CN101483945A - Green inorganic thin-film electrofluorescence display - Google Patents
Green inorganic thin-film electrofluorescence display Download PDFInfo
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- CN101483945A CN101483945A CNA2008100325493A CN200810032549A CN101483945A CN 101483945 A CN101483945 A CN 101483945A CN A2008100325493 A CNA2008100325493 A CN A2008100325493A CN 200810032549 A CN200810032549 A CN 200810032549A CN 101483945 A CN101483945 A CN 101483945A
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Abstract
The invention provides a green inorganic thin-film electroluminescent display which belongs to the electroluminescent display field. The display includes a glass substrate, a bottom electrode layer is set on the glass substrate, a down media layer is set on the bottom electrode layer, a down electronic inject layer is set on the down media layer, an irradiation layer is set on the down electronic inject layer, an upper electronic inject layer is set on the irradiation layer, an upper media layer is set on the upper electronic inject layer, a top electrode layer is set on the upper media layer, the top electrode layer connects with one end of a AC pulse electrical power source through lead, another end of the AC pulse electrical power source connects with the bottom electrode layer. The inorganic thin-film electroluminescent display has high brightness, better stability and low threshold voltage.
Description
Technical field
The invention belongs to electroluminescence Display Technique field, relate in particular to a kind of interchange inorganic thin-film electrofluorescence display, specifically is a kind of green inorganic thin-film electrofluorescence display.
Background technology
The development of inorganic thin-film electrofluorescence display (TFELD) has had the history in more than 70 year since G.Destriau finds electro optical phenomenon, though numerous scientists has done unremitting effort for a long time, but also just rest at present on the level of monochromatic and polychrome, wherein main cause is that the brightness and the colour purity of the required red, green, blue three primary colors Smalt of realization full color do not reach requirement.Though developed successfully that the white light that produces with the ZnS:Mn/SrS:Ce stacking produces red, green, blue three primary colors (color-by-white) by colour filter and with BaAl
2S
4: the red, green, blue three primary colors (color-by-blue) that the blue light that Eu produces produces by the color conversion film realize the technology of full color, but do not obtain to have the breakthrough of industrialization meaning so far.Full color based on the red, green, blue three primary colors shows the method that is still most important realization full color in the inorganic EL field.At present, the required redness of inorganic EL can obtain by the ZnS:Mn+ colour filter, has reached 70cd/m under 60Hz
2, near the level of practicability; The thin-film material that produces green glow has sulfide ZnS:TbOF, SrS:Ce and ZnS:Mn+ colour filter, and the brightness of ZnS:TbOF has reached 100cd/m under 60Hz
2, luminous for blue-green, SrS:Ce has reached 110cd/m under 60Hz
2The ZnS:Mn+ colour filter has reached 160cd/m under 60Hz
2, near the requirement of practicability.Monochromatic red, the green multicolor displaying that shows or pass through the realization of ZnS:Mn+ colour filter of at present commercial TFELD, all need to use sulfide luminescent material to damp vapour sensitivity, not only need strict packaging technology, and the preparation technology of light-emitting film is restricted bigger, generally can only adopt the relatively poor electron beam evaporation method of uniformity, and the color saturation red, green glow that obtains by colour filter is not enough.The another kind of material of realizing green glow EL is the oxide luminescent material that is causing concern, and outstanding representative wherein is Zn
2Si
xGe
1-xO
4: Mn, it has overcome sulfide and has been afraid of the characteristic of tide, so does not need strict packaging technology, and does not need colour filter just can obtain pure green glow.As far back as 1991, the T.Minami of Japan etc. studied Zn
2SiO
4: the electroluminescence of Mn (Jpn.J.Appl.Phys., 1991,33:L117), because the annealing crystallization temperature more than 900 ℃, has limited the use of glass substrate.The TFT-LCD industry the high temperature resistant TFT glass that generally adopts, its strain point is lower than 660 ℃, can not satisfy the annealing requirement of this material.Afterwards, Canadian T.Xiao etc. had prepared Zn
2Si
xGe
1-xO
4: the Mn film (Can.J.Phys., 1996,74:132), annealing temperature is dropped to 700 ℃, find that simultaneously the x value is best in the brightness of 0.5 o'clock device, under 60Hz, obtained 343cd/m
2Brightness, but that used at that time is BaTiO
3Ceramic substrate.Calendar year 2001, the J.P.Bender of the U.S. has prepared Zn
2GeO
4: Mn TFEL device, find that annealing temperature can drop to 620 ℃, under 60Hz, obtained 70cd/m
2Brightness (J.Lumin., 2002,99:311), but colour purity relatively poor (the EL peak is at 540nm), and a bad secondary peak that causes of luminescent layer crystallization is arranged near 640nm.Recently, T.Minami points out that by composite powder target experiment the x value is that the brightness of 0.6 o'clock device is best, has obtained 1536cd/m under 60Hz
2Brightness, but its driving voltage is difficult to be put to practical application (Thin Solid Films, 2006,494 (1): 33) up to 600V.Find out Zn from above-mentioned work
2Si
xGe
1-xO
4: Mn is the most promising at present oxide green glow EL material, the result of its compositional optimization, and promptly the x value is between 0.5-0.6, and Mn is 2-4% with respect to the molar content of Zn, and the expert by this field is generally acknowledged.Other oxide green light material such as Ga
2O
3: Mn and ZnGa
2O
4: the brightness of Mn and colour purity all also have problems.But, Zn
2Si
xGe
1-xO
4: Mn film TFEL device enters the production phase far away, also needs to reduce threshold voltage, further improves brightness and reliability, also need improve annealing conditions simultaneously to adapt to the requirement of substrate.The threshold voltage of the TFEL device of this luminescent material is generally 170-260V at present, and higher relatively driving voltage is to the demands for higher performance of dielectric layer.In order to address this problem, A.H.Kitai has proposed SrTiO
3(50nm, sputter)/Zn
2Si
0.5Ge
0.5O
4: Mn (700nm)/SrTiO
3(2 μ m, sputter-sol-gel-sputter) device architecture, attempt the quality factor that Ca-Ti ore type compound medium layer by high-k improves dielectric layer and make have more voltage to be loaded on the luminescent layer when loading, thereby reduce the threshold voltage of device.Adopt the TFEL device of this method preparation, the threshold voltage under 60Hz is 170V, L
40Be 205cd/m
2(US PatApp12003/0039813A1).But this device architecture is difficult to obtain practical application.Mainly be sputtering sedimentation SrTiO on the ito glass substrate
3Film can cause large-area peeling off.According to our result of study, the SrTiO of 550 ℃ of following sputtering sedimentations on ITO
3Film, intact zone in the pixel and the polarized light microscopy photo that peels off the zone are seen Fig. 2 (a) and (b) respectively, the zone of peeling off is spherical one by one bubbling.Ba for 500 ℃ of following sputtering sedimentations on ITO
0.5Sr
0.5TiO
3Film, intact zone in the pixel and the polarized light microscopy photo that peels off the zone are seen Fig. 3 (a) and (b) respectively, peel off with the form that cohesion is ftractureed, with SrTiO
3The film difference.The reason of peeling off is ITO and SrTiO
3Between exist oxygen affinity to close reaction, the problem that is combined with at interface.Because the above-mentioned defective of end medium, even make single pixel El element begin just to produce sparking at 30V, and almost every increase 1V voltage will produce sparking, and most devices just burn less than 150V.We have studied sputtering parameter to deposit SrTiO on ITO
3, Ba
0.5Sr
0.5TiO
3High depositing temperature, low sputter gas O are found in the influence of film separation phenomenon
2Content, thin thickness helps to alleviate peeling phenomenon, and the variation of target-substrate distance, sputtering power and air pressure is less to the peeling phenomenon influence of film.In the scheme of A.H.Kitai, the elemental area of use is 0.8mm only
2, just have the higher probability that do not peel off.This patent adopts dual mode to solve up hill and dale and deposit SrTiO on ITO
3Film or Ba
xSr
1-xTiO
3Peeling phenomenon: 1) at ITO and SrTiO
3Or Ba
xSr
1-xTiO
3Insert reactive sputtering or the aluminum oxide film of electron beam evaporation or the sialon film of rf magnetron sputtering of a bed thickness 50-150nm between the film; 2) adopt non-sputtering method deposition, we have adopted electron beam evaporation to prepare SrTiO
3Or Ba
xSr
1-xTiO
3Film.Found that,, still fail effectively to overcome the spark phenomenon under the low-voltage though a kind of method in back has overcome film separation effectively.Because the SrTiO of electron beam evaporation
3Or Ba
xSr
1-xTiO
3The poor adhesive force of film and ITO.And preceding a kind of scheme can be brought up to the voltage of initial sparking more than the 150V, and the lasting spark phenomenon when up voltage not occurring, has significantly improved the voltage that device burns simultaneously.
Second problem of the above-mentioned device architecture of A.H.Kitai is self-cure type SrTiO
3(2 μ m sputter/sol-gel/sputter) go up medium and are difficult to obtain, and bigger realization probability can only just be arranged on very little electrode area.And the elemental area that the display device of Practical significance is arranged wants big 3 more than the order of magnitude.We have repeated above-mentioned dielectric structure, the SrTiO that is adopted
3Or Ba
xSr
1-xTiO
3Film is though quality factor is up to 50 μ C/cm
2, exceed an order of magnitude than the quality factor of generic media, but its disruptive field intensity has only 30MV/m.We find that the dielectric layer electric leakage is serious in addition, and the Δ vy that records with the Sawyer-Tower circuit (reflects the parameter of ac leakage, is directly proportional with tan δ) up to 1 volt, and the thick Ta of the 200nm of pulse reaction sputter
2O
5The Δ vy of film is only about 0.02V.Above-mentioned elaboration points out that the reason that the result difference of our data and A.H.Kitai is big mainly is that the area of electrode wants big 57 times.
The 3rd problem of the above-mentioned device architecture of A.H.Kitai is self-cure type SrTiO
3(2 μ m sputter/sol-gel/sputter) go up medium, be through 3 road high-temperature technologies, sputtering sedimentation SrTiO
3The substrate temperature of film is usually more than 500 ℃, and the SrTiO of sol-gel deposition
3Film will be through the crystallinity of 600 ℃ of high temperature sinterings to obtain.This will produce the destruction that is difficult to expect to following dielectric layer, increase the oxygen defect of medium down, under conduction band, produce shallow donor's energy level that numerous degree of depth differs, thereby the L-V performance produces serious conditions of streaking when loading, promptly just bright at the following device of threshold voltage, reduce the contrast of device, reduce the steepness of L-V curve, promptly reduce L
50Another problem is possible cause that harmful substance is diffused into luminescent layer in the medium, has perhaps increased the thickness of the dielectric dead layer of luminescent layer-dielectric layer, thereby makes the electronics at interface be injected into the luminescent layer difficulty that becomes.
Even there are the problems referred to above, the initiative work of A.H.Kitai is still be worth to use for reference.
In fact, high-k SrTiO
3, Ba
xSr
1-xTiO
3Film can provide good electronics to inject the interface, and thickness does not need very thick usually, and is best at 100-200nm according to our result of study to the ZnS:Mn device, and key is to obtain good crystallinity and interface.Below 50nm because the poor effect that the dielectric dead layer effect electronics at interface injects, the too thick outstanding problem that then has stress and light absorption.SrTiO
3, Ba
xSr
1-xTiO
3The dielectric constant of film is subjected to the influence of deposition process and process conditions very remarkable, and difference is up to 1-2 the order of magnitude sometimes.If thin film composition control is improper, can cause dielectric constant with temperature to change greatly, be unfavorable for the steady operation of the TFEL device of AC driving.Simultaneously,, need to adopt 500 ℃ of high temperature deposition or annealing (〉 for the crystallinity that obtains), this also can influence the withstand voltage properties of end dielectric layer.Therefore, adopt SrTiO
3, Ba
xSr
1-xTiO
3Film also has certain limitation as the electron injecting layer material of TFEL device.Therefore, HfO has also been attempted in this work
2, Y
2O
3, TiO
2, ATO, ZrO
2, Y
2O
3Deng material, and with adopt SrTiO
3, Ba
xSr
1-xTiO
3Film is that the performance of the device of electron injecting layer is contrasted.
In order further to improve the withstand voltage properties of device, we have groped can be used as the material preferably of medium, mainly are the Ta of reactive sputtering
2O
5, Al
2O
3With the sialon of rf magnetron sputtering, be according to its sedimentary condition is optimized with dielectric property.
In addition, we to the brightness of device and the influence of threshold voltage, have done detailed research to the thickness of luminescent layer and sedimentary condition.In the above-mentioned example, the light emitting layer thickness of employings such as A.H.Kitai is 0.7 μ m, and the light emitting layer thickness of employings such as T.Miyata is 1 μ m, and the thickness range of this work is 0.3-1.25 μ m.Set about from the preparation of target simultaneously, to improve the performance of luminescent layer.
In a word, from prior art level both domestic and external, with Zn
2Si
xGe
1-xO
4: Mn is that the inorganic thin-film electrofluorescence display spare of luminescent layer enters before the industrialization, also needs to improve brightness, efficient and reliability, and threshold voltage is reduced to the zone of reasonableness below the 180V, further reduces manufacturing cost.And the solution of these problems relies on the selection of performance good electron implanted layer, dielectric material and the technology of optimization to a great extent.
Summary of the invention
The object of the present invention is to provide a kind of green inorganic thin-film electrofluorescence display, described this green inorganic thin-film electrofluorescence display will solve of the prior art with Zn
2Si
xGe
1-xO
4: Mn is that the inorganic thin-film electrofluorescence display brightness of luminescent layer is low, poor reliability, technical problem that threshold voltage is high.
The invention provides a kind of green inorganic thin-film electrofluorescence display, comprise a glass substrate, described glass substrate is provided with a bottom electrode layer, described bottom electrode layer is provided with a following dielectric layer, described dielectric layer down is provided with down electron injecting layer, described electron injecting layer down is provided with luminescent layer, described luminescent layer is provided with electron injecting layer, electron injecting layer is provided with dielectric layer on described, dielectric layer is provided with top electrode layer on described, described top electrode layer is connected by an end of a lead and an alternating-current pulse power supply, and an other end of described alternating-current pulse power supply is connected with described bottom electrode layer.
Further, described dielectric layer down adopts sialon or Al
2O
3Film or sialon and Al
2O
3Laminated film.
Further, described sialon film adopted the Y-alpha-beta sialon solid-phase sintering target and the radio-frequency magnetron sputter method preparation of high compaction, and wherein, α accounts for 30% mutually in the Y-alpha-beta sialon target, 1800 ℃ of following gas pressure sinterings 5 hours.
Further, when described sialon film adopted radio-frequency magnetron sputter method to prepare, its working gas was Ar+O
2Or Ar+N
2, sedimentary condition is: base vacuum is 1.0-5.0 * 10
-3Pa, power are 200-300W, and substrate temperature is 100-300 ℃, N
2/ (Ar+N
2) or O
2/ (Ar+O
2) than being 20-35%, air pressure is 0.4-0.7Pa, target-substrate distance is 6.0-8.4cm, deposition rate is between 3.0-6.5nm/min.
Further, the thickness of described sialon film is between 50-150nm.
Further, described Al
2O
3Film adopts the preparation of pulse reaction sputtering method, and its working gas is Ar+O
2, sedimentary condition is: base vacuum is 1.0-3.0 * 10
-3Pa, power are 100-400W, and substrate temperature is 100-300 ℃, O
2/ (Ar+O
2) than being 70-90%, air pressure is 1.5-2.5Pa, target-substrate distance is 6.0-8.4cm, deposition rate is between 0.5-1.5nm/min.
Further, described Al
2O
3Film adopts the electron-beam vapor deposition method preparation, and its sedimentary condition is: base vacuum is 2.5-3.5 * 10
-3Pa, substrate temperature are 100-200 ℃, and deposition rate is 12.0-18.0nm/min.
Further, described Al
2O
3The thickness of film is between the 50-150nm.
Further, described electron injecting layer down is high K oxide, is selected from Ba
xSi
1-xTiO
3, or SrTiO
3, or HfO
2, or TiO
2, or Al
2O
3-TiO
2, or Y
2O
3, or ZrO
2
Further, described electron injecting layer down adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described Ba
xSi
1-xTiO
3The sputtering sedimentation condition of film: base vacuum is 1.6 * 10
-3Pa, substrate temperature are 450 ℃, and radio-frequency power is 500W, O
2/ (Ar+O
2) than for 10-20%, air pressure 0.1Pa,, deposition rate is 0.3-1.0nm/min.The depositing device that is adopted is a SP450 rf magnetron sputtering continuous coating system.
Further, employed Ba
xSi
1-xTiO
3The sintering target is of a size of 55 * 11cm
2, by 5 11 * 11cm
2Block is spliced.
Further, described electron injecting layer down adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described SrTiO
3The evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O2 air pressure are 3.0 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 3.0-9.0nm/min.The equipment that is adopted is the ZZSX-800 electron beam coater.
Further, described electron injecting layer down adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described HfO
2The evaporation conditions of film: base vacuum is 2.0-3.0 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 6.0-18.0nm/min.The equipment that is adopted is the ZZSX-800 electron beam coater.
Further, described electron injecting layer down adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described Y
2O
3The evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, 12.0-18.0nm/min.The equipment that is adopted is the ZZSX-800 electron beam coater.
Further, described electron injecting layer down adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described TiO
2And Al
2O
3-TiO
2(ATO) evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 12.0-18.0nm/min.The equipment that is adopted is the ZZSX-800 electron beam coater.
Further, the thickness of described electron injecting layer down is between 50-300nm.Preferably, the thickness of described electron injecting layer down is between 100-200nm.
Further, the material of described luminescent layer is Zn
2Si
xGe
1-xO
4: Mn.The x value of described luminescent layer is between 0.5-0.6.
Further, described luminescent layer adopts the radio-frequency magnetron sputter method preparation, and its target is 3 inches dry-pressing solid-phase sintering targets, and employed original powder is high-purity Zn
2SiO
4: Mn, ZnO, GeO
2, MnO
2, briquetting pressure 5-10MPa.Sintering condition is that temperature 1150-1250 ℃, time 2-5 hour, atmosphere are argon gas or air.
Further, three inches sintering circle targets depositions that described luminescent layer adopts, its condition are, substrate temperature 150-350 ℃, and power 300-400W, O
2/ (O
2+ Ar) than 10-30%, air pressure 0.4-2.5Pa, target-substrate distance 6.0-8.4cm.
Further, described luminescent layer adopts the radio-frequency magnetron sputter method preparation, and its target is the powder circle target that 3 inches dry-pressing or isostatic cool pressing are handled, and dry-pressing pressure is 5-10MPa, and the isostatic cool pressing processing pressure is 180-200MPa.
Further, described luminescent layer adopt for three inches powder circle targets, its sedimentary condition is, substrate temperature 150-300 ℃, power 100-200W, O
2/ (O
2+ Ar) than 10-30%, air pressure 0.4-2.5Pa, target-substrate distance 6.0-8.4cm.
Further, described luminescent layer adopts the radio-frequency magnetron sputter method preparation, and its target is 8 * 15cm
2Dry-pressing or the rectangular target of powder handled of isostatic cool pressing, dry-pressing pressure 12-17MPa, isostatic cool pressing processing pressure 180-200MPa.
Further, the rectangular target deposition of the powder that described luminescent layer adopts, its condition be, substrate temperature 150-300 ℃, and power 200-300W, O
2/ (O
2+ Ar) than 10-30%, air pressure 0.4-2.5Pa, target-substrate distance 6.0-8.4cm.
Further, the thickness of described luminescent layer is between 300-1250nm
Further, described upward electron injecting layer is high K oxide, is selected from Ba
xSi
1-xTiO
3, or SrTiO
3, or HfO
2, or TiO
2, or Al
2O
3-TiO
2, or Y
2O
3, or ZrO
2
Further, the described electron injecting layer of going up adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described Ba
xSi
1-xTiO
3The sputtering sedimentation condition of film: base vacuum is 1.6 * 10
-3Pa, substrate temperature are 450 ℃, and radio-frequency power is 500W, O
2/ (Ar+O
2) than for 10-20%, air pressure 0.1Pa,, deposition rate is 0.3-1.0nm/min.The depositing device that is adopted is a SP450 rf magnetron sputtering continuous coating system.
Further, employed Ba
xSi
1-xTiO
3The sintering target is of a size of 55 * 11cm
2, by 5 11 * 11cm
2Block is spliced.
Further, the described electron injecting layer of going up adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described SrTiO
3The evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O2 air pressure are 3.0 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 3.0-9.0nm/min.The equipment that is adopted is the ZZSX-800 electron beam coater.
Further, the described electron injecting layer of going up adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described HfO
2The evaporation conditions of film: base vacuum is 2.0-3.0 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 6.0-18.0nm/min.The equipment that is adopted is the ZZSX-800 electron beam coater.
Further, the described electron injecting layer of going up adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described Y
2O
3The evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 12.0-18.0nm/min.The equipment that is adopted is the ZZSX-800 electron beam coater.
Further, the described electron injecting layer of going up adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described TiO
2And Al
2O
3-TiO
2(ATO) evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 12.0-18.0nm/min.The equipment that is adopted is the ZZSX-800 electron beam coater.
Further, the described thickness of electron injecting layer of going up is between 50-300nm.Preferably, the described thickness of electron injecting layer of going up is between 50-150nm.
Further, the described dielectric layer of going up adopts Ta
2O
5, or sialon or Al
2O
3Film or its any laminated film that combines more than two kinds or two kinds.
Further, described sialon film adopted the Y-alpha-beta sialon solid-phase sintering target and the radio-frequency magnetron sputter method preparation of high compaction, and wherein, α accounts for 30% mutually in the Y-alpha-beta sialon target, 1800 ℃ of following gas pressure sinterings 5 hours.
Further, described Ta
2O
5The pulse reaction sputtering condition of film is: base vacuum 2-4 * 10
-3Pa, substrate temperature are 50-80 ℃, the about 6cm of target-substrate distance, pulse frequency 70kHz, duty ratio 30%, power density 2.8-3.1W/cm
2, air pressure 0.5-1.0Pa, O
2/ (O
2+ Ar) compare 50-80%.The depositing device that is adopted is a SP450 rf magnetron sputtering continuous coating system.
Further, the Ta of pulse reaction sputter
2O
5The thickness of film is between 150-400nm.
Further, described Al
2O
3The condition of pulse reaction sputter is: base vacuum 2-3 * 10
-3Pa, substrate temperature room temperature, the about 6cm of target-substrate distance, pulse frequency 70kHz, duty ratio 30%, power density 2.9-3.1W/cm
2, air pressure 0.4-0.6Pa, O
2/ (O
2+ Ar) compare 80-90%.The equipment that is adopted is SP450 vacuum continuous coating system.
Further, employed high-purity Ta target (5N) is of a size of 12 * 56cm
2
Further, described Al
2O
3The condition of radio frequency magnetron reactive sputtering is: base vacuum 1-3 * 10
-3Pa, substrate temperature 100-300 ℃, target-substrate distance 7cm, power 200-300W, air pressure 2.0-3.0Pa, O
2/ (O
2+ Ar) than being 70-90%.The equipment that is adopted is CS500 rf magnetron sputtering continuous coating system.
Further, use the Al target of 3 inches purity of diameter as 5N.
Further, the described medium A l that goes up
2O
3Thickness be between 30-300nm.
Further, the sedimentary condition of the last medium of described sialon is: base vacuum 1.0-5.0 * 10
-3Pa, power are that 200-300W, substrate temperature are 100-300 ℃, N
2/ (Ar+N
2) or O
2/ (Ar+O
2) than being that 0.4-0.7Pa, target-substrate distance are 6.0-8.4cm for 20-35%, air pressure.
Further, described sialon goes up the thickness of medium between 50-350nm.
Aspect the preparation method of target, the present invention adopts five kinds of targets: three inches targets (to call the A target in the following text), and to be mixed with the Zn of 1.1wt.%Mn
2SiO
4Powder (2N), MnO
2Powder (4N), ZnO (4N), GeO
2Powder (5N) does mixed back (the x value is 0.5) dry-pressing and at 1250 ℃/5h sintering, its apparent density is 2.9g/cm
3Second is that above-mentioned powder (the x value is 0.6) mixes back 180 ℃ of following oven dry three of the CIP moulding inches targets (to call the B1 target in the following text) under 200MPa again in alcohol.For mixing back 180 ℃ times in alcohol, above-mentioned powder (x value is 0.5) dries again three inches targets ((to call the B2 target in the following text) dry-pressing formed under 50MPa for the 3rd.Dry and in 740 ℃/2.5h, Ar atmosphere, calcine again for above-mentioned powder (x value is 0.55) mixes back 180 ℃ times in alcohol for the 4th, then 8 * 15cm of dry-pressing under 150MPa
2Rectangular target (to call the C1 target in the following text).The 5th is that above-mentioned powder (the x value is 0.55) mixes back oven dry 8 * 15cm of dry-pressing under 150MPa again in alcohol
2Rectangular target (to call the C2 target in the following text).And these targets are compared the influence of device brightness.
From the device of the green glow film of powder target and sintering target deposition, the powder target also obtains brightness and the colour purity suitable with the sintering target.But the preparation of powder target is simple, and this has just reduced the cost of system target.Another prior advantage is to utilize the easier maintenance of composition consistency of the green glow film target-film of powder target deposition, thereby can obtain more approaching stoichiometric light-emitting film by the composition of control target.The 3rd advantage be, with CIP or dry-pressing formed powder target under the same conditions deposition rate in addition substantially exceeded the sintering target.But we also find, powder target less stable, and the easy moisture absorption, and deposition rate changes after using a period of time, and therefore, the powder target is not easy to long-term use.
Another work, we calcine the powder that mixes in 740 ℃/2.5h, Ar gas, carry out Passivation Treatment, and compare with the performance of the film of the powder target deposition of calcining not.
Though sintering target and powder target are the methods of the most frequently used system target.We are to have adopted CIP method system target first in the innovation part of this work, and have done finer work.
Display device structure Design and improvement are the core contents of this patent.We know, obtain the inorganic EL medium of application at present, as Ta
2O
5, Si
3N
4, SiO
2, Y
2O
3, Al
2O
3, SiON, sialon, ATO, SrTiO
3, BaTiO
3, BST, HfO
2, TiO
2, BaTa
2O
6, Sm
2O
3, PbNbO
6, Ba (Zr, Ti) O
3, PrMnO
3, MnTiO
3, PbTiO
3, PbTeO
3, Nb
2O
5, Bi
2O
3, La
2O
3, ThO
2, SnO
2, PbO, SrO, BaO, WO
2Deng, adopting the form of stacking, the coupling of the coupling of the coupling between the medium, medium and luminescent layer, medium and electrode usually is rather to be particular about, physics and chemical compatibility between considering.The physics compatible main diffusion of considering stress and harmful species, the chemical reaction under the effect of chemically compatible main consideration extra electric field and interface degradation.This patent has designed novel device architecture, and has adopted novel medium.Compare with work in the past, the present invention introduces conductive formation as electron injecting layer, original ITO/SrTiO between upper and lower medium and luminescent layer
3(200nm)/Zn
1.96Mn
0.04Si
0.5Ge
0.5O
4(500nm)/SrTiO
3(300nm)/Ta
2O
5(400nm)/maximum brightness of Al device architecture is from 200cd/m
2Bring up to 250cd/m
2And kept than low threshold voltage 220V (Xiao field, etc., functional material and device journal, 2006,12 (2): 99), more outstanding progress is that the withstand voltage properties of device improves greatly.
In order to improve the puncture voltage of device, this patent has been done useful improvement to the end dielectric device structure of A.H.Kitai etc., overcome effectively on the ITO hearth electrode directly the deposition Ca-Ti ore type ferroelectric/the vaporific phenomenon of peeling off of dielectric film occurrence of large-area, original mode of propagation puncture form is improved to self-cure type punctures form, and the voltage of initial sparking brought up to more than the 150V about by original 50V, thereby greatly improved the withstand voltage properties of device.
For radio frequency magnetron reactive sputtering Al
2O
3, we find the O in the working gas at work in the past
2Content is the most critical factor that influences the special leakage current density of its dielectric property, O
2Content the film of 70-100% deposit have the good insulation performance (Huang Hao, etc., inorganic EL display insulation media process exploitation and application, Chinese patent, application number: 200610029809.2).This experiment finds that also when target-substrate distance was reduced to 4.0cm from 8.4cm, leakage current density increased the 1-2 order of magnitude, concrete result such as Fig. 4, and other dielectric property change little.In order to improve the puncture voltage of device, this patent has proposed the concrete manufacture method of the transition zone sialon film of bottom electron implanted layer and bottom electrode.3 inches round targets of thick 6mm diameter are Y-alpha-beta Sialon material, and α accounts for 30% mutually, and the quality chemistry consists of: Y:6.05%, Al:6.96%, Si:48.66%, all the other are N, O.Gas pressure sintering condition: 1800 ℃, 5 hours.Depositing device is a CS500 rf magnetron sputtering instrument.Table 1, table 2 have been listed Sialon depositing of thin film condition and dielectric property test result under different sedimentary conditions respectively.The effective area 46.25mm of electrode in the mim structure (ITO/Sialon/Al)
2Dielectric property tests is carried out being furnished with on follow-on Sawyer-Tower circuit of nanoammeter.Relative dielectric constant ε in the table 2
r, the reflection dielectric loss parameter Δ V
yUnder 20kHz, test disruptive field intensity E
bTest adopt the triangular wave of direct current or 500Hz, forward leakage current J
+The Al electrode is being for just during test, otherwise the Al electrode is for negative.As seen, no matter at Ar+O
2Or Ar+N
2Deposit in the atmosphere, all have good resistance and wear intensity and leakage current performance.Forward and reverse leakage current J in the table 2
+, J
-Having appeared of having is unusual, this be because the acquisition of these data not at one time, front and back reach half a year, vacuum chamber also is used to deposit multiple semiconductive thin film in the meantime, exists to pollute.It seems that from the data of table 2 leakage current of Sialon film is the most responsive to the pollution of vacuum chamber.
Table 1 Sialon depositing of thin film condition
NO | Base vacuum MPa | Power W | Substrate temperature ℃ | Air pressure Pa | Ar/O 2Compare sccm/sccm | Ar/N 2Compare sccm/sccm | Target-substrate distance cm |
DS1 | 3.5×10 -3 | 250 | 180 | 0.35 | 28/5 | 7.0 | |
DS2 | 3.5×10 -3 | 250 | 180 | 0.35 | 28/5 | 7.0 | |
DS3 | 3.8×10 -3 | 300 | 180 | 0.44 | 30/10 | 8.4 | |
DS4 | 1.8×10 -3 | 300 | 180 | 0.65 | 45/15 | 8.4 | |
DS5 | 1.8×10 -3 | 300 | 180 | 1.30 | 90/10 | 8.4 | |
DS6 | 1.8×10 -3 | 300 | 180 | 1.95 | 134/45 | 8.4 | |
DS7 | 1.8×10 -3 | 300 | 180 | 2.60 | 180/60 | 8.4 | |
DS8 | 3.8×10 -3 | 300 | 180 | 3.50 | 240/80 | 8.4 | |
DS9 | 3.5×10 -3 | 300 | 27 | 0.65 | 45/15 | 3.5 | |
DS10 | 3.5×10 -3 | 300 | 27 | 0.65 | 45/15 | 8.4 | |
DS11 | 3.0×10 -3 | 350 | 260 | 0.65 | 45/15 | 8.4 | |
DS12 | 3.0×10 -3 | 300 | 260 | 0.65 | 45/15 | 8.4 | |
DS13 | 3.5×10 -3 | 250 | 180 | 0.35 | 28/5 | 7.0 | |
DS14 | 3.5×10 -3 | 250 | 180 | 0.35 | 28/5 | 7.0 |
The dielectric property of table 2 Sialon film under different sedimentary conditions
NO | Thickness/nm | ε r | ΔVy/V | E b/MV/m | J.@0.05V/nm A | J_@0.05V/nm A |
DS1 | 195 | 4.37 | >640 | 0.016@500Hz | 5.0×10 -10 | 5.0×10 -8 |
DS2 | 98 | 4.77 | 318 | 0.020@500Hz | 4.0×10 -9 | 5.0×10 -6 |
DS3 | 87 | 2.13 | 0.072 | 402 direct currents | 5.7 X 10 -6 | 1.2 X 10 -7 |
DS4 | 128 | 4.17 | 0.02 | 344@500Hz | <10 -10 | <10 -10 |
DS5 | 127 | 3.62 | 0.02 | 299@500Hz | <10 -10 | <10 -10 |
DS6 | 144 | 3.75 | 0.02 | 347@500Hz | <10 -10 | <10 -10 |
DS7 | 119 | 3.78 | 0.02 | 387@500Hz | <10 -10 | <10 -10 |
DS8 | 119 | 3.54 | 0.02 | 546 direct currents | 8.0 X 10 -8 | 2.7 X 10 -9 |
DS9 | 251 | 4.91 | 0.02 | 311@500Hz | <10 -10 | <10 -10 |
DS10 | 130 | 4.19 | 0.068 | 269 direct currents | 9.5 X 10 -8 | 1.2 X 10 -8 |
|
170 | 4.23 | 0.10 | 265 direct currents | 9.7 X 10 -7 | 4.5 X 10 -8 |
DS12 | 119 | 4.25 | 0.10 | 546 direct currents | 2.0 X 10 -7 | 4.2 X 10 -7 |
DS13 | 124 | 4.25 | 0.010 | 362@500Hz | 3.5×10 -7 | 9.8×10 -6 |
DS14 | 311 | 4.56 | 0.0025 | >402@500Hz | 6.0×10 -10 | 4.0×10 -8 |
For improve device puncture voltage, this patent has proposed novel last dielectric stack structure.
In order to improve the puncture voltage of device, last medium adopts and end medium A l
2O
3, the Sialon unanimity optimized process conditions, Ta
2O
5Last medium adopt in the past optimized conditions (Xu Yi, etc., dc magnetron reactive sputtering is made Ta
2O
5Technology and electrology characteristic research, Shanghai: 2004 Chinese flat panel display academic meeting paper collection, 198-201).
In order to obtain appropriate threshold voltage and high brightness, this patent is groped the light emitting layer thickness that above-mentioned device architecture allowed.Having prepared light emitting layer thickness is the single-phase plain device of 300-1250nm, finds the suitableeest thickness 300-700nm, more relevantly says 350-550nm.
Say that further light emitting layer thickness is 350-450nm, the threshold value of device can be low to moderate below the 160V under 200Hz, pulsewidth 50 μ s test conditions, and L
50Can reach 70cd/m
2More than.
Simultaneously, the sedimentary condition optimization for the solid-phase sintering target found that O
2Content, substrate temperature are to L
50Influence faint, and air pressure is high more, L
50Good more; But, do not find L for the powder target
50Air pressure there is significant dependence.Also be to say,, have the depositing operation scope of broad for the powder target.
Say further, in order to improve the L of device
50, this patent has been done Study on thinning to the composition of target on (T.Xiao, et al, x=0.5, T.Minami, the et al x=0.6) basis of in the past working, and the target of preparation x=0.6, x=0.50 and three kinds of compositions of x=0.55 is found L
50Influence very not remarkable.
In order to improve the L of device
50, this patent is annealed in oxygen atmosphere under the temperature that substrate allows, in the hope of reducing the oxygen room in the film, to obtain near stoichiometric light-emitting film, to improve the luminous colour purity of device.
Say further, in order to improve the L of device
50With colour purity, after the luminescent layer deposition, in oxygen atmosphere, to anneal, air pressure is between 0.01-0.08Pa.
Say further, in order to improve the L of device
50With colour purity, after the luminescent layer deposition, annealing temperature is between 700-710 ℃.
In order to realize above-mentioned target, we have organized three batches of experiments.
One, first experiment
The first round experimental design sialon/Al
2O
3, siaoln, Al
2O
3Dielectric structure at the bottom of three kinds, following electron injecting layer is Ba
0.5Sr
0.5TiO
3, last electron injecting layer is HfO
2, last medium adopts Ta
2O
5/ Al
2O
3Stack architecture.The deposition of luminescent layer adopt three inches sintering circle targets (the A target, x=0.5), three inches powder circle targets (the B1 target, x=0.6), rectangular target (the Cl target, x=0.55).
It is the Zn that is mixed with 1.1wt%Mn that target prepares employed starting powder
2SiO
4: Mn powder (2N, East China Electronics Co., Ltd fluorescent material Co., Ltd), ZnO powder (4N, Tianjin good fortune chemical reagent in morning factory), GeO
2Powder (5N, the safe copper industry of last oceanic rise Co., Ltd), MnO powder (3N, the Huaihua milky way in Hunan is smelted Co., Ltd).Each component powders of sintering target (A target, x=0.5)) is done and is mixed the back dry-pressing, and pressure is about 8MPa, and sintering condition is 1250 ℃/5h, and atmosphere is atmosphere.(the B1 target, raw material x=0.60) mixes in analyzing the absolute alcohol medium three inches powder targets, dries after CIP handles pressure 200MPa for 180 ℃.15 * 8cm
2Rectangular target (the C1 target, raw material x=0.55) mixes in analyzing the absolute alcohol medium, and Passivation Treatment in the Ar of 0.04Pa atmosphere and under the 740 ℃/2.5h is dry-pressing formed under 150MPa pressure then after 180 ℃ of oven dry.
Glass substrate and cleaning method have been made detailed elaboration (Huang Hao etc., inorganic EL display insulation media process exploitation and application, application number: 200610029809.2) in our preceding a patent.The structure of designed various devices and EL performance are listed in the table 3.The deposition process of luminescent layer sees Table 4, and the luminescent layer annealing conditions is 710 ℃/1h, and atmosphere is pure O
2, pressure 0.01Pa.The deposition process of upper and lower electron injecting layer and medium sees Table 5.The L-V performance test is carried out on the High-voltage Signal Generator of self assembly, and frequency is 200Hz, and pulsewidth is 50 μ s.Luminance test adopts LS-100 brightness instrument.The testing apparatus of CIE chromaticity coordinates is PR-705 type spectrascanspectraradiometer.Table 6 has been listed the L-V test result of this batch experiment.
This batch of experiment Main Conclusions has: from brightness, 3 inches sintering targets are good slightly, but also can obtain suitable with it brightness with the powder target of straightforward procedure preparation; Luminescent layer is with powder target deposition, and its threshold value will exceed the about 30V of solid sintering target, and its reason may be that x is higher, and the temperature of annealing crystallization is higher; The threshold value of the device of device of no electron injecting layer (sample 1-2) and single electron implanted layer exceeds the device 30-50V of bielectron implanted layer, but withstand voltagely also exceeds 30-50V; From L
50See that the influence of sputtering power is not remarkable; Imperfect crystal made the distortion of Mn ligand cause when sample 1-1,1-4,1-6 existed orange-yellow secondary peak to be film annealing.
The 1st batch of device architecture of table 3 and EL performance
The 1st batch of device luminescent layer sedimentary condition of table 4
The 1st batch of upper and lower dielectric deposition condition of device of table 5
Annotate: sample 1-2 sialon under medium at Ar/O
2Middle deposition, all the other are at Ar/N
2Middle deposition.
The 1st batch of device L-V data of table 6
Two, second batch of experiment
The 2nd batch of experiment divides two groups.Adopting target is powder B2 target (x=0.5) and C2 target (x=0.55).The 1st group of device architecture and EL performance see Table 7.The luminescent layer sedimentary condition sees Table 8.Annealing conditions is the pure O of 700 ℃/2h, 0.02Pa
2Atmosphere, substrate flexural deformation is obvious.The sedimentary condition of upper and lower electron injecting layer and medium sees Table 9.The L-V performance sees Table 10.Following electron injecting layer adopts 125nm or the thick BST of 190nm, closes the film separation that reaction causes in order to overcome BST and hearth electrode because of oxygen affinity, has introduced the sialon of the rf magnetron sputtering of 50-150nm between BST and hearth electrode.The result shows, no matter sialon is at Ar/O
2Or Ar/N
2Deposit in the atmosphere, all can improve the interface of BST/ITO effectively.Simultaneously, last electron injecting layer adopts thick BST of 200nm or the HfO of 100nm
2, last medium then changes the sialon of rf magnetron sputtering or the Al of radio frequency magnetron reactive sputtering into
2O
3The 1st group last medium is thinner, and resultant device is less than L
50Just burn.
Just begin sparking at tens volts in these samples, and continue sparking in the up voltage process, the withstand voltage 270V that is no more than of all devices, majority burns below 200V.Have only 120V though its threshold voltage is minimum, most devices are less than L
50Just burn.The form of burning is mode of propagation.Its reason is to go up the thickness low LCL of medium sialon.Maximum brightness is the L of sample 2-6
40Be 121cd/m
2As can be seen, last electron injecting layer HfO
2Effect be better than BST, this is because be amorphous state basically at the BST of 450 ℃ of deposit.
The 2nd batch of the 1st group of device architecture of table 7 and EL performance
The 2nd batch of the 1st group of device luminescent layer sedimentary condition of table 8
NO | Target | Base vacuum Pa | Power W | Substrate temperature ℃ | Ar/O 2Ratio | Air pressure Pa | Target-substrate distance cm | Speed nm/min |
2-1 | B2 | 5.7×10 -4 | 128 | 220 | 210/30 | 2.7 | 7.0 | 2.8 |
2-2 | C2 | 9.0×10 -4 | 300 | 210 | 140/20 | 1.8 | 8.4 | 9.7 |
2-3 | B2 | 1.0×10 -3 | 125 | 220 | 140/20 | 1.8 | 7.0 | 4.4 |
2-4 | B2 | 2.3×10 -3 | 125 | 220 | 140/20 | 1.8 | 7.0 | 2.9 |
2-5 | B2 | 2.3×10 -3 | 125 | 220 | 140/20 | 1.8 | 7.0 | 3.9 |
2-6 | B2 | 2.3×10 -3 | 125 | 220 | 210/30 | 2.7 | 7.0 | 3.8 |
2-7 | B2 | 5.7×10 -4 | 128 | 220 | 210/30 | 2.7 | 7.0 | 3.3 |
2-8 | B2 | 5.7×10 -4 | 128 | 220 | 210/30 | 2.7 | 7.0 | 2.9 |
2-9 | B2 | 5.7×10 -4 | 128 | 220 | 210/30 | 2.7 | 7.0 | 3.3 |
The 2nd batch the 1st group upper and lower dielectric deposition condition of device of table 9
The 2nd batch of the 1st group of device L-V data of table 10
The 2nd batch the 2nd group experiment increased last medium sialon, Al
2O
3Thickness.Device architecture and EL performance see Table 11.The luminescent layer sedimentary condition sees Table 12.Annealing conditions is: 700 ℃/2h, the pure O of 0.02Pa
2Atmosphere, the substrate distortion obviously.The sedimentary condition of upper and lower electron injecting layer and medium sees Table 13.The L-V performance sees Table 14.
The 2nd group of device increased dielectric thickness, and the sparking point has clear improvement, and the voltage that device burns also obviously improves.L
50Be significantly improved, 2-19 reaches 128cd/m
2This brightness differs still far away with the result who has abroad delivered, but looked back in background technology as this patent, and abroad these results are put to practicality and also have all difficulties technically.We think that the reason of this species diversity is on the crystallinity of the light-emitting film that obtained.Compare with the 1st batch of device, the initial sparking point of the 2nd batch of the 2nd group of device is lower, particularly sample 2-14,2-18 just sparking about 50V, its reason is that annealing time length has destruction to glass substrate, in other words the strain point of employed glass substrate lower (660 ℃).
The 2nd batch of the 2nd group of device architecture of table 11 and EL performance
The 2nd batch of the 2nd group of device luminescent layer sedimentary condition of table 12
NO | Target | Base vacuum Pa | Power W | Substrate temperature ℃ | Ar/O 2Compare sccm/sccm | Air pressure Pa | Target-substrate distance cm | Speed nm/min |
2-10 | C2 | 9.0×10 -4 | 300 | 210 | 140/20 | 1.8 | 8.4 | 11.2 |
2-11 | C2 | 9.0×10 -1 | 300 | 210 | 140/20 | 1.8 | 8.4 | 12.0 |
2-12 | C2 | 9.0×10 -1 | 300 | 220 | 140/20 | 1.8 | 8.4 | 10.6 |
2-13 | C2 | 1.3×10 -3 | 300 | 220 | 140/20 | 1.8 | 8.4 | 6.7 |
2-14 | C2 | 1.3×10 -3 | 300 | 220 | 210/30 | 2.7 | 8.4 | 8.5 |
2-15 | B2 | 2.3×10 -3 | 250 | 220 | 140/20 | 1.8 | 8.4 | 4.3 |
2-16 | C2 | 1.3×10 -3 | 300 | 220 | 210/30 | 2.7 | 8.4 | 8.5 |
2-17 | C2 | 1.3×10 -3 | 300 | 220 | 210/30 | 2.7 | 8.4 | 8.5 |
2-18 | B2 | 2.3×10 -3 | 250 | 220 | 140/20 | 1.8 | 8.4 | 4.3 |
2-19 | B2 | 2.3×10 -3 | 200 | 220 | 140/20 | 1.8 | 8.4 | 3.5 |
2-20 | C2 | 1.3×10 -3 | 300 | 210 | 210/30 | 2.7 | 8.4 | 8.5 |
2-21 | B2 | 2.0×10 -1 | 125 | 210 | 210/30 | 2.7 | 7.0 | 3.3 |
The 2nd batch the 2nd group upper and lower dielectric deposition condition of device of table 13
The 2nd batch of the 2nd group of device L-V data of table 14
Three, the 3rd batch of test
The 3rd batch of designs time medium be sialon and Al
2O
3, following electron injecting layer is HfO
2And SrTiO
3, last electron injecting layer is HfO
2And ATO.Device architecture and EL performance see Table 15.The luminescent layer sedimentary condition sees Table 16.Annealing conditions is: 700 ℃/1h, and the pure O of 0.08Pa
2Atmosphere.The sedimentary condition of upper and lower electron injecting layer and medium sees Table 17.The L-V performance sees Table 18.This batch of device maximum brightness has reached 254cd/m at 200Hz
2, be the highest domestic brightness known today, still, threshold voltage is up to 220V, and we think the too high inadequate reason of annealing that makes of luminescent layer x value.
The 3rd batch of device architecture of table 15 and EL performance
The 3rd batch of device luminescent layer sedimentary condition of table 16
NO | Target | Base vacuum Pa | Power W | Substrate temperature ℃ | Ar/O 2Compare sccm/sccm | Air pressure Pa | Target-substrate distance cm | Speed nm/min |
3-1 | C2 | 4.8×10 -4 | 300 | 210 | 210/30 | 2.7 | 8.4 | 5.8 |
3-2 | C2 | 4.8×10 -4 | 300 | 210 | 210/30 | 2.7 | 8.4 | 5.7 |
3-3 | C2 | 4.8×10 -4 | 300 | 210 | 210/30 | 2.7 | 8.4 | 5.3 |
3-4 | C2 | 4.8×10 -4 | 300 | 210 | 210/30 | 2.7 | 8.4 | 5.8 |
3-5 | C2 | 1.2×10 -3 | 300 | 210 | 210/30 | 2.7 | 8.4 | 4.9 |
3-6 | C2 | 1.2×10 -3 | 300 | 210 | 210/30 | 2.7 | 8.4 | 4.9 |
3-7 | C2 | 1.2×10 -3 | 800 | 210 | 210/30 | 2.7 | 8.4 | 4.9 |
3-8 | C2 | 1.2×10 -3 | 300 | 210 | 210/30 | 2.7 | 8.4 | 5.0 |
3-9 | C2 | 1.2×10 -3 | 00 | 210 | 210/30 | 2.7 | 8.4 | 4.9 |
The 3rd batch of upper and lower dielectric deposition condition of device of table 17
* sample 1 and 3-4.
The 3rd batch of device L-V data of table 18
The present invention compares with prior art, and its technique effect is significant.Utilize the beneficial effect of green inorganic EL display structural design provided by the invention and manufacture method to be: 1) from use BST, SrTiO
3, Al
2O
3, Sialon, ATO, TiO
2Electron injecting layer is seen, HfO
2And SrTiO
3Be the following electron injecting layer of better performances, its thickness 100-250nm is advisable.And the good BST that in the past worked does not obtain a good result, and its reason is its depositing temperature lower (~ 450 ℃), and crystallinity is poor, and the dielectric constant of amorphous bst thin film is lower.We adopt with HfO
2For the threshold voltage of green glow TFEL device under 200Hz and 50 μ s ac pulse voltages of list or bielectron implanted layer at 200-230V, L
50Be respectively 180cd/m
2And 194cd/m
22) another important results of this patent is, is introducing the electron beam evaporation of 50nm or the Al of sputter down between electron injecting layer and the ITO
2O
3Or Sialon improved the reliability of device significantly, for Zn
2Si
xGe
1-xO
4: Mn is that a step has been pushed ahead in the industrialization of the green glow EL display device of luminescent layer.
We also find, with HfO
2As the following device luminescent properties instability of electron injecting layer, in the process that increases voltage, on the pixel beginning several seconds very bright, deepening immediately some.From the relevant HfO that is found
2The document of film sees, after luminescent layer annealing, and HfO
2The crystalline state of film should be monocline or quadrature phase.HfO
2The film conduct value of electron injecting layer down need continue demonstration.If can remain on brightness initial several seconds when increasing voltage, the brightness of the device of said structure is expected original position and improves more than 1/4th.
Description of drawings
The structural representation of Fig. 1 inorganic thin-film electrofluorescence display spare;
The SrTiO of Fig. 2 550 ℃ of following sputtering sedimentations on ITO
3Film (a) normal region; (b) peel off the zone;
The Ba of Fig. 3 500 ℃ of following sputtering sedimentations on ITO
0.5Sr
0.5TiO
3Film (a) normal region; (b) peel off the zone;
Fig. 4 radio frequency magnetron reactive sputtering Al
2O
3The graph of a relation of leakage current density and target-substrate distance;
The L-V curve (a) of Fig. 5 embodiment 1 and EL spectrum (b);
The L-V curve (a) of Fig. 6 embodiment 2 and EL spectrum (b);
The L-V curve of Fig. 7 embodiment 3;
The L-V curve (a) of Fig. 8 embodiment 4 and EL spectrum (b);
The L-V curve of Fig. 9 embodiment 5;
L-V curve (a) the EL spectrum (b) of Figure 10 embodiment 6;
The L-V curve (a) of Figure 11 embodiment 7 and EL spectrum (b);
The L-V curve of Figure 12 embodiment 8;
The L-V curve (a) of Figure 13 embodiment 9 and EL spectrum (b);
The L-V curve (a) of Figure 14 embodiment 10 and EL spectrum (b);
The L-V curve (a) of Figure 15 embodiment 11 and EL spectrum (b);
The L-V curve (a) of Figure 16 embodiment 12 and EL spectrum (b);
The L-V curve (a) of Figure 17 embodiment 13 and EL spectrum (b);
The L-V curve (a) of Figure 18 embodiment 14 and EL spectrum (b).
Embodiment
Below in conjunction with description of drawings embodiments of the invention are described in further detail, but present embodiment is not limited to the present invention, every employing analog structure of the present invention and similar variation thereof all should be listed protection scope of the present invention in.
In following embodiment, all adopt device architecture as described below:
A kind of green inorganic thin-film electrofluorescence display, comprise a glass substrate 1, described glass substrate 1 is provided with a bottom electrode layer 2, described bottom electrode layer 2 is provided with a following dielectric layer 3, described dielectric layer 3 down is provided with down electron injecting layer 4, described electron injecting layer 4 down is provided with luminescent layer 5, described luminescent layer 5 is provided with electron injecting layer 6, electron injecting layer 6 is provided with dielectric layer 7 on described, dielectric layer 7 is provided with top electrode layer 8 on described, described top electrode layer 8 is connected by an end of a lead and an alternating-current pulse power supply 9, and an other end of described alternating-current pulse power supply 9 is connected with described bottom electrode layer 2.
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (150nm)/Al
2O
3(100nm)/Zn
1.96Mn
0.04Si
0.5Ge
0.5O
4(the A target, 260nm)+Zn
1.96Mn
0.04Si
0.6Ge
0.4O
4(B1 target 350nm)/HfO
2(100nm)/Ta
2O
5(300nm)/Al
2O
3(150nm)/Al (150nm).The Corning Eagle2000TFT bottom electrode ITO that plates on glass is square, and this figure obtains through photoetching, and effective area is 46.25mm
2Substrate adopts the three-step approach standardization program to clean, and promptly 5%NaOH glass cleaner, acetone, each ultrasonic cleaning 30min of absolute ethyl alcohol clean three times in deionized water for ultrasonic again, each 5min.Deposit medium Sialon and Al down then successively
2O
3, luminescent layer, go up electron injecting layer medium HfO
2, go up medium T a
2O
5And Al
2O
3And top electrode Al.The Sialon film adopts the radio-frequency magnetron sputter method preparation, and equipment is CS500 rf magnetron sputtering instrument.The round target that thick 6mm, diameter are 3 inches is the Y-alpha-beta Sialon material of high compaction, and α accounts for 30% mutually.The quality chemistry of target consists of: Y:6.05%, Al:6.96%, Si:48.66%, all the other are N, O.Sintering condition: gas pressure sintering, 1800 ℃, insulation 5 hours.Sedimentary condition is: base vacuum 1.5 * 10
-3Pa, power 250W, 210 ℃ of substrate temperatures, Ar/N
2Than 28sccm/14sccm, air pressure 0.46Pa, deposition rate 6.2nm/min.Al
2O
3Adopt pulse reaction magnetron sputtering method deposition, equipment is SP450 rf magnetron sputtering continuous coating system, and the Al target contains 1wt.%Si, size 55 * 11cm
2Sedimentary condition is: base vacuum 1.5 * 10
-3Pa, power density 3.0W/cm
2, substrate temperature room temperature, Ar/O2 be than 200sccm/50sccm, air pressure 0.48Pa, target-substrate distance 6cm, pulse frequency 70kHz, duty ratio 30%, deposition rate 1.3nm/min.Last polarization layer HfO
2The preparation of employing electron-beam vapor deposition method, equipment is SSZX-800 electron beam evaporation deposition machine.Sedimentary condition is: base vacuum 3.5 * 10
-3Pa, O
2Dividing potential drop 1.6 * 10
-2Pa, 65 ℃ of temperature, deposition 12nm/min.Last medium T a
2O
5Adopt DC pulse reactive magnetron sputtering method deposition, equipment is SP450 rf magnetron sputtering continuous coating system.Size 55 * 11cm of high-purity Ta (5N)
2Sedimentary condition is: base vacuum 2.3 * 10
-3Pa, power density 2.9W/cm
2, substrate temperature room temperature, Ar/O
2Than 230sccm/250sccm, air pressure 0.48Pa, target-substrate distance 6cm, pulse frequency 70kHz, duty ratio 30%, deposition rate 3.9nm/min.Last medium A l
2O
3Sedimentary condition identical with following medium.Luminescent layer deposits on the CS500 magnetic control sputtering device.Adopt two kinds of targets, consist of Zn
1.96Mn
0.04Si
0.5Ge
0.5O
43 inches solid-phase sintering targets (A target), consist of Zn
1.96Mn
0.04Si
0.6Ge
0.4O
43 inches CIP targets (B1 target).It is the Zn that is mixed with 1.1wt%Mn that target prepares employed starting powder
2SiO
4: Mn powder (2N, East China Electronics Co., Ltd fluorescent material Co., Ltd), ZnO powder (4N, Tianjin good fortune chemical reagent in morning factory), GeO
2Powder (5N, the safe copper industry of last oceanic rise Co., Ltd), MnO powder (3N, the Huaihua milky way in Hunan is smelted Co., Ltd).Each component powders of three inches sintering targets (A target) is done and is mixed the back dry-pressing, and pressure is about 8MPa, and sintering condition is 1250 ℃/5h, and atmosphere is atmosphere.Three inches powder targets (B1 target) adopt same raw material, mix at the alcohol medium, and 180 ℃ of oven dry are after CIP handles pressure 200MPa.The sedimentary condition of luminescent layer is: A target, base vacuum 5.0 * 10
-4Pa, power 350W, 280 ℃ of substrate temperatures, Ar/O
2Than 80sccm:20sccm, air pressure 1.1Pa, target-substrate distance 7.0cm, deposition rate 7.3nm/min; The B1 target, base vacuum 7.1 * 10
-4Pa, power 200W, 250 ℃ of substrate temperatures, Ar/O
2Than 35sccm:5sccm, air pressure 0.5Pa, target-substrate distance 5.8cm, deposition rate 5.8nm/min.After the luminescent layer deposition, annealing is carried out 710 ℃ of temperature, time 60min in pressure is the pure oxygen atmosphere of 0.01Pa.The Al electrode adopts electron-beam vapor deposition method preparation, equipment SSZX-800 electron beam evaporation deposition machine.Sedimentary condition is: base vacuum 2.5 * 10
-3Pa, normal temperature, deposition rate 12nm/min.Used Ar, N during each layer film deposition
2, O
2Purity be respectively 99.999%, 99.999%, 99.995%.The L-V performance test of device is carried out on the high frequency signal generator of self assembly, and luminance test adopts Minolta LS-100 type brightness instrument.CIEx, the testing apparatus of y are the SpectraScan Spectraradiometer Model PR-705 of Photo Research.The frequency of the two poles of the earth square wave that test is adopted is 200Hz, pulsewidth 50 μ s.The threshold voltage V of this device
ThBe 260V, the withstand voltage 334V that is higher than of device, the brightness L of 50V on the threshold voltage
50Be 26cd/m
2, CIEx, y is respectively 0.35,0.62, and there is the Interference Peaks of a 560nm in emission peak at 522nm, may be the insufficient generation of annealing crystallization.Fig. 5 (a) shows the L-V curve, and Fig. 5 (b) shows the EL spectrum.
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Al
2O
3(50nm)/BST (130nm)/Zn
1.96Mn
0.04Si
0.6Ge
0.4O
4(604nm)/HfO
2(100nm)/Ta
2O
5(300nm)/Al
2O
3(150nm)/Al (150nm).Substrate cleans, goes up electron injecting layer HfO
2, Ta
2O
5, Al
2O
3Deposition and the EL test condition with embodiment 2.Wherein descend medium A l
2O
3The preparation of employing electron beam evaporation, equipment is SSZX-800 electron beam evaporation deposition machine, sedimentary condition is: base vacuum 3.8 * 10
-3150 ℃ of Pa, depositing temperatures, deposition rate 24nm/min.Ba
0.5Sr
0.5TiO
3(BST) film adopts the rf magnetron sputtering deposition, and depositing device is that equipment is SP450 rf magnetron sputtering continuous coating system, the size 55 * 11cm of BST target
2, by 5 11 * 11cm
2The block of high temperature sintering is spliced, and is bundled on the copper target stand with indium; Sedimentary condition is: base vacuum 1.6 * 10
-3Pa, power 500W, 450 ℃ of substrate temperatures, Ar/O
2Than 200:20, air pressure 0.1Pa, target-substrate distance 6cm, deposition rate 0.45nm/min.Luminescent layer adopts three inches powder targets (B1 target) deposition, and its preparation method is seen embodiment 2; Depositing device is CS500, and sedimentary condition is: base vacuum 7.5 * 10
-4Pa, power 200W, 250 ℃ of substrate temperatures, Ar/O
2Than 35sccm:5sccm, air pressure 0.50Pa, target-substrate distance 7.0cm, deposition rate 12.4nm/min.After the luminescent layer deposition, annealing is carried out 710 ℃ of temperature, time 60min in pressure is the pure oxygen atmosphere of 0.01Pa.The threshold voltage V of this device
ThBe 255V, the withstand voltage 320V of device, the brightness L of 50V on the threshold voltage
50Be 123cd/m
2, CIEx, y is respectively 0.34,0.62, and emission peak is at 540nm.Fig. 6 (a) shows the L-V curve, and Fig. 6 (b) shows the EL spectrum.
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (50nm)/BST (125nm)/Zn
1.96Mn
0.04Si
0.5Ge
0.5O
4(499nm)/HfO
2(100nm)/Sialon (130nm)/Al (150nm).Embodiment 2 is seen in the preparation of the preparation of substrate, 3 inches sialon targets.The sedimentary condition of following medium sialon is: base vacuum 2.3 * 10
-3Pa, power 250W, 250 ℃ of substrate temperatures, Ar/N
2Than 28sccm/14sccm, air pressure 0.50Pa, target-substrate distance 7.0cm, deposition rate 6.2nm/min.Last polarization layer HfO
2The preparation of employing electron-beam vapor deposition method, equipment is SSZX-800 electron beam evaporation deposition machine.Sedimentary condition is: base vacuum 3.3 * 10
-3Pa, O
2Dividing potential drop 1.5 * 10
-2Pa, 65 ℃ of temperature, deposition rate 12nm/min.The sedimentary condition of last medium Sialon is: base vacuum 2.3 * 10
-3Pa, power 300W, 250 ℃ of substrate temperatures, Ar/O
2Than 45sccm/15sccm, air pressure 0.65Pa, target-substrate distance 8.4cm, deposition rate 5nm/min.The luminescent layer deposition adopts 3 inches powder targets (B2 target), and condition is: base vacuum 2.3 * 10
-3Pa, power 125W, 220 ℃ of substrate temperatures, Ar/O
2Ratio 210/30, air pressure 2.7Pa, target-substrate distance 7.0cm, deposition rate 3.8nm/min.The deposition back is at the pure O of 700 ℃/2h, 0.02Pa
2Following annealing.The pure green emitting of this device, threshold voltage is 155V, the brightness L40 of 40V is 121cd/m on the threshold voltage
2, burn at 200V.Fig. 7 shows the L-V curve.
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (50nm)/Zn
1.96Mn
0.04Si
0.5Ge
0.5O
4(470nm)/HfO
2(100nm)/Sialon (130nm)/Al
2O
3(160nm)/Al (150nm).The preparation of substrate and employed Sialon target are with embodiment 2.Following medium Sialon is deposited as CS500, and condition is: base vacuum 1.5 * 10
-3Pa, power 250W, 250 ℃ of substrate temperatures, Ar/N
2Than 28sccm/14sccm, air pressure 0.45Pa, target-substrate distance 7.0cm, deposition rate 6.2nm/min.Last polarization layer HfO
2The preparation of employing electron-beam vapor deposition method, equipment is SSZX-800 electron beam evaporation deposition machine; Sedimentary condition is: base vacuum 3.5 * 10
-3Pa, O
2Dividing potential drop 1.6 * 10
-2Pa, 65 ℃ of temperature, deposition rate 12nm/min.The sedimentary condition of last medium Sialon is: base vacuum 2.4 * 10
-3Pa, power 300W, 250 ℃ of substrate temperatures, Ar/O
2Ratio 45/15, air pressure 0.65Pa, target-substrate distance 8.4cm, deposition rate 5nm/min.Last medium A l
2O
3Depositing of thin film equipment is CS500, and target is high-purity Al target (5N) of 3 inches, and condition is: 210 ℃ of power 250W, substrate temperatures, Ar/O
2Than 150sccm/50sccm, air pressure 2.2Pa, target-substrate distance 8.4cm.The luminescent layer deposition adopts 3 inches powder targets (B2 target).Condition is: base vacuum 2.3 * 10
-3Pa, power 200W, 220 ℃ of substrate temperatures, Ar/O
2Than 140sccm/20sccm, air pressure 1.8Pa, target-substrate distance 8.4cm, deposition rate 3.5nm/min.The deposition back is at the pure O of 700 ℃/2h, 0.02Pa
2Following annealing.The threshold voltage V of a pixel of this device
ThBe 185V, the withstand voltage 280V of device, the brightness L of 50V on the threshold voltage
50Be 180Cd/m
2, CIEx, y is respectively 0.32,0.64, and emission peak is at 536nm.The threshold voltage V of the one other pixel of this device
ThBe 180V, the withstand voltage 300V of device, the brightness L of 50V on the threshold voltage
50Be 128cd/m
2Fig. 8 (a) shows the L-V curve, and Fig. 8 (b) shows the EL spectrum.
Device architecture is NSG glass/ITO (150nm)/Sialon (50nm)/BST (190nm)/Zn
1.96Mn
0.04Si
0.55Ge
0.45O
4(615nm)/HfO
2(100nm)/Sialon (320nm)/Al (150nm).The preparation of substrate and employed sialon target, time medium Sialon, last polarization layer HfO
2And the sedimentary condition of top electrode Al is with embodiment 5.The sedimentary condition of last medium Sialon is: base vacuum 2.4 * 10
-3Pa, power 300W, 140 ℃ of substrate temperatures, Ar/O
2Than 45sccm/15sccm, air pressure 0.65Pa, target-substrate distance 8.4cm, deposition rate 5nm/min.Luminescent layer adopts 8 * 15cm
2The rectangular target of powder (C2 target), dry-pressing formed, pressure 15MPa.Sedimentary condition is: base vacuum 1.3 * 10
-3Pa, power 300W, 210 ℃ of substrate temperatures, Ar/O
2Than 140sccm/20sccm, air pressure 1.8Pa, target-substrate distance 8.4cm, deposition rate 6.7nm/min.The deposition back is at the pure O of 700 ℃/2h, 0.02Pa
2Following annealing.The threshold voltage V of this device
ThBe 230V, the withstand voltage 290V of device, the brightness L of 40V on the threshold voltage
40Be 122cd/m
2, pure green emitting.Fig. 9 shows the L-V curve.
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (153nm)/BST (125nm)/Zn
1.96Mn
0.04Si
0.55Ge
0.45O
1(843nm)/HfO
2(100nm)/Sialon (320nm)/Al (150nm).Substrate and employed Sialon target are seen embodiment 2.The sedimentary condition of following medium Sialon is with embodiment 4.The target that following electron injecting layer BST is adopted is with embodiment 3, and sedimentary condition is: base vacuum 3.3 * 10
-3Pa, power 500W, 450 ℃ of substrate temperatures, Ar/O
2Than 200sccm/20sccm, air pressure 0.1Pa, target-substrate distance 6cm, deposition rate 0.45nm/min.The used target of the deposition of luminescent layer, preparation and annealing conditions and embodiment 6 are together.As different from Example 6, the deposition rate 11.2nm/min of luminescent layer, this be because when deposition substrate corresponding to the diverse location (interior or sorrowful outward) of target.The threshold voltage V of this device
ThBe 285V, device withstand voltage, the brightness L of 50V on the threshold voltage greater than 334V
50Be 165cd/m
2, CIEx, y is respectively 0.36,0.61, and emission peak is at 540nm.Figure 10 a) shows the L-V curve, and Figure 10 (b) shows the EL spectrum.
Embodiment 7
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (50nm)/BST (125nm)/Zn
1.96Mn
0.04Si
0.5Ge
0.5O
4(393nm)/HfO
2(100nm)/Sialon (250nm)/Al
2O
3(30nm)/Al (150nm).The target of substrate cleaning, Sialon medium is with embodiment 2.The sedimentary condition that following medium sialon and following electronics inject is with embodiment 4.The preparation of following electron injecting layer BST is with embodiment 7.The target that the luminescent layer deposition is adopted is 3 inches powder targets (B2), with embodiment 3; Sedimentary condition is: base vacuum 2.0 * 10
-3Pa, power 125W, 220 ℃ of substrate temperatures, Ar/O
2Than 210sccm/30sccm, air pressure 2.7Pa, target-substrate distance 7.0cm, deposition rate 3.3nm/min.Luminescent layer annealing conditions, last electron injecting layer HfO
2, go up medium Sialon and Al
2O
3Sedimentary condition with embodiment 5.The threshold voltage V of this device
ThBe 200V, about the withstand voltage 300V of device, the brightness L of 50V on the threshold voltage
50Be 71cd/m
2, CIEx, y is respectively 0.35,0.61, and emission peak is at 536nm.Figure 11 (a) shows the L-V curve, and Figure 11 (b) shows the EL spectrum.
Embodiment 8
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (150nm)/BST (125nm)/Zn
1.96Mn
0.04Si
0.5Ge
0.5O
4(429nm)/BST (200nm)/Sialon (110nm)/Al (150nm).The Sialon target that substrate cleans, adopted is with embodiment 2.The sedimentary condition of following medium Sialon, following electron injecting layer BST is with embodiment 4.Last electron injecting layer BST and following electron injecting layer are together.The sedimentary condition of Sialon is 8.4cm except target-substrate distance, and all the other conditions and following medium are together.The target that the luminescent layer deposition is adopted is 3 inches powder targets (B2 targets).The sedimentary condition of deposition and annealing conditions and each layer is with embodiment 8.The threshold voltage V of this device
ThBe 170V, the withstand voltage 200V of device, the brightness L of 30V on the threshold voltage
30Be 70cd/m
2, Figure 12 shows the L-V curve.
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (100nm)/BST (190nm)/Zn
1.96Mn
0.04Si
0.55Ge
0.45O
4(510nm)/Sialon (210nm)/Al
2O
3(120nm)/Al (150nm).Sialon target that substrate cleans, adopted and the deposition of top electrode Al are with embodiment 2.The depositing device of following medium Sialon is CS500, and condition is: base vacuum 2.8 * 10
-3Pa, power 250W, 210 ℃ of substrate temperatures, Ar/N
2Than 28sccm/14sccm, air pressure 0.45Pa, target-substrate distance 7.0cm, deposition rate 6.2nm/min.The sedimentary condition of following electron injecting layer BST is with embodiment 3.Luminescent layer adopts powder side's target deposition (C2 target), and condition is: base vacuum 1.3 * 10
-3Pa, power 300W, 210 ℃ of substrate temperatures, Ar/O
2Than 210sccm/30sccm, air pressure 2.7Pa, target-substrate distance 8.4cm, deposition rate 8.5nm/min.Annealing conditions is 700 ℃/2h, the pure O of 0.02Pa
2Atmosphere.Last medium Sialon, Al
2O
3Depositing temperature be 180 ℃, all the other conditions and embodiment 5 with.The threshold voltage V of this device
ThBe 250V, the withstand voltage 334V that is higher than of device, the brightness L of 50V on the threshold voltage
50Be 36cd/m
2, CIEx, y is respectively 0.35,0.62, and emission peak is at 540nm.Figure 13 (a) shows the L-V curve, and Figure 13 (b) shows the EL spectrum.
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (50nm)/Zn
1.96Mn
0.04Si
0.5Ge
0.5O
4(580nm)/BST (200nm)/Sialon (310nm)/Al (150nm).Sialon target that substrate cleans, adopted and the deposition of top electrode Al are with embodiment 2.The sedimentary condition of following medium sialon is with embodiment 5.The sedimentary condition of last electron injecting layer BST, last medium sialon is with embodiment 5.Luminescent layer adopts powder side's target deposition (B2 target), and condition is: base vacuum 2.3 * 10
-3Pa, power 200W, 220 ℃ of substrate temperatures, Ar/O
2Than 140sccm/20sccm, air pressure 1.8Pa, target-substrate distance 7.0cm, deposition rate 4.3nm/min.Annealing conditions is 700 ℃/2h, the pure O of 0.02Pa
2Atmosphere.The threshold voltage V of this device
ThBe 260V, the withstand voltage 310V of device, the brightness L of 50V on the threshold voltage
50Be 85cd/m
2, CIEx, y is respectively 0.33,0.63, and also there is the not Interference Peaks of complete crystallization of a 565nm in emission peak at 530nm.Figure 14 (a) shows the L-V curve, and Figure 14 (b) shows the EL spectrum.
Embodiment 11
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (50nm)/Zn
1.96Mn
0.04Si
0.5Ge
0.5O
4(580nm)/HfO
2(100nm)/Sialon (300nm)/Al (150nm).Sialon target that substrate cleans, adopted and the deposition of top electrode Al are with embodiment 2.The depositing temperature of following medium and last medium Sialon is 150 ℃, and all the other conditions are with embodiment 4.The deposition of luminescent layer and annealing conditions are with embodiment 11.The threshold voltage V of this device
ThBe 180V, about the withstand voltage 300V of device, the brightness L50 of 50V is 59cd/m on the threshold voltage
2, CIEx, y is respectively 0.32,0.60, and emission peak is at 544nm.Figure 15 (a) shows the L-V curve, and Figure 15 (b) shows the EL spectrum.
Embodiment 12
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (50nm)/BST (190nm)/Zn
1.96Mn
0.04Si
0.55Ge
0.45O
4(725nm)/BST (200nm)/Sialon (310nm)/Al
2O
3(50nm)/Al (150nm).Sialon target that substrate cleans, adopted and the deposition of top electrode Al are with embodiment 2.The sedimentary condition of following medium and last medium Sialon and embodiment 4 are together.The deposition of luminescent layer and annealing conditions are with embodiment 10.The threshold voltage V of this device
ThBe 265V, the withstand voltage 334V that is higher than of device, the brightness L of 50V on the threshold voltage
50Be 55cd/m
2, CIEx, y is respectively 0.34,0.62, and there is a 555nm Interference Peaks in emission peak at 528nm.Figure 16 (a) shows the L-V curve, and Figure 16 (b) shows the EL spectrum.
Embodiment 13
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Sialon (60nm)/HfO2 (100nm)/Zn
1.96Mn
0.04Si
0.55Ge
0.45O
4/ (580nm)/TiO
2(47nm)/ATO (47nm)/Sialon (150nm)/Al
2O
3(140nm)/Al (150nm).Sialon target that substrate cleans, adopted and the deposition of top electrode Al are with embodiment 2.Following medium Sialon is deposited as CS500, and condition is: base vacuum 2.5 * 10
-3Pa, power 280W, 210 ℃ of substrate temperatures, Ar/O
2Than 35sccm/14sccm, air pressure 0.56Pa, target-substrate distance 8.4cm, deposition rate 9.9nm/min.Following electron injecting layer HfO
2Sedimentary condition and the last electron injecting layer HfO of embodiment 2
2Identical.Adopt the rectangular target of powder (C2 target) deposition, sedimentary condition is: base vacuum 4.8 * 10
-4210 ℃ of Pa power 300W, substrate temperatures, Ar/O
2Than 210sccm/30sccm, air pressure 2.7Pa, target-substrate distance 8.4cm, deposition rate 5.8nm/min.Annealing conditions is: 700 ℃/1h, the pure O of 0.08Pa
2Atmosphere.Last electron injecting layer TiO
2/ ATO adopts the electron beam evaporation preparation, and equipment is ZZSX-800; Sedimentary condition is: base vacuum 3.3 * 10
-3Pa, 150 ℃ of substrate temperatures, O
2Pressure 2.2 * 10
-2Pa, substrate speed of rotation 3.3rpm, deposition rate 15nm/min.Last medium Sialon, Al
2O
3The threshold voltage V of this device
ThBe 265V, the withstand voltage 334V that is higher than of device, the brightness L of 50V on the threshold voltage
50Be 118cd/m
2, CIEx, y is respectively 0.32,0.65, and emission peak is at 538nm.Figure 17 (a) shows the L-V curve, and Figure 17 (b) shows the EL spectrum.
Device architecture is Corning Eagle2000 glass/ITO (150nm)/Al
2O
3(50nm)/SrTiO3 (130nm)/Zn
1.96Mn
0.04Si
0.55Ge
0.45O
4(510nm)/HfO2 (130nm)/Al
2O
3(140nm)/Sialon (150nm)/Al (150nm).The Sialon target that substrate cleans, adopted, following medium A l
2O
3And the deposition of top electrode Al is with embodiment 2.SrTiO
3Film is taked the electron beam evaporation preparation equally, and sedimentary condition is: base vacuum 3.6 * 10
-3Pa, 150 ℃ of substrate temperatures, O
2Pressure 1.5 * 10
-2Pa, substrate speed of rotation 3.3rpm, deposition rate 6nm/min.180 ℃ of the depositing temperatures of last medium Sialon, medium A l
2O
3180 ℃ of deposition power 300W, substrate temperatures, all the other conditions and embodiment 5 with.Luminescent layer adopts the rectangular target of powder (C2 target) deposition, and sedimentary condition is: base vacuum 1.2 * 10
-3210 ℃ of Pa power 300W, substrate temperatures, Ar/O
2Than 210sccm/30sccm, air pressure 2.7Pa, target-substrate distance 8.4cm, deposition rate 4.9nm/min.Annealing conditions is: 700 ℃/1h, the pure O of 0.08Pa
2Atmosphere.The threshold voltage V of this device
ThBe 220V, the withstand voltage 300V of device, the brightness L of 50V on the threshold voltage
50Be 194cd/m
2, CIEx, y is respectively 0.35,0.62, and emission peak is at 536nm.Figure 18 (a) shows the L-V curve, and Figure 18 (b) shows the EL spectrum.
Claims (59)
1. green inorganic thin-film electrofluorescence display, comprise a glass substrate, it is characterized in that: described glass substrate is provided with a bottom electrode layer, described bottom electrode layer is provided with a following dielectric layer, described dielectric layer down is provided with down electron injecting layer, described electron injecting layer down is provided with luminescent layer, described luminescent layer is provided with electron injecting layer, electron injecting layer is provided with dielectric layer on described, dielectric layer is provided with top electrode layer on described, described top electrode layer is connected by an end of a lead and an alternating-current pulse power supply, and an other end of described alternating-current pulse power supply is connected with described bottom electrode layer.
2. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 1 is characterized in that: described dielectric layer down adopts sialon or Al
2O
3Film or sialon and Al
2O
3Laminated film.
3. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 2, it is characterized in that: described sialon film adopts the Y-alpha-beta sialon solid-phase sintering target and the radio-frequency magnetron sputter method preparation of high compaction, wherein, α accounted for 30% mutually in the Y-alpha-beta sialon target, 1800 ℃ of following gas pressure sinterings 5 hours.
4. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 3 is characterized in that: when described sialon film adopted radio-frequency magnetron sputter method to prepare, its working gas was Ar+O
2Or Ar+N
2, sedimentary condition is: base vacuum is 1.0-5.0 * 10
-3Pa, power are 200-300W, and substrate temperature is 100-300 ℃, N
2/ (Ar+N
2) or O
2/ (Ar+O
2) than being 20-35%, air pressure is 0.4-0.7Pa, target-substrate distance is 6.0-8.4cm, deposition rate is between 3.0-6.5nm/min.
5. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 2 is characterized in that: the thickness of described sialon film is between 50-150nm.
6. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 2 is characterized in that: described Al
2O
3Film adopts the preparation of pulse reaction sputtering method, and its working gas is Ar+O
2, sedimentary condition is: base vacuum is 1.0-3.0 * 10
-3Pa, power are 100-400W, and substrate temperature is 100-300 ℃, O
2/ (Ar+O
2) than being 70-90%, air pressure is 1.5-2.5Pa, target-substrate distance is 6.0-8.4cm, deposition rate is between 0.5-1.5nm/min.
7. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 2 is characterized in that: described Al
2O
3Film adopts the electron-beam vapor deposition method preparation, and its sedimentary condition is: base vacuum is 2.5-3.5 * 10
-3Pa, substrate temperature are 100-200 ℃, and deposition rate is 12.0-18.0nm/min.
8. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 2 is characterized in that: described Al
2O
3The thickness of film is between the 50-150nm.
9. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 1 is characterized in that: described electron injecting layer down is high K oxide, is selected from Ba
xSi
1-xTiO
3, or SrTiO
3, or HfO
2, or TiO
2, or Al
2O
3-TiO
2, or Y
2O
3, or ZrO
2
10. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 9 is characterized in that: described electron injecting layer down adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described Ba
xSi
1-xTiO
3The sputtering sedimentation condition of film: base vacuum is 1.6 * 10
-3Pa, substrate temperature are 450 ℃, and radio-frequency power is 500W, O
2/ (Ar+O
2) than for 10-20%, air pressure 0.1Pa,, deposition rate is 0.3-1.0nm/min.
11. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 10 is characterized in that: the depositing device that is adopted is a SP450 rf magnetron sputtering continuous coating system.
12. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 10 is characterized in that: employed Ba
xSi
1-xTiO
3The sintering target is of a size of 55 * 11cm
2, by 5 11 * 11cm
2Block is spliced.
13. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 9 is characterized in that: described electron injecting layer down adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described SrTiO
3The evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O
2Air pressure is 3.0 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 3.0-9.0nm/min.
14. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 13 is characterized in that: the equipment that is adopted is the ZZSX-800 electron beam coater.
15. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 9 is characterized in that: described electron injecting layer down adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described HfO
2The evaporation conditions of film: base vacuum is 2.0-3.0 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 6.0-18.0nm/min.
16. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 15 is characterized in that: the equipment that is adopted is the ZZSX-800 electron beam coater.
17. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 9 is characterized in that: described electron injecting layer down adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described Y
2O
3The evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 12.0-18.0nm/min.
18. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 17 is characterized in that: the equipment that is adopted is the ZZSX-800 electron beam coater.
19. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 9 is characterized in that: described electron injecting layer down adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described TiO
2And Al
2O
3-TiO
2(ATO) evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 12.0-18.0nm/min.
20. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 19 is characterized in that: the equipment that is adopted is the ZZSX-800 electron beam coater.
21. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 1 is characterized in that: the thickness of described electron injecting layer down is between 50-300nm.
22. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 21 is characterized in that: the thickness of described electron injecting layer down is between 100-200nm.
23. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 1 is characterized in that: the material of described luminescent layer is Zn
2Si
xGe
1-xO
4: Mn.
24. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 23 is characterized in that: the x value of described luminescent layer is between 0.5-0.6.
25. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 23 is characterized in that: described luminescent layer adopts the radio-frequency magnetron sputter method preparation, and its target is 3 inches dry-pressing solid-phase sintering targets, and employed original powder is high-purity Zn
2SiO
4: Mn, ZnO, GeO
2, MnO
2, briquetting pressure 5-10MPa.Sintering condition is that temperature 1150-1250 ℃, time 2-5 hour, atmosphere are argon gas or air.
26. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 25 is characterized in that: described luminescent layer adopts three inches sintering circle targets depositions, and its condition is, substrate temperature 150-350 ℃, and power 300-400W, O
2/ (O
2+ Ar) than 10-30%, air pressure 0.4-2.5Pa, target-substrate distance 6.0-8.4cm.
27. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 23, it is characterized in that: described luminescent layer adopts the radio-frequency magnetron sputter method preparation, its target is the powder circle target that 3 inches dry-pressing or isostatic cool pressing are handled, dry-pressing pressure is 5-10MPa, and the isostatic cool pressing processing pressure is 180-200MPa.
28. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 27 is characterized in that: described luminescent layer adopts three inches powder circle targets depositions, and its condition is, substrate temperature 150-300 ℃, and power 100-200W, O
2/ (O
2+ Ar) than 10-30%, air pressure 0.4-2.5Pa, target-substrate distance 6.0-8.4cm.
29. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 23 is characterized in that: described luminescent layer adopts the radio-frequency magnetron sputter method preparation, and its target is 8 * 15cm
2Dry-pressing or the rectangular target of powder handled of isostatic cool pressing, dry-pressing pressure 12-17MPa, isostatic cool pressing processing pressure 180-200MPa.
30. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 29 is characterized in that: described luminescent layer adopts the rectangular target deposition of powder, and its condition is, substrate temperature 150-300 ℃, and power 200-300W, O
2/ (O
2+ Ar) than 10-30%, air pressure 0.4-2.5Pa, target-substrate distance 6.0-8.4cm.
31. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 1 is characterized in that: the thickness of described luminescent layer is between 300-1250nm.
32. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 1 is characterized in that: described upward electron injecting layer is high K oxide, is selected from Ba
xSi
1-xTiO
3, or SrTiO
3, or HfO
2, or TiO
2, or Al
2O
3-TiO
2, or Y
2O
3, or ZrO
2
33. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 32 is characterized in that: the described electron injecting layer of going up adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described Ba
xSi
1-xTiO
3The sputtering sedimentation condition of film: base vacuum is 1.6 * 10
-3Pa, substrate temperature are 450 ℃, and radio-frequency power is 500W, O
2/ (Ar+O
2) than for 10-20%, air pressure 0.1Pa,, deposition rate is 0.3-1.0nm/min.
34. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 33 is characterized in that: the depositing device that is adopted is a SP450 rf magnetron sputtering continuous coating system.
35. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 33 is characterized in that: employed Ba
xSi
1-xTiO
3The sintering target is of a size of 55 * 11cm
2, by 5 11 * 11cm
2Block is spliced.
36. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 32 is characterized in that: the described electron injecting layer of going up adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described SrTiO
3The evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O
2Air pressure is 3.0 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 3.0-9.0nm/min.
37. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 36 is characterized in that: the equipment that is adopted is the ZZSX-800 electron beam coater.
38. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 32 is characterized in that: the described electron injecting layer of going up adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described HfO
2The evaporation conditions of film: base vacuum is 2.0-3.0 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 6.0-18.0nm/min.
39. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 38 is characterized in that: the equipment that is adopted is the ZZSX-800 electron beam coater.
40. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 32 is characterized in that: the described electron injecting layer of going up adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described Y
2O
3The evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 12.0-18.0nm/min.
41. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 40 is characterized in that: the equipment that is adopted is the ZZSX-800 electron beam coater.
42. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 32 is characterized in that: the described electron injecting layer of going up adopts electron beam evaporation or radio-frequency magnetron sputter method preparation, described TiO
2And Al
2O
3-TiO
2(ATO) evaporation conditions of film: base vacuum is 2.5-3.5 * 10
-3Pa, O
2Pressure is 1-2 * 10
-2Pa, substrate temperature are 100-200 ℃, and deposition rate is 12.0-18.0nm/min.
43. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 42 is characterized in that: the equipment that is adopted is the ZZSX-800 electron beam coater.
44. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 1 is characterized in that: the described thickness of electron injecting layer of going up is between 50-300nm.
45. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 21 is characterized in that: the described thickness of electron injecting layer of going up is between 50-150nm.
46. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 1 is characterized in that: the described dielectric layer of going up adopts Ta
2O
5, or sialon or Al
2O
3Film or its any laminated film that combines more than two kinds or two kinds.
47. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 46, it is characterized in that: described sialon film adopts the Y-alpha-beta sialon solid-phase sintering target and the radio-frequency magnetron sputter method preparation of high compaction, wherein, α accounted for 30% mutually in the Y-alpha-beta sialon target, 1800 ℃ of following gas pressure sinterings 5 hours.
48. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 46 is characterized in that: described Ta
2O
5The pulse reaction sputtering condition of film is: base vacuum is 2-4 * 10
-3Pa, substrate temperature are 50-80 ℃, and it is that 70kHz, duty ratio are 30%, power density is 2.8-3.1W/cm that target-substrate distance is about 6cm, pulse frequency
2, air pressure is 0.5-1.0Pa, O
2/ (O
2+ Ar) than being 50-80%.
49. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 48 is characterized in that: the depositing device that is adopted is a SP450 rf magnetron sputtering continuous coating system.
50. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 48 is characterized in that: the Ta of pulse reaction sputter
2O
5The thickness of film is between 150-400nm.
51. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 46 is characterized in that: described Al
2O
3The condition of pulse reaction sputter is: base vacuum 2-3 * 10
-3Pa, substrate temperature room temperature, the about 6cm of target-substrate distance, pulse frequency 70kHz, duty ratio 30%, power density 2.9-3.1W/cm
2, air pressure 0.4-0.6Pa, O
2/ (O
2+ Ar) compare 80-90%.
52. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 51 is characterized in that: the equipment that is adopted is SP450 vacuum continuous coating system.
53. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 51 is characterized in that: employed high-purity Ta target (5N) is of a size of 12 * 56cm
2
54. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 46 is characterized in that: described Al
2O
3The condition of radio frequency magnetron reactive sputtering is: base vacuum 1-3 * 10
-3Pa, substrate temperature 100-300 ℃, target-substrate distance 7cm, power 200-300W, air pressure 2.0-3.0Pa, O
2/ (O
2+ Ar) than being 70-90%.
55. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 54 is characterized in that: the equipment that is adopted is CS500 rf magnetron sputtering continuous coating system.
56. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 54 is characterized in that: use the Al target of 3 inches purity of diameter as 5N.
57. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 46 is characterized in that: the described medium A l that goes up
2O
3Thickness between 30-300nm.
58. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 46 is characterized in that: the sedimentary condition that described sialon goes up medium is: base vacuum is 1.0-5.0 * 10
-3Pa, power are 200-300W, and substrate temperature is 100-300 ℃, N
2/ (Ar+N
2) or O
2/ (Ar+O
2) than being 20-35%, air pressure is 0.4-0.7Pa, target-substrate distance is 6.0-8.4cm.
59. a kind of green inorganic thin-film electrofluorescence display as claimed in claim 46 is characterized in that: described sialon goes up the thickness of medium between 50-350nm.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106299063A (en) * | 2016-09-22 | 2017-01-04 | Tcl集团股份有限公司 | The zirconia film of a kind of doping, QLED and preparation method |
CN106796379A (en) * | 2014-07-01 | 2017-05-31 | 株式会社理光 | Electrochromic display device |
CN111233337A (en) * | 2020-03-03 | 2020-06-05 | 五邑大学 | Green light emitting microcrystalline glass for wide color gamut backlight display and preparation method thereof |
-
2008
- 2008-01-11 CN CNA2008100325493A patent/CN101483945A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106796379A (en) * | 2014-07-01 | 2017-05-31 | 株式会社理光 | Electrochromic display device |
CN106299063A (en) * | 2016-09-22 | 2017-01-04 | Tcl集团股份有限公司 | The zirconia film of a kind of doping, QLED and preparation method |
CN106299063B (en) * | 2016-09-22 | 2019-09-10 | Tcl集团股份有限公司 | A kind of zirconia film of doping, QLED and preparation method |
CN111233337A (en) * | 2020-03-03 | 2020-06-05 | 五邑大学 | Green light emitting microcrystalline glass for wide color gamut backlight display and preparation method thereof |
CN111233337B (en) * | 2020-03-03 | 2022-03-22 | 五邑大学 | Green light emitting microcrystalline glass for wide color gamut backlight display and preparation method thereof |
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