CN1932930B - Plasma display device - Google Patents
Plasma display device Download PDFInfo
- Publication number
- CN1932930B CN1932930B CN 200610141650 CN200610141650A CN1932930B CN 1932930 B CN1932930 B CN 1932930B CN 200610141650 CN200610141650 CN 200610141650 CN 200610141650 A CN200610141650 A CN 200610141650A CN 1932930 B CN1932930 B CN 1932930B
- Authority
- CN
- China
- Prior art keywords
- fluorophor
- plasma display
- phosphor
- phosphor layer
- display device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 63
- 229910052727 yttrium Inorganic materials 0.000 claims description 62
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 26
- 229910052693 Europium Inorganic materials 0.000 claims description 18
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 229910052712 strontium Inorganic materials 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 3
- 230000005284 excitation Effects 0.000 abstract description 14
- 239000011572 manganese Substances 0.000 description 36
- 239000011701 zinc Substances 0.000 description 36
- 239000002245 particle Substances 0.000 description 33
- 238000000576 coating method Methods 0.000 description 30
- 238000001259 photo etching Methods 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 27
- 230000004913 activation Effects 0.000 description 17
- 239000000523 sample Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000004615 ingredient Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 230000004075 alteration Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000002688 persistence Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- DXNVUKXMTZHOTP-UHFFFAOYSA-N dialuminum;dimagnesium;barium(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mg+2].[Mg+2].[Al+3].[Al+3].[Ba+2].[Ba+2] DXNVUKXMTZHOTP-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- -1 monox Chemical compound 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 229910017639 MgSi Inorganic materials 0.000 description 5
- 229910052771 Terbium Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 5
- 229910007270 Si2O6 Inorganic materials 0.000 description 4
- 239000013068 control sample Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052909 inorganic silicate Inorganic materials 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 238000003359 percent control normalization Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- WPSIWVSIIUUTJS-UHFFFAOYSA-H gadolinium(3+) yttrium(3+) hexachloride Chemical compound [Gd+3].[Cl-].[Y+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] WPSIWVSIIUUTJS-UHFFFAOYSA-H 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical class [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002178 europium compounds Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Images
Landscapes
- Luminescent Compositions (AREA)
- Gas-Filled Discharge Tubes (AREA)
Abstract
一种动画图像质量优良、长寿命且高性能的等离子体显示装置、发光装置和影像显示系统。该等离子体显示装置备有：至少包括基板，在前述一对基板间所形成的、放电气体空间，在前述一对基板的对峙面上所形成的电极，以及在前述一对基板的接触于前述放电空间的面上所形成的荧光体层的等离子体显示板；和经由前述电极来驱动该板的驱动电路，其中从构成荧光体层的提供发红、绿、蓝色光的各荧光体层发生的光的余辉时间(1/10余辉时间)为8ms以下。上述装置使用在真空紫外区紫外线和低速电子射线激励下具有高性能的蓝色荧光体，其组成式为(Ae)a-c(Ae’)bSixOy:Euc。
A plasma display device, light emitting device and image display system with excellent animation image quality, long life and high performance. The plasma display device is provided with at least substrates, a discharge gas space formed between the aforementioned pair of substrates, electrodes formed on opposing surfaces of the aforementioned pair of substrates, and contacts between the aforementioned pair of substrates and the aforementioned A plasma display panel with a phosphor layer formed on the surface of the discharge space; and a drive circuit for driving the panel via the aforementioned electrodes, wherein the phosphor layers that provide red, green, and blue light that constitute the phosphor layer generate The afterglow time of the light (1/10 afterglow time) is 8ms or less. The above-mentioned device uses a blue phosphor with high performance under the excitation of ultraviolet rays in the vacuum ultraviolet region and low-speed electron rays, and its composition formula is (Ae) ac (Ae') b Six O y :Eu c .
Description
The application be Hitachi Co., Ltd on October 29th, 2002 apply for, application number is 02147086.3, denomination of invention is divided an application for the application for a patent for invention of " plasm display device, light-emitting device and image display system ".
Technical field
The present invention relates to be used for the plasm display device that broadcasting receiver or image show, by the light-emitting device of rare gas resonance ultraviolet ray or the excitation of low-velocity electron ray with use the image display system of this display device, light-emitting device.
Background technology
In recent years, as being used for broadcasting receiver, computing machine, use the plasm display device of plasma display panel (being called PDP to place an order) to produce in batches with the flat display that terminal or image (image) show.
Plasm display device, with the short wavelength ultraviolet that takes place in the negative glow region in the fine discharge space of containing rare gas in its PDP (with the occasion of xenon as rare gas, its resonance line is in 147nm or 172nm) be driving source, make the light-emitting phosphor that is disposed at discharge space, carry out colour and show.
The structure of this gas discharge unit, on the books in for example " color PDP technology and material " (Japan (strain) CMC distribution), typical structure is shown in Fig. 9.Fig. 9 is the decomposition diagram of the formation of the general surface discharge type color plasma display device (PDP) of expression.PDP shown in Fig. 9 pastes the front substrate of being made by glass substrate 10 and back substrate 20 and integrated, is the reflection-type PDP that forms red (R), green (G), blue (B) each luminescent coating 24,25,26 overleaf on the substrate 20.
In addition, these electrodes 11 to 14 cover by dielectric (for example lead glass) layer 15 that AC drives usefulness, and this dielectric layer 15 is provided with the diaphragm of being made by magnesium oxide (MgO) 16.
Magnesium oxide (MgO) is because of anti-sputter, secondary electron yield height, so protection dielectric layer 15, the landing low discharge begins the effect of voltage.
On substrate 20 overleaf and surfaces front substrate 10 relative sides, by with the electrode group of forming by address electrode 21 of 11,12 groups of quadratures of show electrode of front substrate 10, this address electrode 21 is covered by dielectric layer 22.On this dielectric layer 22, the next door (fin) 23 that isolates 21 of address electrodes is set for the dispersion (zone of restriction discharge) that prevents to discharge.Next door 23 is made of low-melting glass, make at interval, highly, all identical shape such as sidewall shape.
Form with the groove face that covers 23 in this next door is being coated with each luminescent coating 24,25,26 that sends red, green, blue successively strip.The formation of these each luminescent coatings 24,25,26, on substrate 20 at first overleaf on the thing in calculated address electrode 21, dielectric layer 22 and next door 23,, remove volatile ingredient and form the phosphor particle that forms each luminescent coating 24,25,26 with after carrying the phosphor paste that photo etching is mixed and made into methods such as serigraphy coatings by firing.
In the discharge space between substrate 10 and the back substrate 20,, enclose discharge gas (for example mixed gas of helium, neon, xenon etc.) in front though do not draw among Fig. 9.
In this PDP, according to one in the show electrode 11,12, for example, show electrode 12 and address electrode 21 are selected discharge cell (unit luminous zone or point of discharge), repeat to carry out gas discharge in the discharge of keeping according to 11,12 of show electrodes in selected discharge cell.
By the vacuum ultraviolet that produces by gas discharge, this regional luminescent coating is energized and obtains visible light, and, obtain colored the demonstration by having with the combination of the luminous quantity of the unit luminous zone of each luminescent coating 24,25,26 of the corresponding red, green, blue of three primary colors.
Color PDP is sought performance every year and is improved, and is substituting direct viewing type cathode-ray tube (CRT) colour television set.For PDP is really popularized as family expenses large-scale tv machine as TV-set broadcasting receiver, must further improve animated image quality and life-span.
Summary of the invention
The object of the present invention is to provide red, the green luminophore layer of a kind of PDP of the high performance that can realize animated image quality and life-span.
Aforementioned and other purposes of the present invention and new feature can be understood by the record and the accompanying drawing of this instructions.
The animated image quality of plasm display device, its quality are subjected to from about after time of the visible light of the fluorophor that sends each coloured light of red, green, blue institute.Drive cycle at display is the occasion of 60Hz, if surpass 16.6ms after time, then because the luminous next cycle of spinning out disturbs so produce in display image.Therefore, be necessary to shorten as far as possible the after time (1/10 after time) of fluorophor.But, if can then can show animated image quite in high quality about shortening to below the 8ms this after time in the practicality.And then, if can then can really show animated image in high quality about shortening to after time below the 6ms.Therefore, manufacture experimently various red fluorophor and green luminophore, estimated the after time of the light-emitting phosphor in PDP.But, at present in PDP employed blue fluorophor because after time extremely lack (below the 1ms), so there is no need carry out short persistenceization especially.
As a result, find in green luminophore, by Zn
2SiO
4: the Mn fluorophor constitutes, and its Mn/Zn ratio of components is best more than 0.05.In addition, find Zn
2SiO
4: the Mn fluorophor with from (Y, Gd, Sc)
2SiO
5: Tb, (Y, Gd)
3(Al, Ga)
5O
12: Tb, (Y, Gd)
3(Al, Ga)
5O
12: Ce, (Y, Gd) B
3O
6: the composition that more than one fluorophor of selecting in the cohort of Tb mix mutually also is good.
In addition, find in red fluorophor (Y, Gd) BO
3: Eu and Y
2O
3: Eu, (Y, Gd) (P, V) O
4: the composition that any above fluorophor among the Eu mixes mutually is best.
In addition, though the present inventor waited and had developed band divalent europium active alkali great soil group silicate phosphor (Japanese kokai publication sho 64-6087 as electron ray with blue emitting phophor in the past, Te Kaiping 01-167394), still use the evaluation of vacuum ultraviolet ultraviolet ray and low-velocity electron ray.Specifically, discovery under vacuum ultraviolet ultraviolet ray and the excitation of low-velocity electron ray has the composition of good tone and high-luminous-efficiency and reaches the present invention about this fluorophor.Fluorophor of the present invention is characterised in that with following composition formula to be represented.
(Ae)
a-c(Ae’)
bSi
xO
y:Eu
c
In the formula, Ae is at least a alkali earths element of selecting from Sr, Ca and Ba.Ae is at least a element of selecting from Mg and Zn.A is 1,2 or 3 in above-mentioned chemical formula, and b is 1 or 0.X is 1 or 2, and y is 4,6,7 or 8.Discovery is suitable from the composition of more than one fluorophor that the composition formula of above-mentioned fluorophor is selected.
And then, by on each luminescent coating of rubescent, the green glow that PDP is provided, using above-mentioned red, green, blue fluorophor, can realize above-mentioned purpose.
Description of drawings
Fig. 1 is the decomposition diagram of formation of plasma display panel of the plasm display device of expression the 1st embodiment of the present invention.
Fig. 2 is the cut-open view of formation of a pixel of the plasma display panel of expression the 1st embodiment of the present invention.
Fig. 3 is the cut-open view of formation of a pixel of the plasma display panel of expression the 2nd embodiment of the present invention.
Fig. 4 is the next door figure at interval of a pixel of plasma display panel of the plasm display device of expression the 3rd embodiment of the present invention.
Fig. 5 is the block scheme that the summary of the plasma display panel portion of the expression plasma display panel that uses aforementioned each embodiment constitutes.
Fig. 6 is that expression has the block scheme that the summary of one of the plasma display module example of the plasma display panel portion shown in Fig. 5 constitutes.
Fig. 7 is that expression has the block scheme that the summary of one of the Plasma Display monitor example of the plasma display module shown in Fig. 6 constitutes.
Fig. 8 is that expression has the block scheme that the summary of one of the plasma scope television system example of the plasma display module shown in Fig. 6 constitutes.
Fig. 9 is the decomposition diagram of formation of the plasma display panel of the general surface discharge type plasma display device of expression.
Figure 10 is the figure that shows the relation of the relative aberration of fluorophor of the 9th embodiment of the present invention and Eu concentration (x).
Figure 11 is the figure that shows the luminous intensity sustainment rate (A) of the 15th embodiment of the present invention.
Figure 12 is the figure that shows the luminous intensity sustainment rate (B) of the 16th embodiment of the present invention.
Embodiment
Explain embodiments of the invention with reference to the accompanying drawings.
(the 1st embodiment)
Fig. 1 is the decomposition diagram of formation of PDP of the plasm display device of expression the 1st embodiment of the present invention.
Fig. 2 is the cut-open view of formation of a pixel of the PDP of expression present embodiment.PDP shown in the formation of the PDP of the plasm display device of present embodiment and the earlier figures 9 is basic identical, and it describes omission in detail.But luminescent coating 24 is filled as the mixing of a feature of the present invention (Y, Gd) BO
3: Eu fluorophor and Y
2O
3: the red fluorophor that the Eu fluorophor obtains.And luminescent coating 25 is filled the Zn that uses as always
2SiO
4: the Mn fluorophor, its 1/10 persistence characteristic demonstrates the green luminophore of 6nm.Moreover, in Fig. 2, front substrate 10 1 sides are turned over ± 90 ° draw.
In the PDP of the surface discharge type PDP as the present embodiment, for example, by on show electrode 12 (being commonly referred to as scan electrode), applying negative voltage, on address electrode 21 and show electrode 11, apply positive voltage (than the positive voltage of voltage that puts on the show electrode 12) and discharge, thus, be formed on the auxiliary wall electric charge (call write) of the usefulness that begins between show electrode 11 and the show electrode 12 to discharge to this.If between show electrode 11 and show electrode 12, applying suitable reverse voltage under this state, then in two electric discharge between electrodes spaces, discharge via dielectric 15 (with protective seam 16).Discharge if make the voltage reversal that puts on show electrode 11 and the show electrode 12, is then discharged after finishing again.Discharge constantly by repeating these (this is called continuous discharge or shows discharge).
The PDP of present embodiment form the address electrode 21 that constitutes by silver etc. overleaf on the substrate 20 and the dielectric layer 22 that constitutes by glass-like materials after, the next door material that thick film screen printing is made of same glass-like materials forms next door 23 with spraying mask by spraying to remove.Then, on this next door 23, each luminescent coating of red, green, blue (24,25,26) is formed strip successively with the form of the groove face that covers 23 in suitable next door.
Here, each luminescent coating (24,25,26) is corresponding to red, green, blue, be taken as red phosphor particle 40 weight % (carrying photo etching 60 weight %), green luminophore particle 35 weight % (carrying photo etching 65 weight %), blue phosphor particle 30 weight % (carrying photo etching 70 weight %), they respectively with carry a photo etching and mix and make phosphor paste, after being coated with by serigraphy, carry out the evaporation and the organic burning removal of the volatile ingredient in the phosphor paste by dry and ablating work procedure.Moreover used in the present embodiment luminescent coating is that each phosphor particle of 3 μ m constitutes by central particle diameter.
In addition, the material of each fluorophor is that red fluorophor is (Y, Gd) BO
3: Eu fluorophor and Y
2O
3: 1: 1 potpourri of Eu fluorophor; Green luminophore is that 6ms adopts and the Mn/Zn ratio of components is taken as 0.07 Zn in order to make for 1/10 after time
2SiO
4: the Mn fluorophor; Blue fluorophor is BaMgAl
10O
14: Eu.
Then, the front substrate 10 and the back substrate 20 sintering sealing that have formed show electrode (11,12), bus electrode (13,14), dielectric layer 15, protective seam 16, injecting after the vacuum exhaust in the plate and sealing discharge gas.The PDP of present embodiment, it is of a size of 42 wide types, and pixel count is equivalent to VGA (852 * 480), and the spacing of a pixel is 490 μ m * 1080 μ m.
Then, in the present embodiment, make making Zn
2SiO
4: the Mn/Zn ratio of components of Mn fluorophor changes between 0.01～0.1, red, blue fluorophor uses same material, green luminophore with each Mn/Zn ratio of components is filled in green luminophore 25 plasm display device once, the picture quality when the investigation animated image shows and the after time of PDP plate.
The Mn/Zn ratio of components is that be 12ms, 10ms, 8ms, 6ms, 4ms, 3ms 1/10 after time of 0.01,0.03,0.05,0.07,0.09,0.1 o'clock green luminophore.But, find, at the Zn of Mn/Zn ratio of components more than 0.09 that demonstrates the persistence characteristic below the 4ms
2SiO
4: in the Mn fluorophor, sharply produce the reduction significantly of briliancy and the reduction of life performance.
In addition, employed in the present embodiment red fluorophor is (Y, Gd) BO
3: Eu fluorophor and Y
2O
3: 1: 1 potpourri of Eu fluorophor, can confirm to be about its 1/10 after time 6ms.In the subjective assessment when animated image shows, find that green luminophore also is that to demonstrate the combination impression of after time of 6ms best, secondly, the combination of 8ms, 4ms obtains the preferable image quality.
(comparative example 1)
Here, red fluorophor is taken as (Y, Gd) BO
3: the single fluorophor of Eu, green luminophore are Zn
2SiO
4: the Mn fluorophor is that 0.01 occasion is made as a comparative example with the Mn/Zn ratio of components, the picture quality the when animated image of each plasm display device among the 1st embodiment is shown and comparing the after time of PDP plate.
Be about 12ms 1/10 after time the when green of the plasm display device of making shows in the 1st comparative example.In addition because also approximately longly be 9ms the after time of red fluorophor, so the display quality of animated image become spin out quite tangible result.Particularly, find that green twilight sunset is very showy.
According to above comparison, can find with (Y, Gd) BO
3: Eu fluorophor and Y
2O
3: the potpourri of Eu fluorophor can be implemented 1/10 after time of the red fluorophor of PDP and adjust.And then find to have the occasion of the after time about 6ms at red fluorophor, green luminophore also the after time about 8ms～4ms be suitable, the occasion with almost same after time of 6ms is best.
In addition, find in order to shorten Zn as green luminophore
2SiO
4: the after time of Mn fluorophor, adjusting the Mn/Zn ratio of components is effectively, and in order to obtain the after time of 8ms～4ms, this ratio of components is 0.05～0.09th, and is suitable.
Moreover, though present embodiment is to BaMgAl
10O
14: Eu is illustrated as the occasion of blue fluorophor, but the invention is not restricted to this, and the present invention also can use fluorescent material and aforementioned in addition the combination of fluorescent material except that aforementioned, and also can equally use various particle diameters, size.
In addition, the size of the PDP that the present invention is suitable for is not particularly limited, and can irrespectively use with the parameter of various definite PDP sizes such as picture dimension (about 20 to 100 inches), resolution, Pixel Dimensions.
(the 2nd embodiment)
The formation of the PDP of the plasm display device of present embodiment is identical with the PDP shown in the earlier figures 9, and it describes omission in detail.In aforementioned the 1st embodiment, illustrate and make Zn
2SiO
4: the persistence characteristic when the Mn/Zn ratio of components of Mn fluorophor changes.Here, to (Y, Gd) BO as red fluorophor
3: Eu fluorophor and Y
2O
3: the mixture ratio of Eu fluorophor makes Y
2O
3: the content of Eu fluorophor becomes 10%, 30%, 50%, 70%, 90% o'clock the after time and the subjective assessment of animated image quality.
Same with aforementioned the 1st embodiment, each luminescent coating (24,25,26) is corresponding to red, green, blue, be taken as the red in any occasion phosphor particle 40 weight % of red fluorophor (carrying photo etching 60 weight %), the green luminophore particle is 35 weight % (carrying photo etching 65 weight %), blue phosphor particle is 30 weight % (carrying photo etching 70 weight %), they are mixed and made into phosphor paste with a year photo etching respectively, after the serigraphy coating, evaporation and the organic burning removal of carrying out the volatile ingredient in the phosphor paste by dry and ablating work procedure form.In addition, blue fluorophor is BaMgAl
10O
14: Eu.
Mixture ratio (the Y of each red fluorophor
2O
3: be to demonstrate the value of 8.5ms, 7.0ms, 6.0ms, 4.0ms, 3.5ms respectively at 10%, 30%, 50%, 70%, 90% o'clock the after time the content of Eu).
The animated image quality is that 7.0～4.0ms place obtains good image demonstration near 6ms.As a result, find that the mixture ratio of red fluorophor is 30%～70%, suitable.
Use (Y, Gd) BO as can be seen
3: Eu fluorophor and Y
2O
3: the potpourri of Eu fluorophor can be implemented 1/10 after time of the red fluorophor of PDP and adjust.And then find to have the occasion of the after time about 6ms at green luminophore, it (in the embodiment research, is suitable the after time of 7ms～4ms) that red fluorophor also has about 8ms～4ms.Have much at one after time 6ms occasion be best.
In addition, discovery is as (Y, Gd) BO of red fluorophor
3: Eu fluorophor and Y
2O
3: the ratio of the potpourri of Eu fluorophor is 30%～70%, for the after time that obtains 8ms～4ms be suitable.And then, to hybrid combining as red fluorophor, (Y, Gd) BO
3: Eu fluorophor and (Y, Gd) (P, V) O
4: the occasion of the potpourri of Eu fluorophor has also been carried out same research.Find to obtain under this occasion mixture ratio ((Y, Gd) (P, V) O of the after time of 8ms～4ms
4: the content of Eu),, suitable 25%～95%.
Though in the present embodiment to BaMgAl
10O
14: Eu is that the occasion of blue fluorophor is illustrated, but the invention is not restricted to this.The present invention also can use except that aforementioned fluorescent material and aforementioned beyond the combination of fluorescent material, and also can equally use various particle diameters, size.
In addition, the size of the PDP that the present invention is suitable for is not particularly limited, and can irrespectively use with the parameter of the size of various definite PDP such as picture dimension (about 20 to 100 inches), resolution, Pixel Dimensions.
(the 3rd embodiment)
Fig. 3 is the cut-open view of formation of a pixel of the PDP of expression present embodiment.In the present embodiment, fill green luminophores to green luminophore layer 25 and adopt silk screen print methods, by at first be demonstrate 5ms after time (Y, Gd)
3(Al, Ga)
5O
12: secondly the Tb fluorophor is the Zn that demonstrates the twilight sunset of 8ms
2SiO
4: the order of Mn fluorophor is carried out twice printing, forms the green luminophore layer 25 of the two kinds of fluorophor of lamination shown in Fig. 3.
Same with aforementioned the 1st embodiment, each luminescent coating (24,25,26) is taken as red phosphor particle 40 weight % (carrying photo etching 60 weight %), as the Zn of a kind of green luminophore particle 14 weight % (carrying photo etching 86 weight %) corresponding to red, green, blue
2SiO
4: the Mn fluorophor and as a kind of green luminophore particle 20% (carry photo etching 80%) (Y, Gd)
3(Al, Ga)
5O
12: Tb fluorophor (Tb concentration 10mol%), blue phosphor particle 30 weight % (carrying photo etching 70 weight %), they respectively with carry a photo etching and mix and make phosphor paste, after being coated with by serigraphy, evaporation and the organic burning removal of carrying out the volatile ingredient in the phosphor paste by dry and ablating work procedure form.In addition, the material of each fluorophor is that red fluorophor is (Y, Gd) BO
3: Eu fluorophor and (Y, Gd) (P, V) O
4: the potpourri of Eu fluorophor, mixture ratio are 60%; Blue fluorophor is BaMgAl
10O
14: Eu; Green luminophore is the Zn for preparing respectively
2SiO
4: Mn fluorophor and Y
3(Al
xGa
1-x)
5O
12: Tb fluorophor (Tb concentration 10mol%).
Be about 6ms 1/10 after time that can obtain red fluorophor this moment, from lamination-type green fluorescence film resulting luminous after time also with the almost equal persistence characteristic of 6ms.Therefore, obtain the also good show image of animated image quality.
In addition, change, prepare Zn respectively in order to make the volume ratio in the lamination green fluorescence film
2SiO
4: Mn green luminophore particle be taken as 25～10 weight % (carry photo etching 75～90 weight %) phosphor paste and (Y, Gd)
3(Al, Ga)
5O
12: Tb fluorophor (Tb concentration 10mol%) green luminophore particle is taken as the phosphor paste of 10～25 weight % (carry photo etching 90～75 weight %), with aforementioned same condition under print formation.
With the weight % that descends phosphor particle on all occasions is that 35 mode makes up.
Persistence characteristic when volume ratio in the occasion of lamination-type green fluorescence film is changed, (Y, Gd)
3(Al, Ga)
5O
12: the content of Tb fluorophor be about 30%, about 40%, about 60%, about 70% o'clock, confirm to be respectively for 1/10 after time 7ms, 6.5ms, 6ms, 5.5ms.
So, even confirmed at a Y that the rare earth element terbium is activated
3(Al
xGa
1- x)
5O
12: Tb fluorophor (Tb concentration 10mol%) and Zn
2SiO
4: Mn fluorophor lamination and in the luminescent coating 25 that forms, also can adjust after time.In addition, adjusting in 1/10 after time of the red fluorophor of PDP is (Y, Gd) BO
3: Eu fluorophor and (Y, Gd) (P, V) O
4: the potpourri of Eu fluorophor, mixture ratio is 60% o'clock, the occasion that arranged the after time about 6ms, confirmed that lamination-type green luminophore film also is (in the embodiment research about 8ms～4ms, be suitable the after time of 7ms～5ms), and the occasion with 6ms after time much at one is best.
Though be BaMgAl to blue fluorophor in the present embodiment
10O
14: the occasion of Eu is illustrated, but the invention is not restricted to this, and the present invention also can use fluorescent material and aforementioned in addition the combination of fluorescent material except that aforementioned, and also can equally use various particle diameters, size.
In addition, the size of the PDP that the present invention is suitable for is not particularly limited, and can irrespectively use with the parameter of the size of various definite PDP such as picture dimension (about 20 to 100 inches), resolution, Pixel Dimensions.
(the 4th embodiment)
The formation of the PDP of the plasm display device of present embodiment is owing to identical with the PDP shown in the earlier figures 9, so omit its detailed description.
Fig. 4 is the next door figure at interval of a pixel of PDP of the plasm display device of expression present embodiment.In the present embodiment, adopt the structure of the back substrate 20 different with previous embodiment.The interval in next door 23 is 100% with green discharge cell size (next door at interval), and then red discharge cell is 80%, and blue discharge cell is 120%, and the next door allows to have maximum about 40% at interval and changes.
In the present embodiment, to making the Zn of the twilight sunset that demonstrates 8ms
2SiO
4: Mn fluorophor and the Y that demonstrates the after time of 4ms
2SiO
5: the mixture ratio (Y of Tb fluorophor
2SiO
5: the occasion of the Bian Huaing content of Tb fluorophor), carry out the evaluation of persistence characteristic.
Fill green luminophore to green luminophore layer 25 and adopt silk screen print method, form each luminescent coating (24,25,26) shown in Fig. 4.
Same with aforementioned the 1st embodiment, each luminescent coating (24,25,26) is taken as red phosphor particle 35 weight % (carrying photo etching 65 weight %) corresponding to red, green, blue, and green luminophore particle 40 weight % (carrying photo etching 60 weight %) also use Zn
2SiO
4: Mn fluorophor and Y
2SiO
5: the potpourri of Tb fluorophor, blue phosphor particle 50 weight % (carrying photo etching 50 weight %), they respectively with carry a photo etching and mix and make phosphor paste, after being coated with by serigraphy, carry out the evaporation and the organic burning removal of the volatile ingredient in the phosphor paste by dry and ablating work procedure.In addition, the material of each fluorophor is that red fluorophor is (Y, Gd) BO
3: Eu fluorophor and (Y, Gd) (P, V) O
4: the potpourri of Eu fluorophor, the mixture ratio with the after time about 6ms is 60%; Blue fluorophor is BaMgAl
10O
14: Eu; Green luminophore is Zn
2SiO
4: Mn fluorophor and Y
2SiO
5: the Tb fluorophor is by the green luminophore that mixes at 1: 1.
Make the mixture ratio (Y in the present embodiment
2SiO
5: the content of Tb fluorophor) become 10%, 30%, 50%, 70%, 90% o'clock persistence characteristic, confirm to be respectively for 1/10 after time 7.5ms, 6.5ms, 6ms, 5ms, 4.5ms.
So, mixing Zn even confirmed
2SiO
4: Mn fluorophor and the Y that the rare earth element terbium is activated
2SiO
5: Tb fluorophor (Tb concentration 10mol%) and in the luminescent coating 25 that forms, also can adjust after time.In addition, adjusting in 1/10 after time of the red fluorophor of PDP is (Y, Gd) BO
3: Eu fluorophor and (Y, Gd) (P, V) O
4: the potpourri of Eu fluorophor, mixture ratio is 60% occasion, arranged the after time about 6ms, confirmed that lamination-type green luminophore film also is (in the embodiment research about 8ms～4ms, 7.5ms be suitable～4.5ms) after time, be best the after time that has much at one during 6ms.
So, it is also high to obtain relative briliancy, the value on the colourity.Make the Y of rare earth element terbium activation
2SiO
5: Tb fluorophor and Zn
2SiO
4: the mixing phosphor of Mn fluorophor, its mixture ratio are not restricted by Tb interpolation concentration also.
And then, carried out as the oxide phosphor that makes rare earth element terbium (Tb) activation the evaluation of the mixed green color fluorescent film of forming by following glow green fluorophor.The green-emitting phosphor of research is to use composition formula YBO
3: Tb, LuBO
3: Tb, GdBO
3: Tb, ScBO
3: Tb, YPO
4: Tb, LaPO
4: select more than one material to carry out the briliancy evaluation successively among the fluorophor group who consists of principal ingredient that Tb expresses.The mixture ratio of this moment is taken as 50% constant, and it is constant that the interpolation concentration of rare earth element terbium (Tb) is taken as 5mol%.At first, a kind of fluorophor and the Zn that glow green is provided that selects from above-mentioned fluorophor mass selection at handle
2SiO
4: the occasion that the Mn fluorophor mixes, can confirm at LuBO
3: Tb, GdBO
3: Tb, ScBO
3: Tb, YPO
4: the occasion short persistenceization of Tb.
Moreover, though be BaMgAl to blue fluorophor in the present embodiment
10O
14: the occasion of Eu is illustrated, but the invention is not restricted to this, and the present invention also can use fluorescent material and aforementioned in addition the combination of fluorescent material except that aforementioned, and then also can equally use various particle diameters, size.
In addition, the size of the PDP that the present invention is suitable for is not particularly limited, and can irrespectively use with the parameter of the size of definite PDP such as various picture dimensions (about 20 to 100 inches), resolution, Pixel Dimensions.
(the 5th embodiment)
Below, just use the display system of the PDP of aforementioned each embodiment to describe.
Fig. 5 is the block scheme that the summary of the plasma display panel portion 100 of the expression PDP that uses aforementioned each embodiment constitutes.As shown in this Fig, plasma display panel portion 100 is by PDP 110, data drive circuit (121,122), and scan drive circuit 130, high-voltage pulse generating circuit (141,142), and the control circuit 150 of controlling aforementioned each circuit constitutes.
Here, PDP 110 is the PDP that illustrate among aforementioned each embodiment, and this PDP 110 drives by picture being cut apart the double-scanning type that drives simultaneously up and down. therefore, these two data driving circuits (121,122) drive address electrode 21. up and down simultaneously
In addition, the side at the short brink of PDP 110 is provided with scan drive circuit 130, and this scan drive circuit 130 drives show electrodes 22.High-voltage pulse generating circuit 141 generates the high-voltage pulse that is applied to show electrode 22 from scan drive circuit 130.
The opposing party at the short brink of PDP 110 is provided with high-voltage pulse generating circuit 142, and this high-voltage pulse generating circuit 142 generates high-voltage pulses, drives show electrode 21.
Fig. 6 is that expression has the block scheme that the summary of one of plasma display module 200 example of the plasma display panel portion 100 shown in Fig. 5 constitutes.As shown in this Fig, plasma display module 200 is by the signal processing circuit of being made up of input signal treatment circuit 211, image quality improvement treatment circuit 212, frame memory 213, scanning/data driver control circuit 214 210, electric power is adjusted circuit 220, and high-voltage power circuit 230 and plasma display panel portion 100 constitute.The received image signal of importing this plasma display module 200 imposes signal Processing such as γ correction in input signal treatment circuit 211 and image quality improvement treatment circuit 212 after, be stored in frame memory 213.In this occasion, be the occasion of simulating signal at received image signal, in input signal treatment circuit 211, convert digital signal to.
Scanning/data driver control circuit 214 controlling and driving aforementioned data driving circuit (121,122) and scan drive circuits 130.
Fig. 7 is that expression has the block scheme that the summary of one of Plasma Display monitor 300 example of the plasma display module 200 shown in Fig. 6 constitutes.In addition, Fig. 8 is that expression has the block scheme that the summary of one of PDP television system 400 example of the plasma display module 200 shown in Fig. 6 constitutes.In Fig. 7, Fig. 8, the 310th, loudspeaker, in addition, and the 410th, TV tuner.At the Plasma Display monitor 300 shown in this Fig. 7, in the plasma electrically viewing system 400 shown in Fig. 8, supply with image, sound and power supply from outside source (for example personal computer, video recorder movement, CD/DVD player, internet terminal, telephone wire, derived digital signal etc.).
Resulting picture quality in these display systems can confirm that high briliancy and quality are good, spins out phenomenon, animation quality height when particularly reducing animated image and showing.
(the 6th embodiment)
Typical fluorophor in the embodiments of the invention is synthetic as following.As phosphor raw material, with zinc compounds such as alkali earths carbonate compounds such as strontium carbonate, zinc carbonates, europium compounds such as europium, silicon compounds such as monox, ammonium halide compounds such as ammonium chloride, these each raw materials are pressed the composition formula weighing, with wet type of taking or the fully good mixing of dry type.This potpourri is filled in heatproof containers such as aloxite (AI crucible, carries out 2 times and fire.First fires in air, carries out under 800 ℃, fires under 1250 ℃ temperature in containing the mixing nitrogen atmosphere of 5% hydrogen for the 2nd time.After this is fired thing and pulverizes, wash, dry and obtain blue-fluorescence fluorophor of the present invention.
The composition of fluorophor shown in the table 1 and relative luminous intensity.
[table 1]
| The sample sequence number | Fluorophor is formed | Relative luminous intensity (%, 147nm excitation) |
| 1 | |
110％ |
| The sample sequence number | Fluorophor is formed | Relative luminous intensity (%, 147nm excitation) |
| 2 | |
110％ |
| 3 | |
100％ |
| 4 | Ba1.9Eu0.1MgSiO4 | 105％ |
| 5 | (Ba，Sr.Ca)0.9 |
110％ |
| 6 | (Ba，Sr，Ca)0.9Eu0.1(Mg0.9，Zn0.1)SiO4 | 115％ |
| 7 | (Ca)0.9 |
100％ |
| 8 | (Ba，Sr，Ca)0.9Eu0.1(Mg0.9，Zn0.1) |
110％ |
| Control sample | Ba0.9MgAl10O17:Eu0.1 | 100％ |
Wherein the fluorophor of sample 5 is following synthetic.That is to say, take by weighing following raw material BaCO
3: 0.3mol * 0.15.92g, SrCO
3: 0.3mol * 0.14.42g, CaCO
3: 0.3mol * 0.13.00g, MgCO
3: 1mol * 0.18.43g, SiO
2: 1mol * 1mol 0.16.01g, Eu
2O
3: 0.1mol * 0.051.76g, NH
4Cl:0.1g after the amount of fully good mixing necessity, is filled in this potpourri heatproof containers such as aloxite (AI crucible, under 800 ℃, then fires under 1250 ℃ temperature in 5% hydrogen mixing nitrogen atmosphere in air.After this is fired thing and pulverizes, wash, the dry and coloured light fluorophor that obtains turning blue.Other fluorophor are synthetic too.Then, the glorious degrees of obtaining this fluorophor under the 147nm vacuum ultraviolet excitation is the relative luminous intensity of each sample of occasion of 100% with the glorious degrees of existing fluorophor BAM.Its result is as shown in table 1, is 100%～115%.In addition, the life characteristic comparison of having confirmed these fluorophor improves than sample.
(the 7th embodiment)
With previous described raw material, synthesize in the table 2 fluorophor (sample 9～20) of partly replacing with Ca, Sr, Ba and Mg or Zn of record by same synthesis technique.Each all has than higher glorious degrees under 147nm is ultraviolet ray exited to find these fluorophor.Concrete luminous intensity is shown in table 2.In addition, the life characteristic comparison of having confirmed these fluorophor improves than sample.
(the 8th embodiment)
Make plasma display panel (PDP) as the blue-fluorescence body and function that constitutes the blue-fluorescence film according to divalent europium activation alkali earths silicate phosphor of the present invention (composition shown in table 1 and the table 2).
[table 2]
| The sample sequence number | Fluorophor is formed | Relative luminous intensity (%, 147nm excitation) |
| 9 | (Ba，Sr，Ca)0.99Eu0.01MgSiO4 | 105％ |
| 10 | (Ba，Sr，Ca)0.95Eu0.05MgSiO4 | 108％ |
| 11 | (Ba，Sr，Ca)0.8Eu0.2MgSiO4 | 105％ |
| 12 | (Ba，Sr，Ca)0.7 |
100％ |
| 13 | Ba0.9Eu0.1(Mg0.9，Zn0.1)SiO4 | 110％ |
| 14 | Ba0.9Eu0.1(Mg0.8，Zn0.2)SiO4 | 110％ |
| 15 | Ba0.9Eu0.1(Mg0.5，Zn0.5)SiO4 | 100％ |
| 16 | |
90％ |
| 17 | Ca(Mg0.99，Zn0.01)Si2O6 | 115％ |
| 18 | Ca(Mg0.9，Zn0.1) |
110％ |
| 19 | Ca(Mg0.8，Zn0.2) |
100％ |
| 20 | CaZnSi2O6 | 80％ |
| Control sample | Ba0.9MgAl10O17:Eu0.1 | 100％ |
In the PDP of this surface discharge type color PDP of present embodiment, for example, by negative voltage is put on show electrode (being commonly referred to as scan electrode), positive voltage is put on address electrode and show electrode (than the positive voltage of the voltage that puts on show electrode) and discharge, whereby, be formed on the auxiliary wall electric charge (call write) of the usefulness that begins between show electrode to discharge to this.If, then in two electric discharge between electrodes spaces, discharge via dielectric (and protective seam) between show electrode and show electrode, applying suitable reverse voltage under this state.Discharge if make the voltage reversal that puts on show electrode and the show electrode, is then discharged after finishing again.Discharge constantly by repeating these (this is called continuous discharge or shows discharge).
The PDP of present embodiment form the address electrode that constitutes by silver etc. overleaf on the substrate and the dielectric layer that constitutes by glass-like materials after, the next door material that thick film screen printing is made of same glass-like materials, form the next door with spraying mask by spraying to remove. then, on this next door, red, green, blue each luminescent coating forms strip successively with the form that covers the groove face between suitable next door. here, each luminescent coating is corresponding to red, green, blue, be taken as red phosphor particle 40 weight % (carrying photo etching 60 weight %), green luminophore particle 35 weight % (carrying photo etching 65 weight %), blue phosphor particle 30 weight % (carrying photo etching 70 weight %), they respectively with carry a photo etching and mix and make phosphor paste, after being coated with by serigraphy, carry out the evaporation and the organic burning of the volatile ingredient in the phosphor paste removes by dry and ablating work procedure. moreover, used in the present embodiment luminescent coating is that each phosphor particle of 3 μ m constitutes by central particle diameter. in addition, the material of each fluorophor, red fluorophor is (Y, Gd) BO
3: Eu fluorophor and Y
2O
3: 1: 1 potpourri of Eu fluorophor, green luminophore are Zn
2SiO
4: the Mn fluorophor.Then, the front substrate and the sealing of back substrate sintering that have formed show electrode, bus electrode, dielectric layer, protective seam, injecting after the vacuum exhaust in the plate and sealing discharge gas.The PDP of present embodiment, it is of a size of 3 types, and the spacing of a pixel is 1000 μ m * 1000 μ m.
Then, make of each fluorophor of forming among the 6th and the 7th embodiment, red, green luminophore uses same material, is filled in the plasm display device of each luminescent coating 25, has investigated initial stage briliancy and life characteristic.The existing situation that this plate is made with only blue emitting phophor being replaced as divalent europium activation barium magnesium aluminate as fluorescent substance is compared tone and will be got well, and has high briliancy and long-life.The initial stage briliancy obtains the almost equal result of relative luminous intensity about the powder of each fluorophor record with table 2.Fluorophor (all shown in table 1 and the table 2 are formed) all on this external life performance demonstrate the result who surpasses the contrast fluorophor.
In addition, in the present embodiment about red and green luminophore, though detailed result of study is not shown, even can make PDP too with each fluorophor formed shown in following.In red fluorophor, can comprise (Y, Gd) BO
3: Eu, (Y, Gd)
2O
3: Eu, (Y, Gd) (P, V) O
4: any above fluorophor among the Eu.In addition, green luminophore can comprise from Zn
2SiO
4: Mn, (Y, Gd, Sc)
2SiO
5: Tb, (Y, Gd)
3(Al, Ga)
5O
12: Tb, (Y, Gd)
3(Al, Ga)
5O
12: Ce, (Y, Gd) B
3O
6: Tb, (Y, Gd) PO
4: the fluorophor of more than one that select in the group of Tb.Can also use combination at this unshowned fluorophor.
(the 9th embodiment)
Figure 10 be illustrated in 147nE vacuum ultraviolet excitation iridescent down etc. the colourity coordinate figure (U V) with the aberration of NTSC benchmark blue dot with the value of existing fluorophor BAM is 100% o'clock Sr
3-xMgSi
2O
8: the relative aberration of Eu is to the dependence of Eu concentration.From then on figure as can be seen, Eu concentration (x) in the scope of 0.01≤x≤0 than existing BAM fluorophor more near the NTSC blue dot, tone is good.In addition, luminescence efficiency is in the peer-level with BAM, also is the long-life.The composition of fluorophor shown in the table 3 and relative luminous aberration.
[table 3]
| The sample sequence number | Fluorophor is formed | Relative luminous intensity (%, 147nm excitation) |
| 21 | Sr2.99Eu0.01MgSi2O8 | 99％ |
| 22 | Sr2.98Eu0.02MgSi2O8 | 86％ |
| 23 | Sr2.97Eu0.03MgSi2O8 | 82％ |
| 24 | |
80％ |
| 25 | Sr2.90Eu0.10MgSi2O8 | 98％ |
| Control sample | Ba0.9MgAl10O17:Eu0.1 | 100％ |
Wherein the fluorophor of sample 24 is synthetic as following.That is to say, following raw material, i.e. SrCO
3: 4.385g, MgCO
3: 0.907g, SiO
2: 1.00g, Eu
2O
3: 0.053g, NH
4After the fully good mixing of Cl:0.022g, this potpourri is filled in heatproof containers such as aloxite (AI crucible, in air, under 800 ℃, then in containing the mixing nitrogen atmosphere of 5% hydrogen, under 1250 ℃ temperature, fires.After this is fired thing and pulverizes, wash, the dry and coloured light fluorophor that obtains turning blue.The iridescent of this fluorophor under 147nm vacuum ultraviolet excitation is waiting value on the colourity coordinate, and (U is that the relative aberration of this sample 4 of 100% occasion is 80% with the value of existing fluorophor BAM with the aberration of NTSC benchmark blue dot V).More near NTSC benchmark blue dot, tone is good than existing BAM in this expression.The fluorophor that has similarly synthesized sample 21,22,23 and 25.The relative aberration of these fluorophor demonstrates 99,86,82 and 87% good value respectively.
Figure 10 illustrates above result as the relative aberration of this fluorophor to the interdependence of Eu concentration (x).From then on scheme as can be seen, the effective range of Eu is 0.01≤x≤0.1.Moreover the glorious degrees of the fluorophor of this Eu concentration range is in the almost equal level with BAM.
(the 10th embodiment)
With previous described raw material, synthesize in the table 3 fluorophor (sample 26～40) of partly replacing with Ca, Sr, Ba and Mg or Zn of record by same synthesis technique.Find these fluorophor each all has high glorious degrees under 147nm is ultraviolet ray exited.
(the 11st embodiment)
As the blue emitting phophor that constitutes the blue-fluorescence film, adopt according to divalent europium activation alkali earths silicate phosphor (composition shown in table 3 and the table 4) of the present invention, make plasma display panel (PDP).
[table 4]
| The sample sequence number | Fluorophor is formed | Relative luminous intensity (%, 147nm excitation) |
| 26 | Sr2. |
100％ |
| 27 | Sr2.96Eu0. |
100％ |
| 28 | Sr2.87Ca0.1Eu0.03Mg0.99Zn0.01Si2O8 | 103％ |
| 29 | |
100％ |
| 30 | Ca2.4Ba0.5Eu0.1MgSi2O8 | 105％ |
| 31 | Sr2. |
100％ |
| 32 | Sr2. |
110％ |
| 33 | Sr1.9Ba1.0Eu0.1MgSi2O8 | 115％ |
| 34 | Sr0.9Ba2.0Eu0.1MgSi2O8 | 115％ |
| The sample sequence number | Fluorophor is formed | Relative luminous intensity (%, 147nm excitation) |
| 35 | |
110％ |
| 36 | Sr2.4Ba0.5Eu0.1Mg0.99Zn0.01Si2O8 | 115％ |
| 37 | Sr2.3Ba0.5Ca0.1Eu0.1Mg0.99Zn0.01Si2O8 | 115％ |
| 38 | Sr2. |
100％ |
| 39 | Sr2.45Ba0.5Eu0.05MgSi2O8 | 105％ |
| 40 | Sr2. |
110％ |
| Control sample | Ba0.9MgAl10O17:Eu0.1 | 100％ |
In the PDP of this surface discharge type color PDP of present embodiment, for example, by negative voltage is put on show electrode (being commonly referred to as scan electrode), positive voltage is put on address electrode and show electrode (than the positive voltage of the voltage that puts on show electrode) and discharge, thus, be formed on the auxiliary wall electric charge (call write) of the usefulness that begins between show electrode to discharge to it.If, then in two electric discharge between electrodes spaces, discharge via dielectric (and protective seam) between show electrode and show electrode, applying suitable reverse voltage under this state.Discharge if make the voltage reversal that puts on show electrode and the show electrode, is then discharged after finishing again.Discharge constantly by repeating these (it is called continuous discharge or shows discharge).
The PDP of present embodiment form the address electrode that constitutes by silver etc. overleaf on the substrate and the dielectric layer that constitutes by glass-like materials after, the next door material that thick film screen printing is made of same glass-like materials forms the next door with spraying mask by spraying to remove.Then, on this next door, each luminescent coating of red, green, blue is formed strip successively with the form that covers the groove face between suitable next door.Here, each luminescent coating is corresponding to red, green, blue.Be taken as red phosphor particle 40 weight % (carrying photo etching 60 weight %), green luminophore particle 35 weight % (carrying photo etching 65 weight %), blue phosphor particle 30 weight % (carrying photo etching 70 weight %), they respectively with carry a photo etching and mix and make phosphor paste, after being coated with by serigraphy, carry out the evaporation and the organic burning removal of the volatile ingredient in the phosphor paste by dry and ablating work procedure.Used in the present embodiment luminescent coating is that each phosphor particle of 3 μ m constitutes by central particle diameter.In addition, the material of each fluorophor, red fluorophor are (Y, Gd) BO
3: Eu fluorophor and Y
2O
3: 1: 1 potpourri of Eu fluorophor; Green luminophore is Zn
2SiO
4: the Mn fluorophor.Then, the front substrate and the sealing of back substrate sintering that have formed show electrode, bus electrode, dielectric layer, protective seam, injecting after the vacuum exhaust in the plate and sealing discharge gas.The PDP of present embodiment, it is of a size of 3 types, and the spacing of a pixel is 1000 μ m * 1000 μ m.
Then, make of each fluorophor of forming among the 6th and the 7th embodiment, red, green luminophore uses same material, is filled in the plasm display device of each luminescent coating, has investigated initial stage briliancy and life characteristic.
This plate with only blue emitting phophor is replaced as existing situation that divalent europium activation barium magnesium aluminate as fluorescent substance makes and compares tone and will get well, and have high briliancy and long-life.
The initial stage briliancy obtains the relative luminous intensity about the record of each fluorophor with table 4, and each all obtains the result more than the divalent europium activation barium magnesium aluminate as fluorescent substance of sample as a comparison is equal.Also be that all fluorophor (all shown in table 3 and the table 4 are formed) demonstrate the result who surpasses the contrast fluorophor on this external life performance.
In addition, in the present embodiment about red and green luminophore, though detailed result of study is not shown, even can make PDP too with each fluorophor formed shown in following.In red fluorophor, can comprise (Y, Gd) BO
3: Eu, (Y, Gd)
2O
3: Eu, (Y, Gd) (P, V) O
4: any above fluorophor among the Eu.In addition, green luminophore comprises from Zn
2SiO
4: Mn, (Y, Gd, Sc)
2SiO
5: Tb, (Y, Gd)
3(Al, Ga)
5O
12: Tb, (Y, Gd)
3(Al, Ga)
5O
12: Ge, (Y, Gd) B
3O
6: SiO
5: Tb, (Y, Gd) PO
4: the fluorophor of more than one that select in the group of Tb.Can also use and the combination of unshowned fluorophor here.
(the 12nd embodiment)
Blue emitting phophor adopts according to divalent europium activation alkali earths silicate phosphor (composition shown in table 1 and the table 3) of the present invention, green fluorescence body and function divalent manganese activated zinc silicate fluorophor, and red fluorescence body and function 3 valency europiums activation yttrium chloride gadolinium fluorophor is made rare gas (xenon) discharge white fluorescent lamp.The existing situation that this lamp is made with only blue emitting phophor being replaced as divalent europium activation barium magnesium aluminate as fluorescent substance is compared to be had high-luminous-efficiency and long-life.
(the 13rd embodiment)
Blue emitting phophor adopts according to divalent europium activation alkali earths silicate phosphor (composition shown in table 2 and the table 4) of the present invention, green fluorescence body and function divalent manganese activated zinc silicate fluorophor, and red fluorescence body and function 3 valency europiums activation yttrium chloride gadolinium fluorophor is made plane rare gas (xenon) discharge white fluorescent lamp.The existing situation that this lamp is made with only blue emitting phophor being replaced as divalent europium activation barium magnesium aluminate as fluorescent substance is compared to be had high-luminous-efficiency and long-life.
(the 14th embodiment)
Here, at first on the inside surface of the glass substrate that forms fluorescent film, form the transparency electrode of homogeneous.Then, form according to divalent europium activation alkali earths silicate phosphor (composition shown in table 1～table 4) of the present invention as the blue emitting phophor that constitutes the blue-fluorescence film successively, form divalent manganese activated zinc silicate fluorophor as the green-emitting phosphor that constitutes green fluorescent membrane, and form 3 valency europiums activation yttrium chloride gadolinium fluorophor as the red-emitting phosphors that constitutes the red fluorescence film.This glass substrate and small electronic radial source do into the sealing altogether of another glass substrate, make electric field transmitted escope (FED) plate of 10 types after the vacuum exhaust.This plate than always only blue emitting phophor is changed into divalent europium activation barium magnesium aluminate as fluorescent substance and the FED plate made demonstrates more high-level efficiency, and long-life.Confirmed to constitute display board, when using, obtained superior display quality as the display system of televisor, video recorder, automobile etc. with this plate.As mentioned above, the blue emitting phophor (divalent europium activation alkali earths silicate phosphor) that efficient is high under vacuum ultraviolet ultraviolet ray and the excitation of low-velocity electron ray is used for noble gas discharge demonstration and light-emitting device or field emission display device (FED), can realizes long lifetime and high image qualityization thus.
(the 15th embodiment)
As raw material, weighing also mixes BaCO
3(2.98x mol%) (0≤x≤1), SrCO
3(2.98 (1-x) mol%), MgCO
3(1mol%), SiO
2(2mol%), Eu
2O
3(0.01mol%), resulting potpourri in alumina crucible, in air atmosphere, was fired under 1300 ℃ 3 hours.After firing the thing pulverizing, in reducing atmosphere, under 1300 ℃, fired 3 hours., wash, screen, dry and obtain to use (Ba after firing thing and pulverizing with bowl mill
xSr
1-x)
2.98MgSi
2O
8: Eu
0.02The fluorophor that express (0≤x≤1).This fluorophor 40 weight % are mixed and made into phosphor paste with carrying photo etching 60 weight %, coat on the glass substrate, remove, form fluorescent membrane by removal dry, that ablating work procedure carries out the volatile ingredient in the paste and organic burning by serigraphy.
Peel off this fluorophor and make paste and fire powder from glass substrate, with the luminous intensity (A1) that swashs when source lamp (centre wavelength 146nm) is measured excitation. at this moment, do not print and fire, measure the luminous intensity (A0) of original fluorophor powder. as the index of the deterioration in the expression paste sintering procedure, with luminous intensity sustainment rate (A=A1/A0 * 100). in addition for relatively, at also having carried out same mensuration as the general employed BAM fluorophor of blue fluorophor. the sustainment rate of luminous intensity shown in Figure 11 (A). according to (Ba of the present invention
xSr
1-x)
3-aMgSi
2O
8: the luminous intensity sustainment rate of Eua fluorophor (0≤x≤0.1 or 0.65≤x≤1) when paste is fired is bigger than BAM fluorophor, shows to have the superperformance that suppresses deterioration.
(the 16th embodiment)
Make PDP with fluorophor according to the present invention, measured the driving degradation characteristic.The skeleton diagram of the display board shown in Fig. 9 among the PDP.PDP is front substrate and that this body of back substrate person.Overleaf on the substrate behind calculated address electrode and the next door, by forming Ba between following step next door
3MgSi
2O
8: Eu
0.02 Luminescent coating.Fluorophor 40 weight % and year photo etching 60 weight % are mixed and made into phosphor paste, be coated with by serigraphy, remove by removal dry, that ablating work procedure carries out the volatile ingredient in the paste and organic burning, make the plasma display panel of this back substrate that forms luminescent coating and front substrate stickup and inclosure discharge gas, measure the driving time characteristic of luminous intensity.Luminous intensity (B1) when luminous intensity (B0) when assay plate drives beginning and plate drive back 500h, the index of the deterioration that driving causes as display plate is with luminous intensity sustainment rate (B=B1/B0 * 100).It the results are shown in Figure 12.In addition for relatively, at also having carried out same mensuration as the general employed BAM fluorophor of blue fluorophor.
According to (Ba of the present invention
xSr
1-x)
3-aMgSi
2O
8: Eu
aThe luminous intensity sustainment rate of fluorophor (0≤x≤0.1 or 0.65≤x≤1) when plate drives is bigger than BAM fluorophor, shows to have the superperformance that suppresses deterioration.
Though the above invention of finishing based on the clear specifically inventor of embodiment, the present invention is not limited to the foregoing description, certainly carries out various changes in the scope that does not break away from its purport.
If use the present invention, then can shorten the after time of plasm display device and light-emitting device, improve the display quality of animated image, can realize the image display system of long-life and high picture quality.
Claims (9)
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP331855/2001 | 2001-10-30 | ||
| JP2001331855A JP4122752B2 (en) | 2001-10-30 | 2001-10-30 | Light emitting device |
| JP333675/2001 | 2001-10-31 | ||
| JP2001333675A JP4123758B2 (en) | 2001-10-31 | 2001-10-31 | Light emitting device |
| JP2001333681A JP4333064B2 (en) | 2001-10-31 | 2001-10-31 | Plasma display display device and video display system using the same |
| JP333681/2001 | 2001-10-31 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021470863A Division CN100405522C (en) | 2001-10-30 | 2002-10-29 | plasma display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1932930A CN1932930A (en) | 2007-03-21 |
| CN1932930B true CN1932930B (en) | 2010-05-12 |
Family
ID=19147355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610141650 Expired - Fee Related CN1932930B (en) | 2001-10-30 | 2002-10-29 | Plasma display device |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4122752B2 (en) |
| CN (1) | CN1932930B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005068169A (en) * | 2003-08-21 | 2005-03-17 | Sumitomo Chemical Co Ltd | Eu-activated phosphor |
| JP2006012770A (en) | 2004-05-27 | 2006-01-12 | Hitachi Ltd | Light-emitting device and image display device using this light-emitting device |
| CN101010413B (en) * | 2004-09-07 | 2010-08-25 | 住友化学株式会社 | Phosphor, phosphor paste and light-emitting device |
| KR100666265B1 (en) * | 2004-10-18 | 2007-01-09 | 엘지이노텍 주식회사 | Phosphor and light emitting device using same |
| JP2006312654A (en) * | 2005-04-07 | 2006-11-16 | Sumitomo Chemical Co Ltd | Phosphor |
| WO2007013515A1 (en) * | 2005-07-27 | 2007-02-01 | Matsushita Electric Industrial Co., Ltd. | Gas discharge light emitting panel |
| WO2007020798A1 (en) * | 2005-08-18 | 2007-02-22 | Sumitomo Chemical Company, Limited | Phosphor particle, phosphor paste and light-emitting device |
| JP4156020B2 (en) * | 2006-02-07 | 2008-09-24 | 松下電器産業株式会社 | Phosphor, light emitting device and plasma display panel |
| WO2007123183A1 (en) * | 2006-04-19 | 2007-11-01 | Mitsubishi Chemical Corporation | Color image display device |
| WO2007135926A1 (en) * | 2006-05-18 | 2007-11-29 | Panasonic Corporation | Method for producing silicate blue phosphor, silicate blue phosphor and light-emitting device |
| CN101460589B (en) | 2006-05-26 | 2012-06-13 | 松下电器产业株式会社 | Phosphor and light emitting device |
| JP2008038050A (en) * | 2006-08-08 | 2008-02-21 | Sumitomo Chemical Co Ltd | Phosphor |
| CN101541919B (en) | 2007-06-08 | 2013-03-20 | 松下电器产业株式会社 | Blue fluorescent material, light emitting device, and plasma display panel |
| JP5094246B2 (en) * | 2007-07-06 | 2012-12-12 | 株式会社日立製作所 | Plasma display device |
| JP2009280793A (en) * | 2008-04-24 | 2009-12-03 | Kyocera Corp | Fluorescent substance, wavelength converter, light emitter and lighting installation |
| JP5154481B2 (en) * | 2009-03-10 | 2013-02-27 | 宇部マテリアルズ株式会社 | Blue light emitting phosphor |
| US8883309B2 (en) * | 2010-04-14 | 2014-11-11 | Ube Material Industries, Ltd. | Silicate-based blue light-emitting phosphor and method for producing same |
| JP5689407B2 (en) * | 2011-12-28 | 2015-03-25 | 宇部マテリアルズ株式会社 | Silicate green light emitting phosphor |
| DE102012021570A1 (en) * | 2012-11-02 | 2014-05-22 | Merck Patent Gmbh | Eu-activated phosphors |
| CN102925144B (en) * | 2012-11-14 | 2015-07-01 | 合肥工业大学 | A kind of white light LED blue fluorescent material suitable for near ultraviolet wavelength excitation and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543080A (en) * | 1989-09-20 | 1996-08-06 | Fujitsu Limited | Method of forming an x-ray image using photostimulable phosphor |
| CN1207758A (en) * | 1996-01-22 | 1999-02-10 | 化成光学仪器株式会社 | Photostimulable phosphor |
| US6284156B1 (en) * | 1998-11-19 | 2001-09-04 | Kabushiki Kaisha Ohara | Long-lasting phosphor, powdered long-lasting phosphor and method for manufacturing the powdered long-lasting phosphor |
-
2001
- 2001-10-30 JP JP2001331855A patent/JP4122752B2/en not_active Expired - Fee Related
-
2002
- 2002-10-29 CN CN 200610141650 patent/CN1932930B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543080A (en) * | 1989-09-20 | 1996-08-06 | Fujitsu Limited | Method of forming an x-ray image using photostimulable phosphor |
| CN1207758A (en) * | 1996-01-22 | 1999-02-10 | 化成光学仪器株式会社 | Photostimulable phosphor |
| US6284156B1 (en) * | 1998-11-19 | 2001-09-04 | Kabushiki Kaisha Ohara | Long-lasting phosphor, powdered long-lasting phosphor and method for manufacturing the powdered long-lasting phosphor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003132803A (en) | 2003-05-09 |
| CN1932930A (en) | 2007-03-21 |
| JP4122752B2 (en) | 2008-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100405522C (en) | plasma display device | |
| CN1932930B (en) | Plasma display device | |
| EP1506989A1 (en) | Plasma display unit | |
| JP4415578B2 (en) | Plasma display device | |
| JP4244727B2 (en) | Plasma display device | |
| JP4244726B2 (en) | Plasma display device | |
| JP2008050523A (en) | Plasma display device and light-emitting device | |
| JP4333064B2 (en) | Plasma display display device and video display system using the same | |
| US20090058254A1 (en) | Phosphor and light-emitting device | |
| CN101160372B (en) | Phosphor and light emitting device | |
| KR100621125B1 (en) | Plasma display device | |
| US7410599B2 (en) | Stable green phosphor and plasma display panel using the same | |
| JP2001135239A (en) | Plasma display unit and picture image display system using the same | |
| JP2003151444A (en) | Plasma image screen | |
| JP5212553B2 (en) | Plasma display panel | |
| US6967440B2 (en) | Plasma display panel with a green phosphor composed of a mixture of aluminates of spinel structure | |
| JPH11172241A (en) | Phosphor material, phosphor film, and plasma display panel | |
| JP2004010706A (en) | Blue phosphor and display device using the same | |
| JP2010177073A (en) | Plasma display panel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: HITACHI LTD. Free format text: FORMER OWNER: HITACHI,LTD. Effective date: 20130718 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20130718 Address after: Tokyo, Japan Patentee after: Hitachi Consumer Electronics Co.,Ltd. Address before: Tokyo, Japan Patentee before: Hitachi Manufacturing Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100512 Termination date: 20151029 |
|
| EXPY | Termination of patent right or utility model |