bly, a ~ on oxidc lay~r ~nct ahown) o~ abou~
1,000 ~ngstrom~ o~ th~ckn~ d~po~ d ~v~x tha ~ant~l~m oxide strlp~s by ~putter~ng or chamlaul vapor deposltion, for pr~tection witlh minimal llght attenua~ion. Se~uential layers of Ta205 e~nd g10~ i.e" ~veral ~Ise~s~ each typically two or three ma~ b~ udded to enhanc~ or "peak" th~ tre~nsmission percentage e~nd provide brighter response. This is shown, as applied to stripes 26B, 26G in ~IG. 3D with tantalum repeats 42-l, 42-3, 43-3 and t ~ um oxide repeats 44-l, 44-2, 44-3.
~ IG. 4 is a fa oe illustraticn of stripes of adjacent color sets overlaying the high resolution filter defin3d e~s x-, y- array of activatable ligh~ passage (or blockage) spots. Ihe x- an~ y- electrales (22, 24 in PIG. 1 or æ, 25 in PIG. 3A) of light fitter 20 enable uniform cor~trolled ~ts 20L o~ selectable liS~ht passage or blockage. These can be of essentially cim~
~c~m of, sa3,r, .0001 inc~h d~er wit~h mini~ overlap, if any, o~ adjac~t ~pcrts. I~e stripea 26B/ 26G, 2~ o~ a ~e~ 26S can be ..: .. ... ... . . . . . .. .. .. . ... ..
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of .0002 inch width with i ~ stripes 26I, batween stripes of a set and between adjacent sets, o~ .0001 inch width, to produce a ~ ~ le set color span wid~h of .0009 mch. For purpcses of FI~. 4, the use of ~ s 20L aligned with cpaque intexval stripes 26I is assumed; these are, of oourse, superfluous ~nd can be omitted in high volume ~ tion designs (or at least electrical controls for such cross-over locations can be omitted or set at a de~ault llght blocking mode as shcwn in FIG. 4).
Ihe x-, y- electrodes can be controlled with a pixel st~ategy d uniform size pixels d width d one or more dots (crosscvers) or sets of doks and ;height o~ one or more dots or sets of dogs in integral ~r non-integral units. Each such pixel as arbltrarily de~ined ha~ a selectablllty o~ s ~ and intenslty cholce~, ~hr~ugh s~lectl~e passage or blo~kags o~ ligh~
in ~ele ~ l am ~ ~r ~ o~ s ao~iva ~ l) ~ rough colar Ihe usual t~rm 'p~l', as a Pund2men¢al uni~ o~ display resolution is an arbitrlry ccnitru~t a~ applied to the present inv~ntion (thcu3h correspondlng to a phy8ical 3pO~ in a raster ~can cath~de ra~ tube, llght emitting diode matxix, discharge tube matrix, inca~descent lamp ma~rix or like state-of-~he-art displays). ~ccrpting the ccnventional te~m pixel arbitrarily, as applied to FIG. 4 and defining a piXf~ width PW as cne set width and pixEl hQight EH as a height equal to that wiæ h, then a .0009" x .0009" pixel is establishsd (i.e., abcut one ~;1 x cne ~il). This may be compared with the so called high d0finltion television ~ d pixel, which - in mLst currently commer~ial or proposed-as-oommercial e=b~rimlr¢m has a pixel o~ eight to ten mils x ei~ht to ten mils wi ~ i~ht dimensions; NT~C ~U.S.) co~venti~nal television (in bome s8ks) of abcut thirty mil9 X
thirty mils; or pr~ecklQn ~elevislon systems o~ 9ixty to eighty W O 90/16057 2 ~ 3 ~ PCT/US90/03335 use fifteen mil x fifteen mil pixel standard and stabe of the art LLD oomputer monitors use a twenty-five mil x twen~y-five mil pixel. hven if thP~ FIG. 4 e=bcdlment is derated by a factor of five times (i.e., to a five mil by five mil 'pLxel'), it still exceeds state of the art resolution. Mor~over, the distinct pixæl limitation can be avoided in the present invention, with a computer controlled x-, y- electrode control affording intRrleaved pi~Els (or to put lt another way referring to the spoks 20L as th~ ~bnd~r*al ~ ts Or resolution).
Staying with th~ exampl~ of a FIG. 4 as deEined above and assuming each sF3t 20L to be normally light tDac=p rent when not activated and ~paque (as shown by shading-in in the ~igure) when activa~ed by a voltage appli~d ~rom it3 c~nssing x-, y-electrcde~ (the blocking strategy), then it is se~n hcw colox is constructed r~or the 'pixel' o~ PW/P~ width ~nd h~igh~ (.0009" x .0009", or nlna ~ x nir~ ~ts, 20~ as p~v~o~ql~ d~:~in~l).
}latctlir~ ac~a~ n ~G. 4 ~a~ ~ntroll0d bloedcir)g:
~ o~ all ~t3 aligned witlh the ver~ical interval stripes, as a ~le~t to, or in lie~ of, cpaque materials of ~he stripes per se, f~r ~xntrastJ
-- some of the red vertical stripe's s~s;
-- none of the green vertical stripe's spots; and -- all Oæ ~he blue vertical stripe's spots.
~he net effect is a predominantly green pixel of maximum intensity with a contributed red compcn~nt Oæ abcut forty percent n2uc~mlm intensity which a human viewer ~or machina imaging viewer o~ human resolution and percæptian capacity, mor~ or lQss) W O 90/16057 2 0 ~ 9 1 ~ ~ PC~/US90/03335 -16~
detects only as a compo~ite color. This together with dozens, or hundrEds of adjacent oontrolled pixels prcvides the viewer color impression. It will be appreciated that apart from intensity control, there is a high redundancy of color selection signals impo6ed on a single 'pixel' to assure reliable response even in the ~vent of partial control system failure.
FIGS. 5 ~ 6 show c~hex variant~ o~ pixel control (in ~ace view a~ in PIG. 4, but with d~ts indicated as rectangles).
Both e=bod1ments have a one spot plxel. In FIG. 6 interval striping 46I is shcwn. In FIG. 5 thR array of y- electrodes (ur~nooat oomponent 25 of stripes ~6 in FIGS. 3A - 3D) and~or X-electrodes (2 V FIGS. 1 - 3D) may have to be thinned dcwn to avoid sh~rting o~ ad~acent such electrodes, e.g., a .0035~ condNctive elect~ode wld~h in relat~on to a .005" color s~ripe.
Xn F~GS~ 5 and 6 red, grE~n and blu~ altQrnat~ in 1~
relation ~n the s~xipc~ ~R, ~G, ~6~. ~ut it will b~ understood that other ratlos can be prov~ded. For example, human observation favors repeating multiples of ~:2:6 of blu2:green"red, respec*lvely, ~or optimum control. Ihis kind of balanced xatlo can also be used to compensat~ for variances in phosphor tor LCD) or lamp s ~ range or guality in the light passage/blocka~e/origination sec*icns of the display system.
FIG. 7 shcws a ~ such e=tx~L~nent with a -horizontal stripe width 22 equal to the a ~ te of five vertical electrode stripes 25 and associated intervals 25I (all buried m a single oolor stripe layer 46B/blue). Astivation of a cross-over pair (one x- electrode, cne y el ~ e~ wfill light up (or block light) in ten doks, if the ccnductive strips 25 are ganged or ~ . Alternatively separate electrode connections can be m3de to 25-l, 25-2, etc. for mcra precis~ ccn~rol.
.. , w o go/16057 2 0 ~ ~1 3 ~ pcT/usgo/o333s -17- :
F~GS. 8 and 8B show usage of the oolor control section withcut strip m g or other areal configuration, used 6imply as a f;lter in transmission t8A) and re~lective ~8B) ~odes.
FIG. 9 shows (in transverse section, as in FIG. 2) a display s~stem whÆre ths y- elec~rodes 25 ~e~, s.g., FIG. 3A) are prov.id~ wi~h ku~s-~ars, e.g. B(Y), at interval~ to establish low resistance path lengths to all regions o~ the y- electrodes and in turn ~o each dok d~ined by a cr~s~ ove~ of such a y-electrode wi~h an x- electrode 22. Similar ~Lr~tegy can be p m vided for electrodes 22. qhe r ~ tan~ equivalent circuit is shown in FIG. 10 ~ e sec~ions o~ anodic oxide coat m 3s 44 together with crossing-ovcr x-, y- el ~ e portion~ 22, ~5 act ~ an a~ray o~ capacltor~. m e lnsulativ~ value o~ tha anodic oxide i~ ~upplemantRd by that o~ the pho5phor clectx~luminescan~ !
layer.
min indium/tin oxida lay~r~ c~n ba u ed ~or t ~ ~ ne~ ~ut u~ing tha kLss bar~ to l~mit voltage drcps along electrode length~.
Tha ~ontrol o~ spct ~lection and pre5entation o~ a screen display can (advantagecusly) be simLlkanecusly lmplemented over a whole screen (or large section of a screen) - in contrast to a raster scan or like roll m g implementation` of display control. 2ut roll m g implementation can be adm~JI~b~o~d in the present case ~or some aesthetic reasons and/or to utilize While color e~ltL~l in terms of primary colors of additive synthesis have been descr~bed, other repeating color stripes of additlve or Eub~tr~ctive s,y~thesis systems can be applied. ~h~ available rang~ o~ colors can be ccrstantl~ varied ~rcm sec*l~n to ~ecti~n o~ a di~pla~.
W O ~0/16057 PCT/US90/~335 2~59:L3.~ ~
Cuntr~l ~ystems utilizlng the above display formats can comprise use of one or more o~ the following exemplars, extrapolations therefrom or equivalents or extensions now apparent to those skilled in the relevant display art, given benefit of availabil~ty of the present invention and its disclosure herein.
qha d1splay sys~em can be made in selecked small or laLge sizes with uni~rmity o~ performance unlimited by edge or corner e~fects o~ the types associated with CRr displays or the like. Resistance over lengths of x-, y- control electrodes can be a limitation at very long lengths (e.g., several hundrsd light spots l~ng~h); but thi~ can ba circumv~nted b~ modular con~truotion o~ th~ ~ilter portion and/or usa o~ (p m ~x~ably tzansp~rcnt) buss bar~ ov~rlapping tha ~ilt~r el~ctrodo Wi~9 to carry high~r vol~a~ ncdo~ to tha ~nt~ior o~ t~h~ r ax~a.
Th~ gla~s 30 (or a precu~sor tx~n~r ~uustrata) can ba o~
lndo~ini~a length ~n manu~aabure or m~de in conveni~nt bakch ~izes and cut to end-user sizes c~g needed. lhe basic filter construction i~ ~imilarly ~laxi~ble as to economical stock ~anu~acture c~nd custom selection o~ usable si~es.
Several variations have been discussed abcve relative to a oore e~bKdirent. Several further vzriations can be made ~ sistent with the scope an~ spirit of one or re aspects of the present invention. For example, color control matexials other thc~n tan~alum ~ ide can be used - e.g., oxides of other valve metals af~ording an adherent film.
Ihe indium/tin oxide stripes, or equivale~ts, are usable for the~r optical prcperties and for thair electrical prcFerties (carrying current to provide a mcnolithic anode electr3de or distinct ancdes in th~ anodic ~xidati~n step) and n~chanical ....... .. . . . . . . . . .
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wo 90/16057 2 V ~ 5 PCM~S9OJo3335 ~ies as a glass to tar~tal~n substrate }:)ridge, all as slla~
a~ove. But further, in eTxl use, i~i~tin ~ide stripes can be us~ as electrodes to ccxntrol re~se (and,/or on-off re~onse) of averlying coating layers.
Ihe basic color stripes ~and inten~al stripes, w~en used) are sha ~ above as arrays o~ long st~ in a single direction. Bu~ Gros~ etching, a~er a need for eleY~brical ccntinuity ha~ passed and using appropriate masking or selective etching ~an pro*uce lands (isolat0d mesas or islands) of color responsive oxid~ spoks.
Ihe light souroe spectral range ~nd intensity and4or glass ~oreen trau~xlrIocy characteri~tics are further distinct variables co~r~llable in design selection or utilizAtion to ~urth~r impact ~ d~spl~y.
While x-, y~ orthcgon~l coondln~ hcwn ab~ or ~ilter al~ctrode arrangements, one could use various non-orthogonal coordinata sy~tems, e.g., polar coordinate6. A
varia~y o~ llnsar or non-linear ~ n~s ~e.g., lo~arithmic) ~an ba impc~ed in each coordinate se~.
Ih0 areas of applica~i~n o~ the i ~ ion include - ~ut a ~ not limited to - consumer and industrial video, computer mcnitors, ins~rumentlti~n display6, military displays, sports arens scoreboards and cther variable public billkoards. lhe Invention is also utilizable as a ~ontrolled light source independent of d;splay purpcses in sizes ranging from very small t~ v~ry large, taking advan~age o~ one or m~re o~ the flexibility of~ control control, resolution, economy o~ nEunufacture andVor ckher aspects of the present invention.
Ih~ inv ~ on al~o ocmprises mean~ ~or enhan~ing the ' .
, .
.' . . ~ ! ~; ' ' ' ' W O 90/16057 ~ ~ ~ 9 1 3 PCTtVS90/03335 ocnductivity of the indiumrtin-oxide underlayer or overlayer material (where used) and resultant enhanced indiumrtin-oxide prcduct (a coating) and enhanced coated pro*uct. Ihis aspect of the invention can be applied to materials for electrical conductivity compatibly with high light transmission.
h this last-mentioned aspect of the invention, ~heet reslstivity on tha order of belcw 2.0 (in s~me instances, below 1. O) Ohms~p~r~guare i5 achi~vable ~cmpared to five to ~ifty ohms-per-square in the state of the art. Ihe impact of thLs is to enable longer linear runs andVor reduc~d thickness of conductive strLpes of indium-tin-oxLde (or the like).
The realization of reduced electrical re~istivity/higher alectrlcal c~nductivity is achieved with only a modest lo~s o~ optical tran~mis~ivity typically less than twQnty p~rcent at m~st ~p~ctral rang~ o~ int~xe~t in ~lect~ow cptic d~splay or ~iltQr application, ~uch a~ tho~n ~l~ed abcve.
Realizaticn o~ SU~l improvement is preferrably made thxcugh th~ follcwing prcces~ ~t~ps:
~ 1.1) Establish a base layer free of external i~ns li.e. alkali ions as applied to a glass substrate), preferrable by beginning with a glass such as sode lime or Corning 7059.
ClPar the substrate with detergent an~Vor solvents and dry it at 150 in air or inert gas for about half an hour to remsve isture and follow up by sFutter~etDh or like radiant energy ~ to removs residual ccnt~=inonts. qhe sputter etching ~c at Gre-h~lf to one ~ owatt und2r abcut 8 millitorr vacuum and after prior evacuation and argon backfill.
(1.2) Cover its sur~ace to b~ o~ated with a (sFL~IY~cposited or chemical-vapor-depositiQn deposi~ oon W O 90/16057 2 ~ 5 9 ~3 3 ~ PCT/US90/03335 dioxide layer of about 2,000 Pnqstrc=s thickness to mask the aIkali ions or okher ex*ernal species from interacting with =ubsequent coating and provide sukstrate for further coating. A
pre-processed silicon glass substrate free of such surface species LS another approach to the same end.
(1.3) Then the so-coated glass is heated at 350-450 C ~or abcNt ~i~te~n minutes under 5 x 10-7 mm ~g. pre~sure.
~ 2) A layer o~ 7000-10,000 2r~stloms of indium~tin-oxide is sputter deposited an the so-treated substrate.
(2.1) Ihe ~irst 100 to 200 ~ngstroms o~ such deposition ~eqyivalQnt to the ~irs~ ~w monola~ers the~eo~) is ocrduoted undRr bia5 ~ ring cQndit~ns to maxlmiæe pur.i~y and density. ~ha 0pUt~sr~n~ o~ th~ indiumrkln-oxide i~ ccnduated ~n atmc~Fhe~s init~ally ~vacua~cd to 5~10-7 mm. ~g., then back-L~ w~ a~o~3 w~ nl p~ ~n 4 to 5x10~5 mm ~g ~ 2.2~ Withcuk ~emcval from the sputter system, the ~putt~ring d~scha~ge is ~hen termin~ted and a vacuum bake of 400-500 C ~or abcut 15 ~ s at 4 to 5x10-7 mm. Hg. is applied to create oxygen vacancies.
., .
FIG. ll shows the develcFment of enhanced (reduoed) shRet resistivity of tWD sa~ples of (l.l) soda lime and (1.2) Corning 7059 coated with indio=-tln--xldb as described above.
l~e y-axis (l~thmic) i cit~ are arxl ~e x~
(lir~3ar) ~s time in minut~ of the final bakir~ step of (2.2) to . :~:
create a~en vacancies. Ihe ~heet resistivit~ of the san~les :
begins at s~ cllms per s~are and d~ dramatically to well with no ~urth~r change aft~r abo~t an haur and a bal~.
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W o 90/16057 ~ ~ ~ 9 1 3 ~ PCT/US90/03335 Bulk resistivity o~ the coating is also reduced to about 0.5x10-4 chm-cm, a ~=bstantial impruvement over commonly available indiumrtin-oxide ma~erials.
lhe processing as described above can be implemented over a broad area or through masking to provide mLltiple stripes o~ conductive coating (alternat.tvely interval stripes can be ~tched or mach~n0d cut o~ a broad area oo~ting).
Some o~ t~le processing steps dPcrribed abcve can be supple ~ or supplanted by laser or electron beam etching, micrc~achining, ion deposition, electroplating, electrcphoresis and okher processes.
m e enhanced matallic co~ting can be und~r 20,000 Ang~kroms but i~ pro~rab~y w~ll undar 10,000. ~here a ~Ub9~rat0 d1~P1AY~ a.g. ~ Qpkl~al ~ransmi~8icn ~n v~ble ~a~g~
the metallic oo~0~ gl~s~ ~lth low ~heet resi~tiviky o~ the aoating) will di~play over 80-~, pre~errably 85~ or more ~ransmis8ivlty in the 8am~ 9pec~r21 range, i.e. re~uction of less than 20~, pre~errably less than 10~ via ~he coat~ng. In contrast withcut th~ special enhJnce3ent a 10,000 Arystrom cc~ventional coating of indium-tin-oxide on such glass would typically re*uce to about 60% ~ ssion and w~uld have higher electrical sheet resistivity.
.
qhe above de~czibed enb=nccmc~t pr w 2ssing mcdifies semicund~ctive charar~Qristics of the indium-t m-uxide coating or the like thrcugh axygen vacancy creation (or equivalent neans) to yield the lo~ered resistivity with a higher degree of F4~ rVation o~ ç ical tra0smiYsivity Filter applica~lons d th~ ~nvantion - in re~lectiv~
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W o 90/16057 2 ~ 5 ~ ~ 3 ~ PCT/US90/03335 , . ....
and trans=ds~ive mcdes - are characterizel by abrasian, thermal and environment rasistance, including super-saturated salt solutions and/or -55 C to +550 C range consistent with 90%
transmission/reflection, ease and low cost of tailoring to pæticular applications.
It will now be app~rent to those skilled in the art ~hat oth~r embodlmRnt3, i~prcvements, details, and uses can be madR consistent wlth the letter and spirit o~ the foregoing disclosure and within the sccpe o~ this patent, which is limited anly by the follcwing d aims, ccçscruei in aocordance with the patent law, including the doctrine of eguiv21ents.
Wh~t i~ claimed i~:
:
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matrix liquid crystal display (ICD) means. See, e.g., Sakai et ali. (NTT), "A DefectJTolerant 5echnology ~or An Astive-Matrix LCD Integrated With Peripheral Circuits~ SID (Society for : Information Display) 88 Digest pp. 400 - 403. ~hin film diode or .. :. transis~or light emitter arrays can be provided in similar fashion. The foregoing publlcations are incorpo~ated herein by reference as thcugh s~t out at length herein. ~ The present i~ventlon prcvides ~ignl~icant bene~its compared to the s~ate of ', the art and camm~raial practice thereo~.
i, u It i5 an object o~ the present invention to pravide,~ displays o~ high resoluticn dot area (pixel) selection, with high intensity o~ color availability selectable avQr a large spectral ra~gQ in cus~m tailored de~ign and production-~, . It is A ~urth~r ck~ect 0~ the in~nt~n to pr~vid~
~ ~ ei~h~ VQ percont-plu~ ~pro~rxably, ovar n~n~t~ F~ nk) llgh~
:;~. ~si~r th~cug~u~ ~ v~iblo c~i~al ~pec~ ~alu~ ~d, blu~ een) ~nd ~rab~y al~o in t~ni~ ~pe~ rar~es " l~on~ visible ~e.g., near ~ ar ~, uV) .
It i~ a ~her c~ect o~ t~ invE3ntlon to pra~ride sudh ~-............... di~plays o~ canpact otn~ form.
,; It is a ~er ~bject of the irn~ention to prcnride such dis;plays wi~h lang life an~ lc~ failure vulnerab;l ity.
--: It is a ~urther cbject of the inv~nticn t~ prcvide such displays economically and simply.
It is a further cbjeck of the invenkion to provide such i displays with high ~peed o~ response to control signals and ~ si~nply ~c~ol ~ in c~inati~ t~itll.
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WO 90/~6057 2 0 5 ~ 1 3 a PCr/US90/03335 It is a f~art~r bb~ect oî the invention to pmvide such display free of parallax and/or anisotr~ lim~tations of its ~ptical characteris~ic.
It is a further ~bject of tha i2~ ion to provide such ~play wi~h a high degree of te~perature stability and/or chemical ~tability ~ all cor~litions of marmfacture and ~se.
.. .. ...
Wo 90/16057 2 ~ 5 91~ a PCT/US90/U333~ ~
lhe cbjects of the invention are re21iz~d in a system using thin f~lm technology to pr3vide a key color control section and also using such technology for light oontrol steps other than color ~;ltering.
me display system has a l~ght source and high r~olution light control ~ er p~oducing selected dots o~ light o~lglnation or passage at high resolution (or dots of light blockag~ in an amblent of essentially collimatad light).
In its light passage embodiments, the system is constructed ~nd arranged 80 ~hat a beam oP light impacts a ~hin ~i~m color c~ntrol parel and passes thxou~h it ~or is re~lected by it), and pxeP~rrably al~o pas~es th~ough a pr~t~ctive t3z~q>lrent ~ore~n, to a view~r. Ihe col~r cont~ol panel ccmprlsa~ ~ highly adhQr~nt color r~pon~ m~t~ri~l, p~a~rrabl~
an ~nodically oxi~iz~d ~hin ~ilm Or ~antalum or ~n~alum nitrides or other anodically oxldl~ible metal (valve me~al).
Pre~Qrrably, the color control and light ccntrol ~ilter portions are inte~rated to some extent as hereinafter described to a~ford automatic self-alignment of cross-hatched ~e.~., x-, y-) ele~*rodes to define an array of cross-cvers, automat~cally slaved in cor~ect array positions. Dcts of light are prcduceable at the cross-overs to yield controlled Ip;x~lsl as sm211 as a single dot or with a grcup of dcts ~a few or many) defining each P~.
In acccn~ance with the inventicn ~Plected areas of the tantalum cxide (preferr~bly adjacent stripes in a SQt, wi~h an array of repeatlng such sets o~ ~tripe8) æ e o~ different thicknesses to produce di~erent color responses to wo go/16057 2 ~ 5 913 ~ PCT/US90/03335 ~ ?;,~
., . ~"
incident/transmitted light. AscGrding to a further ~ of the invention ~he tantalum oxide "layer" h~s internal sublay~rs of tantalum oxide and a tr~nsp~rent material, e.g., silicon dioxide.
Ihere can be multiples of such sublaye~s stacked over each other to enhance the brilliance of color response, according to a further asp2ct of the invention.
The color contr~l elements ar~ ~preferrably) side by ~lde in a sin~le thin ~ilm layer or in each of several such ~ublayers therQby a~Pording high intensity. The general illuminating light passin~ thrzugh color bands of the cantrol layer projects aver a wide angle space after passi~g through the color layer with ~nl~c*r~pic cptical resFonse, i.e. aver 90' (pre~errably aver 135') o~ vie ~ angle. ~he tantalum oxide ~ilm, or the like, is vary stable and resistant to savQre conditions o~ t~mp~ratur~ an~or acidia ar alkalin~ anvironme~.
It ~ ~ormed by ancdic oxidation u~ing an und~rlayer o~
t~n3prrcnt khln ~lm net~ coa~in~ o~ ~ha m~t~ a~ ~n ia el~ctrod~. rrh~ m4~al may b~ 1 layQr of e~ectrically eonduative, tran~parent material ~or ~ptimum resistivity ~n end use.
Where th0 anodic oxide separates x-, y- electrodes or the like ~a~ indiea~ed above for prcferred crhxxluDents~ then a very high dieleetric eonstant separati~n of such electrcde groups c2Ln be formed with high ele~t,ieal insulating value, but acoommcdating close spac ~ .
Other objects, features, a~d advan~ages will be apFarent frcm the follcwlng deta;~ed descriptic~ of preferred embodlments taken in c~njunction with the acccrç~vry m g drawing in which:
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WO 90/160~7 2 ~ 5 ~ ~ 3 ~ Pcr/US90/03335 E~ I~IaN OF q~ nRa~
~ IG. 1 is an i~ic sketc~h of an ~r~i~t of a di~play .syst~n of the inven~
~ I:GS. 2 and 3 are lateral ar~l transverse cmss-section sh3tches (tak~ ak the re~ective viewing dlrections II-II and III~I~ o~ EIG. 1) ~N ~n expand~d scale, o:~ a portion of the ~IG.
1 ~bod~nt;
~ IGS. 3A, 3C ar~ 3D are secticned sketctles, further expanded and hiqhly schematic illustratLng stepe of construction of a portion o~ th~ oolor control ~ection (and a part of the pixel s41ection s2cticn) o~ the FIG. 1 embodim:nt and FIG. 3B i9 a flow ch2rt outlln~ o~ those cc*~truction steps ~nnka that there i~ a chang~ ln ccnstrLction ~n FIGg. 3A--3D compnrod to FIG. 3 wh~ra~n th3 ~para~ oleotxodc~ o~ FIG. 3 ar~ o~itt~d and r~placed by y- ~lectr~de~ in~egrn~4d wi~h color ~trip~s in FIGS.
3A, 3D)~
FIG. 4 is an expanded ~ace vi~w o~ the glass substrate (screen) o~ the FIG. 1 embodiment indicating 0electi~ely established doks of light passage an~ blockage an~ a si~gle pixel arbitrarily established as a nine dot by nine dot square (althcugh a pixel could be established m~ch larger or as small as a single dot):
FIGS. 5 - 7 are sim~lar face ~iews for other embodime*ts of pix~l c~*l~mdnation on the di~rlay screen;
FIGS. aA an~ 8~ are dia ~ s of usage o~ the color fil~er of the display ~ystem withcut hi~h resolution areas segrega~ion, bNt rather as a broad area color control ~ilter ln ';' ` ~ ! ' , ~ , . . .
W V 9Q/~6057 2 a ~ 9 l 3 ~ PCT/US9~/0333s .~ .
--7 - ~
~ssi~e (8A) and reflective (8b) m~des;
FIG. g is a sectioned sketch (taXen laterally as in FIG.
2) of a variation of the FIGS. 1-8~ entxxLu~ents using kuss bars to reduce resistivity losses alon~ the elongated conductors; and FIG. 10 is a related cir~uit diagram.
FIG. 11 is a trace of decreasing sheat resistivity of an indium~tin-cxlde coakiny as enhanced thrcugh an aspect of the present invention.
''~
. . . .... ... . . . . .. ..
WO go/16057 ~ ~ 5 ~ ~ 3 P~/US90/03335 a ~.
-8- :~
rEIaIlED DESC~I}TICN OF E513~3~RED ENE01TN~N75 Referr1ng now to FI~. 1, there is shown an embcdlment d the invention comprising a light source 10; a light passage section 20; and a display screen 30 with a color de~i ~ back coating 40 (at the interface-planar region between 20 and 30) hereinafter described. As variants frcm this embod~mcnt, (a) the light ~cuxce can be s~t back at a distance or (b) the light souxc~ and llght ~ilt~r can be in~egrated in vario~ ways as explained bel~w. The viewer's position is indica~ed at E. m e elements 10, 20, 30 are pr~ferrably of compact ~lab-like form and can each be made in thicknescPc mubet~ntlally below an inch.
FIG. 1 al~co ahcws that the section 20, which is electrically controlled has x-electrodes 22 and y-electrode~ 24 in the ~o~ms o~ arrays o~ linear conduc~o~s in spaced paxall~l planes (one plane for each array~. ~hen electrlcal curr~nt is supplied to ons x-el~c~r~d~ c~nduc~or a2 and ono y~el~c~xodc connection 2~, ~he ~ o~ ~iv~ ~m i5 controll~ (~g into aacount voltage drops along the lengths o~ such elongated conducto~s) so that a voltage iB supplied to an essen~ially tubular cro~ cve~ ~pct.
The light sourcc 10 pre~errably comprises a ~ull specbrum, level intensity source, but in specialized applications (or for economy) may be of narrow spec*ral range (wlthin or : :
outside the visible range) or with unusual intensity or attenuation at particular wavelengths. Ihe light scurce material chDices can be electrolu= m escent, ~nc~u~#R~ent, fluorescent, or - other thermal, phckovoltaic or dlsK~nge m2ans.
FIGS. 2 - 3 show the light pass element 20 expanded side and top view sections of the FIG. 1 ar~ul~3n~nt comprising wi~es (or striped coatings or other eguivalents) 22 and 24 ~or x- and ~- electrodÆs, re2pec~1vely. ~h~ ele~trcde wirQs o~ skrip~s ar~
,, " : ,, , , :, , . ::,,: , : j :,. - , .. .
w o go/160~7 2 0 5 ~ 1 3 ~ PCT/US90~03335 .., g of fLne diam~r or span and ~andwich a phokovoltaic liquid ~stal mat~rial 26. When crossing x- and y- electrodes are active a~ a crossover material spanning point, the local material is activated to pass or block light (depending on the selected material) to produce a high resolution spot of light passaga (or blockage) of no higher than .005" x .005" or as lcw as .0001 inches x .0001 mches, preferrably about .0005 to .001 inches (.0125 to .025 mm: l/2 to 1 mil) x .0005 to .001 inches, or circular equivzlents. Generzlly, for uni~orm spacing of x- and y~ electrode arrays the sp~t will be in-between ideal circular and squar~ configuration (an approximate square wlth rcunded corners). But essentially per~ect squares or circles of light passage (or bloc~age) can be pro~uced with specialize~d elec-trode/light-con~rol-material combinations, or elongated spots can be E~xxh~3ed, using ~rti~ac~s well kncwn to those ~killed in the art o~ hlgh resolution displa~s, ~; ;
FlGS~ 2 ~ 3 and 3A ~l~a ahow ~h~ gl~s~ di~play ~reen 30 and ~k~ oolor de~ining back coating 40 a~or~ln~ ~ protec~ed, high re501ution color de~inln~ ~ys~m. Ihe screen can be made o~
varicus ~orm~ o~ glass or glass equivalents suited to various aE~llcations, including tra~p~rent or translucen~ plastla and c~ramic plate ~or mRsh) materlals. Ih~ coating 40 can comprlse (e.g., as in the ~IG. 2 - 3 embcdiment) a base 42 o~ tantalum and an overlayer 44 of anodic lly formed tantalum pentoxide, in turn overlaid with a protective coat 46 of silicon dioxide. The coating 40 preferrably ccmprises (e.g., as in the FIG. 2 - 3 &mh~;mP~t takÆn together with FIGS. 3A--3D) a tranrp rc~t bass portion 25 of, preferrably, about 3,000 Angstroms thick indium/t m oxide which ' ccntrollably coated on the screen 30 (or onto a tempor~ry substrate and then transferred to the screen). Ihe coatlng method is pref~rrably sputtar~ng (under pref d conditlons o~ 1 X 10-5 Torr F~ re (with a partial E4~isure oP ~iK microns o~ oxygen ~n a bac ~ d ~nert :~:' - ' ' ':! , " . . , '` : . . ~ . . . ' ~ .'.'`. . . . . .
WO 90/16057 2 ~ t~ ~ 1 3 a PCT/US90/0333~ ~
--10-- .
ambient gas), one t ~ volts, 1.5 anps discharge, spu~kermg an indium/tm ~ e ca ~ target with deposition conditions adjusted to give akout five ohms per square sheet resistivity indium/tin oxide. Such indium/tin Gxide systems per se are well Xnown and characterized in the display arts. They are transparont in the full visible spectrum and have oon~ul}able electrical resistivlty/conductivity further conditions. The lndium/tin oxide is overcoated with a thin layer 42 o~ tantalum nitride, pre~errably on the order o~ 1,000 Angstroms and applied by vacuum deFcsition, sputtering or electrolytic molecular beam epitaxy (M~E). ~he tantalum nitride ls then anodically oxidized to form a layer 46 of tantalum pentoxide at a thicXness effective as a blue filter. Interval stripes 26I are etched in the coating ~0 dcwn to the glass level. Ih~ remain~ng isolatRd metal/metal oxide stripes ~6G and 46R are th0n ~ ized to di~ering oxide thickne~ses o~ adJacent such skripc~, ~n a x~p~at~n~ s~ries o~
~t~ o~ grad~d tantalum oxide thickne~s ~ yleld~ng di~xent color re~pon9q~ aorre~pon~ng to ~an~al~ oxida ~hiaknc~e ~ndicated ~9 cxi~ atripes 4~, 46G ~nd 46~ (typically wi~h combined tan~alum and tantalum cxide thicknesse~ d about 1,600, 1,400 and 1,200 Asgst~rms ~ ti~ely, based on an original 1,000 Ar~strom tan~alum ~ilm, to de~ins red, green and blue responsiva stripe~, r ~ ively). Ihe isolated strips 42/25 are available as ancdic e~ectrcde conductors to form stripes 46G and 46R to green and red. By "response" or "respo.nsive" to a giv~n color we mean that the stripe will pass that oolor spectral cc=ç=Dsnt of a light source. qhe three adjacent stripes 4~R, 46G, 46B de~ine a set 46S whlch ' one o~ a series of many such se~s spanning the ccating ~o define a full display area.
It will be ncked that in the FI~. 2 - 3 s~bcdim~nt separate y-electrcdes 24 (preferrably o~ optically tr~c~oun3nt, but electrically conductive ma~qr~al such a~ indium~tin oxide, I.q'.O.) ~or light passage elem2n~ 20 and ~an~al~lm str~pes ~6 are .` :: , . : ,:,. :.:: ., ,: . , , ": ,., .. ,.. ;. :.:: ,., ~ .", :, "
WO 90/16057 2 ~ PCr/~ gO/03335 F~
provided (as anodic electrodes and, ultLmately, as color filters). Ih2re is a problem o~ aligning electrodes 2~ and 26 which can be overoome. It can also be avoided. As shown in FIG.
3A, I.T.O. stripes 25 (or a ~ull base layex before etching in the stripe intervals 26I) can be provided under the tantalum layer(s) 42 to enhance oonductivity thereo~ ~or service as y-electrodes of element 20 ~hareby resolving alignment problems, Th~ ~nodlzing (oxidation) conditions ccmprise a series of anodi~ing steps at dif~er~nt voltages applie~ to the sheet of indium/tin oxide overlaid with tantalum (acting as an anode) and a distant ccurtcr-electrode (cathode) to produce the respec*ive stripes, under anodization oonditions and oontrols, a~ ~ll as criteria, well kncwn in the electrnchc=ical art~, inoluding pre~errably, ~or present purpo6e~ ~ use o~ citric acid a~u~cu~
electrol~ta. Cbnventlonal high resolution n~ ng t~chniqu~ m~
~tcp. ~kX~ , ik i5 p~e~arr~d ~ when in~ n~l ~tr~pes break up the indium~tin oxld~ ~tripQ~ - to u~a the in~ium/tin oxlde base layers a~ select~vely activat0d electrodes tor simultanecusly acti~ated a~ diP~erent voltaga levels) to ~acilitate anodization.
qhe pre~erred normal process, as indlcated in FIG. 3B
(for ccrstsuc*ion o~ an i~ted y-electr2de color control stripe array), is to coa~ the glass with I.T.O.: then coat with Ta2N: then anodize to blue transmit: then to etch interval stripes (using conventional photo lithographic processing including a mE~k~ng step to create precise, reliable alignment and width cont m l of intervals and rl=eLsLing raised strires);
~hen anodizing g ~ trar ~ it arxl red trar ~ it s~ripes: then dÆpositing pbokoresist protection mask over the ~hree colors, leaving in~erval stripes between color i~tripes clear: and then deFositing cpaque material over ~he entire plate. Finall~, on~
li~ts o~ unwanted cpa~u~ ma~r~al and r~L~L~ng phLtor~sidue.
" " ~ . ; . " ' ' ' ' ' ', ' ' ' ' ~ ~ , . , ' ' . ', . .
wO 90~16057 ~ ~ 5 ~ ~ 3 ~. PCT/US9o/0333~
m us the adjacent stripes of a resultant set are separated by high resolutian cpaque interval segments. Alterna-tively, high resolution interval defining mask stripes can be applied to the coatm g a~ any other stage of development. Such intervals, when used, provide the cpportunity for sharper relief (contrast) to colors.
FIGS. 3 and 3A prcvide expandRd ~llustration o~ the above described s~riping usin~ intervals between color stripes of an RGB set and between sets. Ihe glass screen 30 is of twenty-~ive to forty m~l thickness depcnling on total size of display for rigidity and coated with repeating sets, each comprising three stripes 46R (red), 46G ~green), 46B (blue), ~ep æated by intexvals 46I. The latt~r may be bar~ or bac~illed with an opaque ma~erial. The interval~ pres~rve el~ctrical saparation o~
stripes ~6R, ~6B, 26G ~3 well a~ ual di~tinctn~ o~ ~uch oolor ~tripe~ n3tcd ab~va, the ~tripe~ ar~ ~hln ~ilnL~ wlth mwltipla l~y~r~ ~he wldth ~pan o~ ~ch o~ stripe~ 26R, 26G, 26B
i5 abaut .005", p~ rrably a~g., .OOlll ~or use at p~ ~ t ~ndustrial goal l~vel~ in the ocnsumer TV field prac*ice (being .0l5"); but, ~or okher applications, e.g. H~TV, the width can be set as low as .OOOl"-.0002"). This is rela~able ~o selected spot sizes of the light filt~r section ~0 and desired display screen color resolution andVor desired pixæl size, as a ~hole, for the end use display, all as dlsI1~;scd further, below. Ihe stripe width is preferrably uniform, but may be non-uniform for scme applications. ~he interval stripes are from twenty to one hL~x~n3d fifty Feroent of adjacent color stripe widths (taking an av~rage where adjaoe nt stripes are of different widths). of ccurse, the ~ s~ripe can be made sm2ller or omitted (i.e~, unber ten peroent o~ adjacent active stripe width).
~ IG. 3A alsD shows th~ associated light source lO pr~du-.,. . :. . , , . :. . .
: ~ ~: . ,: : . . : , "
~ 2 ~ 3 ~ ~
cing a un1form, preferrably collimated light output Ll and electrically controlled filter section 20 (typically abou~ ten to forty ~ils, i.e., .010-.040 in. range) prc~ucing selectively Fx~3d large or small spots of li~ht I2. As note~ above, the reverse stra~egy can be us0d, i.e. selective blocXage. Large spots of light passage ~or blockage) are ccmposites o~ adjacent 3mall spcts of such passage ~or blockage).
Ag m~ntioned abov~, FIGS. 3A ~and FIGS. 3C-3D) also show a further emkodlment o~ the invention wherein light source and control are combined as shown at lO/20-EL using an electrolum1nsccnt material ~or other artifact, e.g., an array of semiconductive light emitting diodes or light emitting Fhw~phor~ he ~lectrode strips 22, 25 prcvide the cross~ng x-, y activi~ation matrix ~or ~lective li~ht emission.
Pra~r~bly, a ~ on oxidc lay~r ~nct ahown) o~ abou~
1,000 ~ngstrom~ o~ th~ckn~ d~po~ d ~v~x tha ~ant~l~m oxide strlp~s by ~putter~ng or chamlaul vapor deposltion, for pr~tection witlh minimal llght attenua~ion. Se~uential layers of Ta205 e~nd g10~ i.e" ~veral ~Ise~s~ each typically two or three ma~ b~ udded to enhanc~ or "peak" th~ tre~nsmission percentage e~nd provide brighter response. This is shown, as applied to stripes 26B, 26G in ~IG. 3D with tantalum repeats 42-l, 42-3, 43-3 and t ~ um oxide repeats 44-l, 44-2, 44-3.
~ IG. 4 is a fa oe illustraticn of stripes of adjacent color sets overlaying the high resolution filter defin3d e~s x-, y- array of activatable ligh~ passage (or blockage) spots. Ihe x- an~ y- electrales (22, 24 in PIG. 1 or æ, 25 in PIG. 3A) of light fitter 20 enable uniform cor~trolled ~ts 20L o~ selectable liS~ht passage or blockage. These can be of essentially cim~
~c~m of, sa3,r, .0001 inc~h d~er wit~h mini~ overlap, if any, o~ adjac~t ~pcrts. I~e stripea 26B/ 26G, 2~ o~ a ~e~ 26S can be ..: .. ... ... . . . . . .. .. .. . ... ..
.. . . . . . ~ . ; . . , -w o so/l60s7 PCT/US90~03335 ~ 0 ~
of .0002 inch width with i ~ stripes 26I, batween stripes of a set and between adjacent sets, o~ .0001 inch width, to produce a ~ ~ le set color span wid~h of .0009 mch. For purpcses of FI~. 4, the use of ~ s 20L aligned with cpaque intexval stripes 26I is assumed; these are, of oourse, superfluous ~nd can be omitted in high volume ~ tion designs (or at least electrical controls for such cross-over locations can be omitted or set at a de~ault llght blocking mode as shcwn in FIG. 4).
Ihe x-, y- electrodes can be controlled with a pixel st~ategy d uniform size pixels d width d one or more dots (crosscvers) or sets of doks and ;height o~ one or more dots or sets of dogs in integral ~r non-integral units. Each such pixel as arbltrarily de~ined ha~ a selectablllty o~ s ~ and intenslty cholce~, ~hr~ugh s~lectl~e passage or blo~kags o~ ligh~
in ~ele ~ l am ~ ~r ~ o~ s ao~iva ~ l) ~ rough colar Ihe usual t~rm 'p~l', as a Pund2men¢al uni~ o~ display resolution is an arbitrlry ccnitru~t a~ applied to the present inv~ntion (thcu3h correspondlng to a phy8ical 3pO~ in a raster ~can cath~de ra~ tube, llght emitting diode matxix, discharge tube matrix, inca~descent lamp ma~rix or like state-of-~he-art displays). ~ccrpting the ccnventional te~m pixel arbitrarily, as applied to FIG. 4 and defining a piXf~ width PW as cne set width and pixEl hQight EH as a height equal to that wiæ h, then a .0009" x .0009" pixel is establishsd (i.e., abcut one ~;1 x cne ~il). This may be compared with the so called high d0finltion television ~ d pixel, which - in mLst currently commer~ial or proposed-as-oommercial e=b~rimlr¢m has a pixel o~ eight to ten mils x ei~ht to ten mils wi ~ i~ht dimensions; NT~C ~U.S.) co~venti~nal television (in bome s8ks) of abcut thirty mil9 X
thirty mils; or pr~ecklQn ~elevislon systems o~ 9ixty to eighty W O 90/16057 2 ~ 3 ~ PCT/US90/03335 use fifteen mil x fifteen mil pixel standard and stabe of the art LLD oomputer monitors use a twenty-five mil x twen~y-five mil pixel. hven if thP~ FIG. 4 e=bcdlment is derated by a factor of five times (i.e., to a five mil by five mil 'pLxel'), it still exceeds state of the art resolution. Mor~over, the distinct pixæl limitation can be avoided in the present invention, with a computer controlled x-, y- electrode control affording intRrleaved pi~Els (or to put lt another way referring to the spoks 20L as th~ ~bnd~r*al ~ ts Or resolution).
Staying with th~ exampl~ of a FIG. 4 as deEined above and assuming each sF3t 20L to be normally light tDac=p rent when not activated and ~paque (as shown by shading-in in the ~igure) when activa~ed by a voltage appli~d ~rom it3 c~nssing x-, y-electrcde~ (the blocking strategy), then it is se~n hcw colox is constructed r~or the 'pixel' o~ PW/P~ width ~nd h~igh~ (.0009" x .0009", or nlna ~ x nir~ ~ts, 20~ as p~v~o~ql~ d~:~in~l).
}latctlir~ ac~a~ n ~G. 4 ~a~ ~ntroll0d bloedcir)g:
~ o~ all ~t3 aligned witlh the ver~ical interval stripes, as a ~le~t to, or in lie~ of, cpaque materials of ~he stripes per se, f~r ~xntrastJ
-- some of the red vertical stripe's s~s;
-- none of the green vertical stripe's spots; and -- all Oæ ~he blue vertical stripe's spots.
~he net effect is a predominantly green pixel of maximum intensity with a contributed red compcn~nt Oæ abcut forty percent n2uc~mlm intensity which a human viewer ~or machina imaging viewer o~ human resolution and percæptian capacity, mor~ or lQss) W O 90/16057 2 0 ~ 9 1 ~ ~ PC~/US90/03335 -16~
detects only as a compo~ite color. This together with dozens, or hundrEds of adjacent oontrolled pixels prcvides the viewer color impression. It will be appreciated that apart from intensity control, there is a high redundancy of color selection signals impo6ed on a single 'pixel' to assure reliable response even in the ~vent of partial control system failure.
FIGS. 5 ~ 6 show c~hex variant~ o~ pixel control (in ~ace view a~ in PIG. 4, but with d~ts indicated as rectangles).
Both e=bod1ments have a one spot plxel. In FIG. 6 interval striping 46I is shcwn. In FIG. 5 thR array of y- electrodes (ur~nooat oomponent 25 of stripes ~6 in FIGS. 3A - 3D) and~or X-electrodes (2 V FIGS. 1 - 3D) may have to be thinned dcwn to avoid sh~rting o~ ad~acent such electrodes, e.g., a .0035~ condNctive elect~ode wld~h in relat~on to a .005" color s~ripe.
Xn F~GS~ 5 and 6 red, grE~n and blu~ altQrnat~ in 1~
relation ~n the s~xipc~ ~R, ~G, ~6~. ~ut it will b~ understood that other ratlos can be prov~ded. For example, human observation favors repeating multiples of ~:2:6 of blu2:green"red, respec*lvely, ~or optimum control. Ihis kind of balanced xatlo can also be used to compensat~ for variances in phosphor tor LCD) or lamp s ~ range or guality in the light passage/blocka~e/origination sec*icns of the display system.
FIG. 7 shcws a ~ such e=tx~L~nent with a -horizontal stripe width 22 equal to the a ~ te of five vertical electrode stripes 25 and associated intervals 25I (all buried m a single oolor stripe layer 46B/blue). Astivation of a cross-over pair (one x- electrode, cne y el ~ e~ wfill light up (or block light) in ten doks, if the ccnductive strips 25 are ganged or ~ . Alternatively separate electrode connections can be m3de to 25-l, 25-2, etc. for mcra precis~ ccn~rol.
.. , w o go/16057 2 0 ~ ~1 3 ~ pcT/usgo/o333s -17- :
F~GS. 8 and 8B show usage of the oolor control section withcut strip m g or other areal configuration, used 6imply as a f;lter in transmission t8A) and re~lective ~8B) ~odes.
FIG. 9 shows (in transverse section, as in FIG. 2) a display s~stem whÆre ths y- elec~rodes 25 ~e~, s.g., FIG. 3A) are prov.id~ wi~h ku~s-~ars, e.g. B(Y), at interval~ to establish low resistance path lengths to all regions o~ the y- electrodes and in turn ~o each dok d~ined by a cr~s~ ove~ of such a y-electrode wi~h an x- electrode 22. Similar ~Lr~tegy can be p m vided for electrodes 22. qhe r ~ tan~ equivalent circuit is shown in FIG. 10 ~ e sec~ions o~ anodic oxide coat m 3s 44 together with crossing-ovcr x-, y- el ~ e portion~ 22, ~5 act ~ an a~ray o~ capacltor~. m e lnsulativ~ value o~ tha anodic oxide i~ ~upplemantRd by that o~ the pho5phor clectx~luminescan~ !
layer.
min indium/tin oxida lay~r~ c~n ba u ed ~or t ~ ~ ne~ ~ut u~ing tha kLss bar~ to l~mit voltage drcps along electrode length~.
Tha ~ontrol o~ spct ~lection and pre5entation o~ a screen display can (advantagecusly) be simLlkanecusly lmplemented over a whole screen (or large section of a screen) - in contrast to a raster scan or like roll m g implementation` of display control. 2ut roll m g implementation can be adm~JI~b~o~d in the present case ~or some aesthetic reasons and/or to utilize While color e~ltL~l in terms of primary colors of additive synthesis have been descr~bed, other repeating color stripes of additlve or Eub~tr~ctive s,y~thesis systems can be applied. ~h~ available rang~ o~ colors can be ccrstantl~ varied ~rcm sec*l~n to ~ecti~n o~ a di~pla~.
W O ~0/16057 PCT/US90/~335 2~59:L3.~ ~
Cuntr~l ~ystems utilizlng the above display formats can comprise use of one or more o~ the following exemplars, extrapolations therefrom or equivalents or extensions now apparent to those skilled in the relevant display art, given benefit of availabil~ty of the present invention and its disclosure herein.
qha d1splay sys~em can be made in selecked small or laLge sizes with uni~rmity o~ performance unlimited by edge or corner e~fects o~ the types associated with CRr displays or the like. Resistance over lengths of x-, y- control electrodes can be a limitation at very long lengths (e.g., several hundrsd light spots l~ng~h); but thi~ can ba circumv~nted b~ modular con~truotion o~ th~ ~ilter portion and/or usa o~ (p m ~x~ably tzansp~rcnt) buss bar~ ov~rlapping tha ~ilt~r el~ctrodo Wi~9 to carry high~r vol~a~ ncdo~ to tha ~nt~ior o~ t~h~ r ax~a.
Th~ gla~s 30 (or a precu~sor tx~n~r ~uustrata) can ba o~
lndo~ini~a length ~n manu~aabure or m~de in conveni~nt bakch ~izes and cut to end-user sizes c~g needed. lhe basic filter construction i~ ~imilarly ~laxi~ble as to economical stock ~anu~acture c~nd custom selection o~ usable si~es.
Several variations have been discussed abcve relative to a oore e~bKdirent. Several further vzriations can be made ~ sistent with the scope an~ spirit of one or re aspects of the present invention. For example, color control matexials other thc~n tan~alum ~ ide can be used - e.g., oxides of other valve metals af~ording an adherent film.
Ihe indium/tin oxide stripes, or equivale~ts, are usable for the~r optical prcperties and for thair electrical prcFerties (carrying current to provide a mcnolithic anode electr3de or distinct ancdes in th~ anodic ~xidati~n step) and n~chanical ....... .. . . . . . . . . .
: ; ~.; ., ... , . :
;, ,, .. .
.
:: ~
wo 90/16057 2 V ~ 5 PCM~S9OJo3335 ~ies as a glass to tar~tal~n substrate }:)ridge, all as slla~
a~ove. But further, in eTxl use, i~i~tin ~ide stripes can be us~ as electrodes to ccxntrol re~se (and,/or on-off re~onse) of averlying coating layers.
Ihe basic color stripes ~and inten~al stripes, w~en used) are sha ~ above as arrays o~ long st~ in a single direction. Bu~ Gros~ etching, a~er a need for eleY~brical ccntinuity ha~ passed and using appropriate masking or selective etching ~an pro*uce lands (isolat0d mesas or islands) of color responsive oxid~ spoks.
Ihe light souroe spectral range ~nd intensity and4or glass ~oreen trau~xlrIocy characteri~tics are further distinct variables co~r~llable in design selection or utilizAtion to ~urth~r impact ~ d~spl~y.
While x-, y~ orthcgon~l coondln~ hcwn ab~ or ~ilter al~ctrode arrangements, one could use various non-orthogonal coordinata sy~tems, e.g., polar coordinate6. A
varia~y o~ llnsar or non-linear ~ n~s ~e.g., lo~arithmic) ~an ba impc~ed in each coordinate se~.
Ih0 areas of applica~i~n o~ the i ~ ion include - ~ut a ~ not limited to - consumer and industrial video, computer mcnitors, ins~rumentlti~n display6, military displays, sports arens scoreboards and cther variable public billkoards. lhe Invention is also utilizable as a ~ontrolled light source independent of d;splay purpcses in sizes ranging from very small t~ v~ry large, taking advan~age o~ one or m~re o~ the flexibility of~ control control, resolution, economy o~ nEunufacture andVor ckher aspects of the present invention.
Ih~ inv ~ on al~o ocmprises mean~ ~or enhan~ing the ' .
, .
.' . . ~ ! ~; ' ' ' ' W O 90/16057 ~ ~ ~ 9 1 3 PCTtVS90/03335 ocnductivity of the indiumrtin-oxide underlayer or overlayer material (where used) and resultant enhanced indiumrtin-oxide prcduct (a coating) and enhanced coated pro*uct. Ihis aspect of the invention can be applied to materials for electrical conductivity compatibly with high light transmission.
h this last-mentioned aspect of the invention, ~heet reslstivity on tha order of belcw 2.0 (in s~me instances, below 1. O) Ohms~p~r~guare i5 achi~vable ~cmpared to five to ~ifty ohms-per-square in the state of the art. Ihe impact of thLs is to enable longer linear runs andVor reduc~d thickness of conductive strLpes of indium-tin-oxLde (or the like).
The realization of reduced electrical re~istivity/higher alectrlcal c~nductivity is achieved with only a modest lo~s o~ optical tran~mis~ivity typically less than twQnty p~rcent at m~st ~p~ctral rang~ o~ int~xe~t in ~lect~ow cptic d~splay or ~iltQr application, ~uch a~ tho~n ~l~ed abcve.
Realizaticn o~ SU~l improvement is preferrably made thxcugh th~ follcwing prcces~ ~t~ps:
~ 1.1) Establish a base layer free of external i~ns li.e. alkali ions as applied to a glass substrate), preferrable by beginning with a glass such as sode lime or Corning 7059.
ClPar the substrate with detergent an~Vor solvents and dry it at 150 in air or inert gas for about half an hour to remsve isture and follow up by sFutter~etDh or like radiant energy ~ to removs residual ccnt~=inonts. qhe sputter etching ~c at Gre-h~lf to one ~ owatt und2r abcut 8 millitorr vacuum and after prior evacuation and argon backfill.
(1.2) Cover its sur~ace to b~ o~ated with a (sFL~IY~cposited or chemical-vapor-depositiQn deposi~ oon W O 90/16057 2 ~ 5 9 ~3 3 ~ PCT/US90/03335 dioxide layer of about 2,000 Pnqstrc=s thickness to mask the aIkali ions or okher ex*ernal species from interacting with =ubsequent coating and provide sukstrate for further coating. A
pre-processed silicon glass substrate free of such surface species LS another approach to the same end.
(1.3) Then the so-coated glass is heated at 350-450 C ~or abcNt ~i~te~n minutes under 5 x 10-7 mm ~g. pre~sure.
~ 2) A layer o~ 7000-10,000 2r~stloms of indium~tin-oxide is sputter deposited an the so-treated substrate.
(2.1) Ihe ~irst 100 to 200 ~ngstroms o~ such deposition ~eqyivalQnt to the ~irs~ ~w monola~ers the~eo~) is ocrduoted undRr bia5 ~ ring cQndit~ns to maxlmiæe pur.i~y and density. ~ha 0pUt~sr~n~ o~ th~ indiumrkln-oxide i~ ccnduated ~n atmc~Fhe~s init~ally ~vacua~cd to 5~10-7 mm. ~g., then back-L~ w~ a~o~3 w~ nl p~ ~n 4 to 5x10~5 mm ~g ~ 2.2~ Withcuk ~emcval from the sputter system, the ~putt~ring d~scha~ge is ~hen termin~ted and a vacuum bake of 400-500 C ~or abcut 15 ~ s at 4 to 5x10-7 mm. Hg. is applied to create oxygen vacancies.
., .
FIG. ll shows the develcFment of enhanced (reduoed) shRet resistivity of tWD sa~ples of (l.l) soda lime and (1.2) Corning 7059 coated with indio=-tln--xldb as described above.
l~e y-axis (l~thmic) i cit~ are arxl ~e x~
(lir~3ar) ~s time in minut~ of the final bakir~ step of (2.2) to . :~:
create a~en vacancies. Ihe ~heet resistivit~ of the san~les :
begins at s~ cllms per s~are and d~ dramatically to well with no ~urth~r change aft~r abo~t an haur and a bal~.
: :..... . . . ............................... : , , , .. . . . . .. . . . .. . . . . .. . . ..
W o 90/16057 ~ ~ ~ 9 1 3 ~ PCT/US90/03335 Bulk resistivity o~ the coating is also reduced to about 0.5x10-4 chm-cm, a ~=bstantial impruvement over commonly available indiumrtin-oxide ma~erials.
lhe processing as described above can be implemented over a broad area or through masking to provide mLltiple stripes o~ conductive coating (alternat.tvely interval stripes can be ~tched or mach~n0d cut o~ a broad area oo~ting).
Some o~ t~le processing steps dPcrribed abcve can be supple ~ or supplanted by laser or electron beam etching, micrc~achining, ion deposition, electroplating, electrcphoresis and okher processes.
m e enhanced matallic co~ting can be und~r 20,000 Ang~kroms but i~ pro~rab~y w~ll undar 10,000. ~here a ~Ub9~rat0 d1~P1AY~ a.g. ~ Qpkl~al ~ransmi~8icn ~n v~ble ~a~g~
the metallic oo~0~ gl~s~ ~lth low ~heet resi~tiviky o~ the aoating) will di~play over 80-~, pre~errably 85~ or more ~ransmis8ivlty in the 8am~ 9pec~r21 range, i.e. re~uction of less than 20~, pre~errably less than 10~ via ~he coat~ng. In contrast withcut th~ special enhJnce3ent a 10,000 Arystrom cc~ventional coating of indium-tin-oxide on such glass would typically re*uce to about 60% ~ ssion and w~uld have higher electrical sheet resistivity.
.
qhe above de~czibed enb=nccmc~t pr w 2ssing mcdifies semicund~ctive charar~Qristics of the indium-t m-uxide coating or the like thrcugh axygen vacancy creation (or equivalent neans) to yield the lo~ered resistivity with a higher degree of F4~ rVation o~ ç ical tra0smiYsivity Filter applica~lons d th~ ~nvantion - in re~lectiv~
;-'' : ' ' : .. '' -.: , . ..
; . ~ i; : . . . ' : : : , . . : - , .; :
, , , :~
. . ~ - .... , .. .. . . . . ... : .. .
. . : . ... . ~
W o 90/16057 2 ~ 5 ~ ~ 3 ~ PCT/US90/03335 , . ....
and trans=ds~ive mcdes - are characterizel by abrasian, thermal and environment rasistance, including super-saturated salt solutions and/or -55 C to +550 C range consistent with 90%
transmission/reflection, ease and low cost of tailoring to pæticular applications.
It will now be app~rent to those skilled in the art ~hat oth~r embodlmRnt3, i~prcvements, details, and uses can be madR consistent wlth the letter and spirit o~ the foregoing disclosure and within the sccpe o~ this patent, which is limited anly by the follcwing d aims, ccçscruei in aocordance with the patent law, including the doctrine of eguiv21ents.
Wh~t i~ claimed i~:
:
: ~, : ;: . :. : .:. .................... ; . , . :
.: :. . :.~ . :,, , , ::.
Claims (46)
1. Display system comprising, in combination:
(a) light source means comprising a first slab like element comprising elongated parallel conductors therein to define a set of first electrodes and comprising a material with light control properties varied by external control, (b) color filter means in the form of a second slab-like element in close spacing and face-to-face opposition to said first element and comprising a series of transparent, color sensitive stripes of elongated conductors with a dielectric top layer to define second electrodes in a cross-hatch array with said first electrodes, the said dielectric layer being thereby sandwiched between said first and second electrode elements in a precisely (c) control means for activating selected ones of said first and second electrodes to effect light response at selected cross-overs thereof and light transmission essentially through the second electrodes.
(a) light source means comprising a first slab like element comprising elongated parallel conductors therein to define a set of first electrodes and comprising a material with light control properties varied by external control, (b) color filter means in the form of a second slab-like element in close spacing and face-to-face opposition to said first element and comprising a series of transparent, color sensitive stripes of elongated conductors with a dielectric top layer to define second electrodes in a cross-hatch array with said first electrodes, the said dielectric layer being thereby sandwiched between said first and second electrode elements in a precisely (c) control means for activating selected ones of said first and second electrodes to effect light response at selected cross-overs thereof and light transmission essentially through the second electrodes.
2. Display system in accordance with claim 1 wherein the second electrodes comprise a transparent elongated conductor, overlaid with a valve metal which is in turn overlaid with an anodic oxide of the valve metal highly adherent to the latter and anodically formed to a selected color control thickness.
3. Display system in accordance with claim 2 wherein the valve metal comprises tantalum and the transparent conductor comprises indium/tin oxide.
4. Display system in accordance with claim 1 wherein the color sensitive stripes include repeating sets of stripes with different members of a set sensitive to different colors.
5. Display system in accordance with claim 1 wherein the color sensitive, second electrode stripes are made in less than .001 inch widths with intervals therebetween of less than .001 inch and utilizable with first electrode width of the same order of magnitude to define high resolution color dots of high intensity.
6. Display system comprising in combination:
(a) light source means, and (b) color filter means for interacting with light from the source to emit, as a display output, a limited spectral range of the source light at a high intensity, in excess of eighty percent of the source intensity of such spectral component, and comprising a valve metal oxide on a substrate of the valve metal per se.
(a) light source means, and (b) color filter means for interacting with light from the source to emit, as a display output, a limited spectral range of the source light at a high intensity, in excess of eighty percent of the source intensity of such spectral component, and comprising a valve metal oxide on a substrate of the valve metal per se.
7. Display system in accordance with claim 6 wherein said valve metal oxide comprises tantalum pentoxide.
8. Display system in accordance with claim 6 wherein said color filter means comprises multiple areas of such valve metal oxide of differing thicknesses to effect differing spectral range responses, all at high intensity.
9. Display system in accordance with claim 8 wherein repeating like sets of such multiple areas are provided in array form to form a display array.
10. Display system in accordance with claim 9 wherein each set comprises side-by-side stripes of differing thickness of and the sets are in a planar array of side by side stripes.
11. Display system in accordance with claim 8 wherein interval areas are provided between areas of valve metal oxide.
12. Display system in accordance with claim 11 wherein the interval areas are opaque.
13. Display system in accordance with claim 6 wherein the color filter means interact with the light from the source by
14. Display system in accordance with claim 6 wherein the color filter means interact with the light from the source by selective spectral range reflection thereof.
15. Display system in accordance with claim 6 wherein said light source means and color filter means are interrelated as follows:
(a) said light source being of an essentially slab form and comprising electrically responsive material and a series of spaced conductors therein to act as first electrodes and means for selectively activating said first electrode, (b) said light filter being also of essentially slab form and having therein an array of second electrodes therein and means for selectively activating said second electrodes, (c) the slabs being in face-to-face opposition and essentially adjacent to each other, (d) whereby selective activation of certain members of the first and second electrodes activates areas of the electrically responsive material at cross-over regions of the activated electrodes to effect selected areas of light control, positively or negatively (by light transmission/origination or light blockage/non-origination), (e) the closest opposing active electrodes from the first and second sets being separated electrically by the said valve metal oxide and having a dielectric constant therein in excess of fifteen.
(a) said light source being of an essentially slab form and comprising electrically responsive material and a series of spaced conductors therein to act as first electrodes and means for selectively activating said first electrode, (b) said light filter being also of essentially slab form and having therein an array of second electrodes therein and means for selectively activating said second electrodes, (c) the slabs being in face-to-face opposition and essentially adjacent to each other, (d) whereby selective activation of certain members of the first and second electrodes activates areas of the electrically responsive material at cross-over regions of the activated electrodes to effect selected areas of light control, positively or negatively (by light transmission/origination or light blockage/non-origination), (e) the closest opposing active electrodes from the first and second sets being separated electrically by the said valve metal oxide and having a dielectric constant therein in excess of fifteen.
16. Display system in accordance with claim 15 wherein said color filter comprises a planar array of valve metal oxide coating areas on metal bases, with sufficient conductivity to serve as one of said second electrodes to interact with a corresponding first electrode of the light source.
17. Display system in accordance with claim 1 wherein said valve metal oxide stripes comprise a combination of (i) an underlying valve metal thin enough to be transparent to the spectral range of light for which the oxide thickness is graded and (ii) an optically transparent underlayer providing sufficient electrical conductivity to serve as the electrode.
18. Display system in accordance with claim 15 wherein said conductive areas of the second electrodes are elongated.
19. Display system in accordance with claim 15 wherein the light source comprises a light pasage/blockage matrix.
20. Display system in accordance with claim 15 wherein the light source comprises a light originating matrix.
21. Display system in accordance with claim 15 wherein the two first and second electrode spacing at cross-overs is in the .001 to 0.1 inch range thereby avoiding parallax and interference effects.
22. High resolution, multi-color, thin film display system with uniform, high intensity comprising:
(a) means forming an essentially two dimensional film array of alternating assigned-color segments of high resolution, i.e., less than 0.05 inches wide, sensitive to incident light to transmit the assigned color(s) portion(s) of incident light at high intensity, with high transient speeds of activation and deactivation, and (b) means for effecting high speed light activation and deactivation of selected segments and groups and portions thereof in the said array, the materials of the system having high chemical inertness and thermal stability under all conditions of manufacture and use and the structure of the system affording a compact display essentially free of parallax and providing an essentially isotropic light output.
(a) means forming an essentially two dimensional film array of alternating assigned-color segments of high resolution, i.e., less than 0.05 inches wide, sensitive to incident light to transmit the assigned color(s) portion(s) of incident light at high intensity, with high transient speeds of activation and deactivation, and (b) means for effecting high speed light activation and deactivation of selected segments and groups and portions thereof in the said array, the materials of the system having high chemical inertness and thermal stability under all conditions of manufacture and use and the structure of the system affording a compact display essentially free of parallax and providing an essentially isotropic light output.
23. Display system in accordance with claim 21 wherein said activation/deactivation means comprise an electrically operated matrix filter of back light.
24. Display system in accordance with claim 21 wherein said activation/deactivation means comprise an electrically operated electroluminescent matrix comprising a photovoltaic layer sandwiched between orthogonally arrayed thin electrode strips.
25. Display system in accordance with claim 21 and further comprising an integral to the film array forward protective cover which is transparent.
26. Display system in accordance with claim 24 wherein said cover comprises a glass substrate supporting said film array as a thin film coating therein.
27. Display system in accordance with claim 21 wherein said film array is a graded layer of a combination of (a) an optically-functional thickness anodic oxide of a valve metal and (b) the valve metal per se.
28. Display system in accordance with claim 21 wherein the high resolution segment patterns of components (a) and (b) are of the same order of magnitude and in respective array registration with each other.
29. Laminate structure for use in color display system comprising, in parallel layers, the following:
(a) means defining a graded thin film, and (b) means defining and opposing generator of high resolution spots of light control of under .001 in. span resolution.
(a) means defining a graded thin film, and (b) means defining and opposing generator of high resolution spots of light control of under .001 in. span resolution.
30. The laminate structure of claim 28 wherein said graded thin film means (a) comprises a repeating array of sets of graded thin film segments in each set with differential responses to incident spots of light applied thereto by said light generator means (b).
31. The laminate structure of claim 28 wherein said graded thin film segments comprise valve metal oxide layers of graded thickness responsive to differential wavelengths of incident light in the visible spectral range.
32. The laminate structure of claim 28 wherein said valve metal oxide is tantalum pentoxide.
33. The laminate structure of claim 28 wherein said generator means is a matrix filter of light.
34. The laminate structure of claim 28 wherein said generator means is a matrix source of light.
35. The laminate structure of claim 28 wherein said film is mounted on a transparent substrate.
36. Method of making color display systems comprising the step of depositing a valve metal thin film and oxidizing adjacent segments thereof to graded oxide thicknesses for differential spectral response to light, whereby multiple spectral response capability is formed in essentially a single plane to enable simplicity of manufacture, intensity of light passage and flexibility of control.
37. Method in accordance with claim 35 wherein the valve metal is tantalum.
38. Method in accordance with claim 36 wherein the valve metal is deposited in a transparent thickness over a transparent and thicker thin film layer of a conductive material to provide an internal electrode system enabling anodic oxidation of the valve metal.
39. Method in accordance with claim 36 wherein the metals are deposited on a protective transparent substrate.
40. Method in accordance with claim 35 and further comprising the step of overlaying graded oxide segments with a high resolution flat pack matrix generator producing selected spots of light control.
41. Method of enhancing (lowering) sheet electrical resistivity of an optically transmissive metallic material comprising the creation of a modified semiconductor characteristic thereof, where the material is a coating of under 20,000 Angstroms thickness on a substrate and has an intrinsic optical transmissivity which is reduced by less than 20% by creation of the semiconductor characteristic.
42. The method of claim 40 wherein the transmissivity reduction is less than 10% and the coating thickness is less than 10,000 Angstroms.
43. The method of claim 40 wherein the coating material is indium-tin-oxide.
44. The method of claim 40 wherein the semiconductor characteristic is induced by creating oxygen vacancies.
45. A coated product is made by any of claims 41, 42 or 43.
46. A coated product as set forth in claim 44 ith a visible light transmission of over 85% with essentially complete ultra violet light blocking throughout a substantial portion of
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US36819789A | 1989-06-17 | 1989-06-17 | |
| US368,197 | 1989-06-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2059135A1 true CA2059135A1 (en) | 1990-12-20 |
Family
ID=23450257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2059135 Abandoned CA2059135A1 (en) | 1989-06-17 | 1990-06-13 | Color display system using thin film color control |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0478621A4 (en) |
| JP (1) | JPH05504002A (en) |
| CA (1) | CA2059135A1 (en) |
| WO (1) | WO1990016057A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7935404B2 (en) * | 2005-01-31 | 2011-05-03 | Hewlett-Packard Development Company, L.P. | System and method for marking an optical disk |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57161882A (en) * | 1981-03-31 | 1982-10-05 | Hitachi Ltd | Display body panel |
| JPS5910988A (en) * | 1982-07-12 | 1984-01-20 | ホシデン株式会社 | Color liquid crystal display |
| EP0112695B1 (en) * | 1982-12-22 | 1987-08-12 | Seiko Instruments Inc. | Method for making a multicoloured member |
| CA1237836A (en) * | 1984-05-25 | 1988-06-07 | Keiichi Tokuyama | Multi-color liquid crystal display system |
| JPS62178906A (en) * | 1986-02-03 | 1987-08-06 | Hitachi Ltd | Multi-layered oxide-metal film and its production |
| JPS63146019A (en) * | 1986-12-10 | 1988-06-18 | Alps Electric Co Ltd | Color liquid crystal display element |
| JPS63148201A (en) * | 1986-12-11 | 1988-06-21 | Fujitsu Ltd | Production of reflection type color filter |
| JPH0827460B2 (en) * | 1987-01-29 | 1996-03-21 | キヤノン株式会社 | Optical modulator |
| JPS63210802A (en) * | 1987-02-26 | 1988-09-01 | Fujitsu Ltd | Transmission type color filter and production thereof |
| JPH0786615B2 (en) * | 1987-10-06 | 1995-09-20 | 日本電気株式会社 | Liquid crystal light valve |
-
1990
- 1990-06-13 JP JP50888290A patent/JPH05504002A/en active Pending
- 1990-06-13 CA CA 2059135 patent/CA2059135A1/en not_active Abandoned
- 1990-06-13 WO PCT/US1990/003335 patent/WO1990016057A1/en not_active Application Discontinuation
- 1990-06-13 EP EP19900909267 patent/EP0478621A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0478621A1 (en) | 1992-04-08 |
| EP0478621A4 (en) | 1993-02-03 |
| WO1990016057A1 (en) | 1990-12-27 |
| JPH05504002A (en) | 1993-06-24 |
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