• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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    • 专利摘要:
    SUMMARY OF THE INVENTION The present invention aims to provide a laminated phosphor and an EL panel suitable for a white monochromatic EL element without requiring a filter, and in particular, to achieve this, it is a laminated phosphor having at least a first thin film and a second thin film. Wherein, the parent material of the first thin film contains barium aluminate as a main component, and the matrix material contains a sulfur element, contains a Eu as a light emitting center, and the second thin film matrix material contains zinc sulfide as a main component. It was set as an EL panel using this laminated phosphor.
    公开号:KR20020005477A
    申请号:KR1020010040282
    申请日:2001-07-06
    公开日:2002-01-17
    发明作者:야노요시히코；나가노가쓰토
    申请人:사토 히로시；티디케이가부시기가이샤；
    IPC主号:
    专利说明:

    Stacked phosphor and electroluminescent panel {Fluorescent Multilayer and EL Panel}
    [3] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting layer used for an inorganic EL element, and more particularly, to a laminate of white phosphor thin films used for a light emitting layer and an EL panel using the same.
    [4] Recently, thin-film EL devices have been actively studied as small or large-sized lightweight flat panel displays. A monochromatic thin film EL display using a phosphor thin film made of manganese-added zinc sulfide of yellow-yellow light emission has already been put into practical use as a double insulated structure using the insulating layers 2 and 4 of the thin film as shown in FIG. In FIG. 2, the lower electrode 5 of a predetermined pattern is formed on the substrate 1, and the first insulating layer 2 is formed on the lower electrode 5. In addition, the light emitting layer 3 and the second insulating layer 4 are formed in this order on the first insulating layer 2, and the upper portion of the second insulating layer 4 forms a matrix circuit with the lower electrode 5. The electrode 6 is formed in a predetermined pattern.
    [5] Coloration is indispensable for a display as a display for personal computers, TVs, and other displays. However, although a thin film EL display using a sulfide phosphor thin film is excellent in reliability and environmental resistance, it is inadequate for color because of the insufficient characteristics of EL phosphors emitting in three primary colors of red, green and blue in the present case. The blue thin phosphor has SrS as a mother material, SrS: Ce or ZnS: Tm using Ce as a light emitting center, ZnS: Sm, CaS: Eu as a red light emitting phosphor, and ZnS: Tb, CaS: Ce as a green light emitting phosphor. It is still being studied as a candidate.
    [6] Phosphor thin films that emit light in these three primary colors of red, green, and blue have problems in light emission luminance, efficiency, and color purity, and have not reached the practical use of color EL panels. In particular, although blue can obtain relatively high luminance by using SrS: Ce, development of a better blue light emitting layer is required because blue color for full color displays lacks luminance and shifts chromaticity toward green.
    [7] In order to solve these problems, Japanese Patent Laid-Open No. 7-122364, Japanese Patent Laid-Open No. Hei 8-134440, Theological Bulletin EID 98-113, pp19-24 and Jpn.J.Appl.Phys. vol38, (1999 years) as described in pp.L1291-1292, SrGa 2 S 4: Ce , CaGa 2 S 4: Ce and BaAl 2 S 4: Reid go thio or alkylthio of blue aluminate-based, such as Eu Phosphors have been developed. Although there is no problem in color purity in these thiogallate-based phosphors, it is difficult to obtain a thin film having a uniform composition because of low luminance and particularly pluripotency. It is thought that a high quality thin film cannot be obtained due to deterioration of crystallinity due to deterioration of composition control property, defects caused by yellow shortage, mixing of impurities, etc., and therefore, luminance is not increased. In particular, thioaluminate is very difficult to control the composition.
    [8] In addition, all monochromatic displays are commercialized using the orange phosphor ZnS: Mn. In view of the ease of display, a monochromatic color of white is required. As described in Display and Imaging (1994) vol 3, pp. 159-171, various white phosphors are examined for this request.
    [9] Conventionally, as the white phosphor, a ZnS: Pr thin film added with Pr as the light emission center is known. However, since the light emission spectrum is composed of bright lines, the thin film interference effect is exhibited, and the brightness is low. On the other hand, various white phosphors are realized by the method of adding red components, such as Eu and Mn, based on the blue green phosphor of SrS: Ce.
    [10] E.g,
    [11] (1) a method by Srs: Ce and Eu in which Ce and Eu are added to the SrS base material as a light emitting center;
    [12] (2) a method by SrS: Ce / SrS: Eu using SrS: Ce and SrS: Eu in a multilayer structure;
    [13] (3) a method by SrS: Ce / CaS: Eu using SrS: Ce and CaS: Eu in a multilayer structure;
    [14] (4) SrS: Ce / ZnS: Mn using SrS: Ce and ZnS: Mn in a multilayer structure.
    [15] Although these SrS: Ce-based white phosphor thin films have broad fluorescence spectra and are ideal materials for white light emission, they are so-called egg-shall whites with low luminance and near white to yellow color, and paper-white from an ergonomic point of view. That is, x = 0.3 and y = 0.3 in the CIE chromaticity coordinates are not obtained except when a filter is used.
    [16] It is an object of the present invention to provide a laminated phosphor and an EL panel suitable for white, in particular, paper-white monocolor-EL panel, having good color purity without using a filter.
    [17] This object is achieved by the configuration of any one of the following (1) to (4).
    [18] (1) A laminated phosphor having at least a first thin film and a second thin film, wherein the base material of the first thin film contains barium aluminate as a main component, and the base material contains sulfur element, and further contains Eu as a light emission center. In doing it,
    [19] The laminated phosphor whose main material of the said 2nd thin film has zinc sulfide as a main component.
    [20] (2) The laminated phosphor of (1), wherein the molar ratio S / (S + O) of the mixed amount of the sulfur element and the oxygen element of the parent material is 0.02 to 0.5.
    [21] (3) The molar ratio S / (S + O) of the mixed amount of the sulfur element and the oxygen element of the parent material is 0.7 to 0.9, and the ratio Al / Ba of the barium element Ba and the aluminum element Al is 1.5 to 3.0. ) Laminated phosphor.
    [22] (4) The laminated phosphor of (1) or (2), wherein the light emitting synthetic color of the first thin film and the second thin film is white in x = 0.27 to 0.39 and y = 0.27 to 0.38 in the CIE chromaticity coordinates.
    [23] (5) An EL panel having the laminated phosphor of any one of (1) to (4).
    [1] 1 is a schematic cross-sectional view showing a configuration example of an apparatus to which the method of the present invention is applicable or a manufacturing apparatus of the present invention;
    [2] Fig. 2 is a partial sectional view showing an example of the configuration of an inorganic EL element which can be produced by the method and apparatus of the present invention.
    [24] EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.
    [25] The present invention is a laminate of a phosphor thin film in which a first thin film and a second thin film are laminated, and the obtained laminated phosphor emits white light by synthesizing light emission of each layer.
    [26] The first thin film of the present invention uses barium aluminate of oxide as the mother material.
    [27] In the past, there have been no examples in which the alkaline metal aluminate thin film is examined as a thin film phosphor for EL. This is presumably because alkaline earth metal aluminate was difficult to obtain a crystallized thin film and thus could not be used as a phosphor thin film to emit EL light. Alkaline metal aluminates are being investigated for PDPs or fluorescent lamps. Ba raw materials, such as barium carbonate, Al raw materials, such as alumina, and Eu are added, and it bakes at 1100 degreeC-1400 degreeC, and powder is synthesize | combined. It is used as a blue fluorescent substance by synthesis | combination.
    [28] The present inventors thinned barium aluminate as a thin film phosphor for EL. An EL device was fabricated using this thin film, but light emission could not be obtained. Better annealing was observed when annealed at 1100 ° C. However, in order to apply to the panel of an EL element with a low luminance of 2 cd / ㎡, high luminance and process temperature were required.
    [29] As a result of the studies on the phosphor thin film of this system, it was found that the brightness was remarkably improved by adding sulfur to the barium aluminate base material.
    [30] The first thin film of the present invention contains sulfur in the barium aluminate base material which is an oxide, and further contains an Eu element as a light emission center.
    [31] The phosphor thin film is preferably represented by the composition formula Ba x Al y O z S w : Eu.
    [32] In the above formula, x, y, z and w represent the molar ratios of the elements Ba, Al, O and S, respectively. x, y, z are preferably
    [33] x = 1 to 5, y = 1 to 15, z = 3 to 30, and w = 3 to 30.
    [34] It is preferable to contain S / (S + O) in the range of 0.01-0.95, especially 0.02-0.7 by sulfur atom ratio with respect to a barium aluminate base material. That is, in the above formula, the value of w / (z + w) is preferably 0.02 to 0.7, preferably 0.02 to 0.50, particularly 0.03 to 0.35. At this time, the range where y / x becomes 5-7 is preferable.
    [35] In particular, in the above formula, when the value of w / (z + w) is 0.7 to 0.9, preferably 0.75 to 0.85, the atomic ratio Al / Ba of the element Ba and the element Al, that is, y / x is 1 to 3, Preferably, it is good to set it as 1.5-3.0, especially the range of 2.0-2.5.
    [36] Sulfur has the effect of dramatically increasing the phosphor thin-film EL light emission luminance. When sulfur is added to the alkali metal aluminate, crystallization is promoted at the time of film formation or during annealing after film formation, the added Eu becomes divalent in the matrix material, and is effectively transferred at the compound crystal site, and has high brightness. It is thought that light emission of is obtained.
    [37] In the light emitting device, there is a lifetime in which the luminance deteriorates with the elapse of the light emission time. Mixed composition of oxygen and sulfur improves the life characteristics and prevents deterioration of luminance. The parent material becomes stable in air as the compound with oxygen mixes compared to pure sulfides. This is considered to be because the stable oxide component protects the sulfur compound component in the film from oxygen. Therefore, according to the inventors' review, there is an optimal value between the composition of sulfide and oxide.
    [38] In addition, in Ba x Al y O z S w : Eu, part of Ba may be substituted with Mg, Ca, Sr, or part of Al may be substituted with B, Ga, In, Tl. The white chromaticity can be adjusted by this substitution.
    [39] It is also preferable to add Eu as the light emitting center. As addition amount of Eu, it is preferable to add 1-10 mol% with respect to a barium atom. In addition, other rare earth elements may be added together with Eu, or may be added alone. For example, the rare earth element is selected from Sc, Y, La, Ce, Pr, Nd, Gd, Tb, Ho, Er, Tm, Lu, Sm, Eu, Dy and Yb, but in addition to Eu, Ce, Tb, Ho, It is preferable to add Sm, Yb, and Nd. The chromaticity of white can be adjusted by adding these other rare earth elements.
    [40] There is no particular limitation on the film thickness, but when the thickness is too thick, the EL driving voltage rises, and when the thickness is too thin, the luminous efficiency decreases. Although it is specifically about 50-1000 nm, especially about 100-400 nm, in order to make a white phosphor, the film thickness ratio with the 2nd thin film mentioned later is important.
    [41] The second thin film of the present invention is a thin film whose main material is zinc sulfide. The base material has ZnS as a main component, and may be a solid solution or a laminate with ZnS such as MgS, SrS, BaS and the like. Examples of the light emitting center include one or more elements selected from transition metal elements such as Mn and Cu, rare earth metal elements, and Pb and Bi. In particular, a ZnS: Mn-based phosphor which is conventionally used as an orange phosphor thin film is preferable. It is preferable to make Mn into a light emission center and add 0.1-1.0 mol%, preferably 0.2-0.6 mol%, especially 0.3-0.4 mol% with respect to a 2nd base material. In addition, according to the solid solution with ZnS, the orange chromaticity adjustment of ZnS: Mn is possible, and the white chromaticity adjustment of the present invention is also possible.
    [42] The film thickness is not particularly limited, but if it is too thick, the EL driving voltage will rise, and if it is too thin, the luminous efficiency will decrease. Specifically, it is about 300-2000 nm, especially about 400-800 nm.
    [43] The stacking order and the number of stacking times of the first thin film and the second thin film are not particularly limited. The first thin film and the second thin film may each be used multiple times in the same or different composition. For example, a ZnS: Mn fluorescent film and a ZnMgS: Mn fluorescent film which is a solid solution can also be used many times with respect to a 2nd thin film. When the white of the present invention is used to emit red, green, and blue colors by a color filter and is applied to a full-color display, red, green, and blue colors can be adjusted by the plurality of films described above. These films may be formed first by forming them under high film forming temperature conditions. That is, it is preferable to make the thin film with a high film formation temperature be a substrate side. Usually, it is preferable to form a second thin film on the first thin film.
    [44] White (chromaticity) can be adjusted by adjusting the ratio T2 / T1 of the total film thickness T1 of the first thin film and the total film thickness T2 of the second thin film. If the value of T2 / T1 is too large, it becomes white close to yellow, and if it is too small, it becomes blue-white white.
    [45] In the laminate of the present invention, the light emitting synthetic color of the first thin film and the second thin film has a high purity of x = 0.27-0.39, y = 0.27-0.38, especially x = 0.30-0.36, y = 0.30-0.35 in the CIE chromaticity coordinates. White is obtained.
    [46] In order to obtain such a 1st thin film, it is preferable by the following reactive vapor deposition methods, for example.
    [47] For example, binary reactive vapor deposition using the addition of barium oxide pellets, alumina pellets, and H 2 S gas; Or binary vacuum deposition without addition of barium sulfide pellets, alumina pellets, or gas; Binary reactive vapor deposition using barium oxide pellets, alumina pellets, and H 2 S gas containing Eu; Barium sulfide pellets containing aluminium, alumina pellets, and binary deposition without using gas; Barium oxide pellets added with Eu, alumina sulfide pellets, binary vacuum deposition without gas; Binary reactive vapor deposition using barium sulfide pellets, alumina sulfide pellets, and H 2 S gas containing Eu; Binary reactive vapor deposition using barium sulfide pellets, alumina sulfide pellets with Eu, and O 2 gas; And the like are preferred. After the sulfide thin film is formed, the sulfur-added barium aluminate thin film can be obtained by annealing in an oxidizing atmosphere.
    [48] Eu to be added is added to the raw materials in the form of metals, fluorides, oxides or sulfides. Since the amount of addition depends on the raw material and the thin film to be formed, the composition of the raw material is adjusted to an appropriate amount of addition.
    [49] The substrate temperature during vapor deposition is 100 to 600 degreeC, Preferably it can be 150 to 300 degreeC. If the substrate temperature is too high, the unevenness of the thin film surface of the mother material becomes severe, pinholes in the thin film are generated, and current leakage occurs in the EL element. Therefore, the above temperature range is preferable. Moreover, it is preferable to perform the annealing process after film-forming. The annealing temperature is preferably 600 ° C to 1000 ° C, in particular 800 ° C to 900 ° C.
    [50] The formed oxide fluorescent thin film is preferably a high crystalline thin film. Crystallinity evaluation can be performed by X-ray diffraction, for example. In order to raise crystallinity, possible substrate temperature is made high temperature. In addition, annealing in vacuum, air, 0 2 , N 2 , Ar, S steam, H 2 S, etc. after thin film formation is also effective.
    [51] The pressure at the time of vapor deposition is preferably 1.33 x 10 -4 to 1.33 x 10 -1 Pa (1 x 10 -6 to 1 x 10 -3 Torr). In addition, when introducing a gas such as H 2 S, it can be made by adjusting the pressure 6.65 x 10 -3 ~6.65 x 10 -2 Pa (5 x 10 -5 ~5 x 10 -4 Torr). If the pressure is higher than this, the operation of the electron gun becomes unstable, and the composition control becomes very difficult. The amount of gas introduced depends on the capability of the vacuum system, but preferably 5 to 200 SCCM, particularly 10 to 30 SCCM.
    [52] In addition, if necessary, the substrate may be moved or diffracted at the time of vapor deposition. By moving and rotating the substrate, the film composition becomes uniform and the variation in the film thickness distribution is reduced.
    [53] When rotating a board | substrate, as a rotation speed of a board | substrate, Preferably it is 10 times / min or more, More preferably, it is 10-50 times / min, Especially about 10-30 times / min. If the rotation speed of the substrate is too fast, problems such as sealing property are likely to occur when the substrate is introduced into the vacuum chamber. In addition, if it is too slow, a composition deviation will occur in the film thickness direction in a bath, and the characteristic of the produced light emitting layer will fall. The rotating means for rotating the substrate can be composed of a power source such as a motor, a hydraulic rotating mechanism, a known rotating mechanism using a power transmission mechanism, a reduction mechanism, and the like combined with a gear, a belt, a pulley, and the like.
    [54] The heating means for heating the evaporation source or the substrate preferably has a predetermined heat capacity, reactivity, and the like, and examples thereof include tantalum heaters, sheath heaters and carbon heaters. Preferably the heating temperature by a heating means is about 100-1400 degreeC, and the precision of temperature control is 1000 degreeC to +/- 1 degreeC, Preferably it is about 0.5 degreeC.
    [55] An example of the structure of the apparatus for forming the light emitting layer of this invention is shown in FIG. Here, an example is a method of producing S-added barium aluminate: Eu with aluminum sulfide and barium sulfide as evaporation sources and introducing oxygen. In the drawing, the substrate 12 and the EB evaporation sources 14 and 15 in which the light emitting layer is formed are disposed in the vacuum layer 11.
    [56] EB (electron beam) evaporators 14 and 15, which consist of evaporation means of aluminum sulfide and barium sulfide, have a "crucible" (40, 50) containing barium sulfide (14a) and aluminum sulfide (15a) with an emission center and electrons. The electron guns 41 and 51 incorporating the emission filaments 41a and 51a are provided. In the electron guns 41 and 51, a mechanism for controlling the beam is incorporated. The electron guns 41 and 51 are connected to the AC power sources 42 and 52 and the bias power sources 43 and 53. The electron beam is controlled from the electron gun, and in turn, the barium sulfide and aluminum sulfide to which the light emitting center is added can be evaporated at a predetermined ratio by a predetermined power source. The deposition method for multi-simultaneous simultaneous deposition with one electron gun is called multi-pulse deposition. In this example, the EB evaporation source is used as the evaporation source of aluminum sulfide and barium sulfide, but one or both can be replaced by another evaporation source such as a resistance heating evaporation source.
    [57] The vacuum chamber 11 has an exhaust port 11a, and as it evacuates from this exhaust port, the inside of the vacuum chamber 11 can be made into the predetermined vacuum degree. The vacuum chamber 11 also has a source gas introduction port 11b for introducing hydrogen sulfide gas or the like.
    [58] The substrate 12 is fixed to the substrate holder 12a, and the fixed shaft 12b of the substrate holder 12a rotates from the outside while maintaining the degree of vacuum in the vacuum chamber 11 by a rotation shaft fixing means (not shown). It is fixed. And, by the rotation means not shown, it is possible to rotate at a predetermined rotation speed as needed. In addition, a heating means 13 made of a heater wire or the like is tightly fixed to the substrate holder 12a, and the substrate can be heated and maintained at a desired temperature.
    [59] Using this apparatus, barium sulfide vapor and aluminum sulfide vapor evaporated from the EB evaporation sources 14 and 15 are deposited on the substrate 12 and combined with the introduced oxygen to form an S-added oxide fluorescent layer. At this time, the composition and the film thickness distribution of the deposited light emitting layer can be made more uniform by rotating the substrate 12 as necessary.
    [60] The second thin film can be formed by a known method such as a vapor deposition method using a ZnS: Mn pellet or a sputtering method using a ZnS target.
    [61] As described above, according to the fluorescent thin film material of the present invention and the manufacturing method by vapor deposition, the phosphor thin film having a laminated structure emitting white light with high brightness can be easily formed.
    [62] What is necessary is just to have a structure as shown in FIG. 2, for example, in order to obtain an inorganic EL element using the light emitting layer 3 of this invention. Between each of the substrate 1, the electrodes 5 and 6, the thick film insulating layer 2 (hereinafter referred to as a thick film insulating layer), and the thin film insulating layer 4, a layer for enhancing adhesion and for relieving stress Intermediate layers, such as a layer and a layer for preventing a reaction, can also be provided. The thick film surface may also be polished or a flattening layer may be used to improve flatness.
    [63] 2 is a partial cross-sectional perspective view showing the structure of an inorganic EL device using the laminated phosphor of the present invention. In FIG. 2, a lower electrode 5 of a predetermined pattern is formed on the substrate 1, and a first insulating layer (thick film dielectric layer) 2 of a thick film is formed on the lower electrode 5. The light emitting layer 3 and the second insulating layer (thick film dielectric layer) 4 are sequentially formed on the first insulating layer 2, and the lower electrode 5 and the matrix circuit are formed on the second insulating layer 4. The upper electrode 6 is formed in a predetermined pattern so as to constitute. The laminated phosphor is used for the light emitting layer.
    [64] The material used as the substrate is a substrate having a heat resistance temperature to melting temperature of 600 ° C. or higher, preferably 700 ° C. or higher, particularly 800 ° C. or higher, capable of withstanding the thick film formation temperature, the EL fluorescent layer formation temperature, and the annealing temperature of the EL element. Then, the EL element can be formed by a functional thin film such as a light emitting layer formed thereon, and there is no particular limitation as long as it can maintain a predetermined intensity. Specifically, glass or alumina (Al 2 O 3 ), pulse territe (2MgO · SiO 2 ), stearite (MgO · SiO 2 ), mullite (3Al 2 O 3 · SiO 2 ), beryllium oxide (BeO), Ceramic substrates, such as aluminum nitride (AlN), silicon nitride (SiN), and silicon carbide (Sic + BeO), and heat resistant glass substrates, such as crystalline glass, are mentioned. Among these, it is preferable that heat resistance temperature is about 1000 degreeC or more. Among these, an alumina substrate and crystallized glass are especially preferable, and when a thermal conductivity is needed, beryllium oxide, aluminum nitride, silicon carbide, etc. are preferable.
    [65] In addition to these, metal substrates such as titanium, stainless steel, inconel, iron, and the like may be used. In the case of using a conductive substrate such as a metal, a structure in which a thick film having electrodes therein is formed on the substrate.
    [66] As the dielectric thick film material (first insulating layer), a known dielectric thick film material can be used, and a material having a relatively high dielectric constant is preferable.
    [67] For example, materials such as lead titanate, lead niobate, and barium titanate can be used.
    [68] The resistivity of the dielectric thick film is 10 8 Ωcm or more, particularly about 10 10 -10 18 Ωcm. Also preferred are materials having a relatively high relative dielectric constant. The ratio electric conductivity ε is preferably about ε = 100 to 10000. 5-50 micrometers is preferable and, as for a film thickness, 10-30 micrometers is especially preferable.
    [69] Although the formation method of an insulating layer thick film does not have a restriction | limiting in particular, Although the method of obtaining a film of 10-50 micrometers thickness comparatively easily is good, the sol-gel method, the printing baking method, etc. are preferable.
    [70] In the case of the printing firing method, the particle size of the material is appropriately evenly mixed with a binder to obtain a paste having a suitable viscosity. This paste is formed on the substrate by screen printing and dried. This green sheet is calcined at an appropriate temperature to obtain a thick film.
    [71] As a constituent material of the thin film insulating layer (second insulating layer), for example, silicon oxide (SiO 2 ), silicon nitride (SiN), tantalum oxide (Ta 2 O 5 ), strontium titanate (SrTi0 3 ), yttrium oxide ( Y 2 O 3 ), barium titanate (BaTiO 3 ), lead titanate (PbTiO 3 ), PZT, zirconia (Zr0 2 ), silicon oxynitride (SiON), alumina (Al 2 O 3 ), lead niobate, PMN- PT type materials and these multilayer or mixed thin films can be mentioned, and existing methods, such as a vapor deposition method, a sputtering method, a CVD method, a sol-gel method, the printing baking method, can be used as a method of forming an insulating layer from these materials. The film thickness of the insulating layer in this case is preferably 50 to 1000 nm, particularly about 100 to 500 nm.
    [72] The electrode (lower electrode) is formed at least in the substrate side or in the first dielectric. In the formation of a thick film, in particular, the electrode layer exposed to high temperature during heat treatment together with the light emitting layer is mainly used as one or two or more commonly used metals such as palladium, rhodium, iridium, rhenium, ruthenium, platinum, tantalum, nickel, chromium and titanium. An electrode can be used.
    [73] Moreover, since the other electrode layer used as an upper electrode emits light emission from the opposite side of a board | substrate normally, the transparent electrode which has transparency in a predetermined light emission wavelength range is preferable. The transparent electrode can also be used as a lower electrode because it is possible to emit emitted light from the substrate side if the substrate is transparent. In this case, it is particularly preferable to use a transparent electrode such as ZnO or ITO. ITO usually contains In 2 O 3 and SnO in stoichiometric composition, but the amount of O may vary somewhat. The mixing ratio of SnO 2 to In 2 O 3 is preferably 1 to 20% by mass, particularly preferably 5 to 12% by mass. In addition, the mixing ratio of ZnO to the In 2 O 3 in IZO is on the order of 12-32% by weight.
    [74] In addition, the electrode preferably has silicon. The silicon electrode layer may be polycrystalline silicon (p-Si), amorphous (a-Si), or monocrystalline silicon as necessary.
    [75] The electrode dopes an impurity for securing conductivity to the main component silicon. The dopant used as an impurity should just be able to ensure predetermined | prescribed electroconductivity, and the normal dopant used for a silicon semiconductor can be used. Specifically, B, P, As, Sb, Al, etc. are mentioned, Among these, B, P, As, Sb, and Al are especially preferable. The concentration of the dopant is preferably about 0.001 to 5 at%.
    [76] Conventional methods such as vapor deposition, sputtering, CVD, sol-gel, and printing firing can be used as a method of forming the electrode layer from these materials, but in particular, a structure in which a thick film having electrodes therein is formed on a substrate. In this case, the same method as that of the dielectric thick film is preferable.
    [77] As a preferable resistivity of an electrode layer, in order to give an efficient electric field to a light emitting layer, 1 ohm cm or less, especially 0.003-0.1 ohm cm are preferable. Although the film thickness of an electrode layer is based on the material to form, Preferably it is 50-2000 nm, Especially about 100-1000 nm is preferable.
    [78] In the above, the case of applying the light emitting layer of the present invention to the inorganic EL device has been described. It can be applied.
    [79] (Example)
    [80] Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.
    [81] (Example 1)
    [82] 1 shows an example of a deposition apparatus that can be used in the manufacturing method of the present invention. Instead of the two-point control gun, one electron gun and one resistance heating cell were used.
    [83] EB source 15 containing BaS powder added with 5 mol% of Eu and resistance heating cell source 14 containing Al 2 O 3 powder were installed in vacuum chamber 11, and evaporated simultaneously from each source to 400 ° C. A Ba x Al y O z S w : Eu layer was formed on the heated and rotated substrate. The evaporation rate of each evaporation source was adjusted so that the thin film obtained would be 1 nm / sec. At this time, H 2 S gas was introduced 20SCCM. After the thin film was formed, the film was annealed for 10 minutes in an atmosphere of 750 ° C. to form a first thin film having a thickness of 300 nm.
    [84] Using the ZnS pellet to which 0.5 mol% Mn was added thereon, the 2nd thin film was formed in 400 nm of thickness by EB evaporation.
    [85] The first thin film Ba x Al y O z S w : Eu thin film was separately prepared and analyzed by fluorescence X-ray analysis, and the atomic ratio Ba: Al: O: S: Eu = 7.40: 19.18: 70.15: 2.90: 0.36 It was.
    [86] In addition, an EL device using this light emitting layer was produced. The white emission luminance of 500 cd / m 2 was obtained with good reproducibility by applying an electric field with a pulse width of 50 Hz to the electrode. The luminescent color of the paper was obtained as x = 0.352, y = 0.303 in the CIE chromaticity coordinates.
    [87] As described above, the laminated phosphor of the present invention can obtain a white phosphor thin film material having good color purity and emitting high brightness without using a filter.
    [88] In addition, the EL element using such a laminated phosphor is excellent in light emission characteristics, and in particular, it is possible to form a white EL element or a monochromatic EL panel, which is of great practical value.
    [89] As described above, according to the present invention, it is possible to provide a laminated phosphor and an EL panel which have good color purity without particularly requiring a filter, and are particularly suitable for white monochrome EL.
    权利要求:
    Claims (5)
    [1" claim-type="Currently amended] A multilayer phosphor having at least a first thin film and a second thin film, wherein the mother material of the first thin film contains barium aluminate as a main component and contains sulfur element in the mother material, and Eu as a light emitting center. A laminated phosphor whose main material of the thin film is zinc sulfide as a main component.
    [2" claim-type="Currently amended] The laminated phosphor according to claim 1, wherein the molar ratio S / (S + O) of the mixed amount of the sulfur element and the oxygen element of the parent material is 0.02 to 0.5.
    [3" claim-type="Currently amended] The molar ratio S / (S + O) of the mixed amount of the sulfur element and the oxygen element of the parent material is 0.7 to 0.9, and the ratio Al / Ba of the barium element Ba and the aluminum element Al is 1.5 to 3.0. Laminated phosphor.
    [4" claim-type="Currently amended] 2. The stacked phosphor of claim 1, wherein the light emission synthetic color of the first thin film and the second thin film is white in x = 0.27 to 0.39 and y = 0.27 to 0.38 in a CIE chromaticity coordinate.
    [5" claim-type="Currently amended] An EL panel having the laminated phosphor of claim 1.
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    同族专利:
    公开号 | 公开日
    US6761835B2|2004-07-13|
    EP1170350B1|2006-11-22|
    CN1192075C|2005-03-09|
    DE60124627T2|2007-09-13|
    DE60124627D1|2007-01-04|
    CA2352499A1|2002-01-07|
    EP1170350A3|2003-11-05|
    CA2352499C|2005-05-10|
    CN1333322A|2002-01-30|
    KR100405184B1|2003-11-12|
    EP1170350A2|2002-01-09|
    TW528791B|2003-04-21|
    US20020005506A1|2002-01-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-07-07|Priority to JPJP-P-2000-00206652
    2000-07-07|Priority to JP2000206652
    2000-10-03|Priority to JPJP-P-2000-00303719
    2000-10-03|Priority to JP2000303718A
    2000-10-03|Priority to JP2000303719
    2000-10-03|Priority to JPJP-P-2000-00303718
    2001-05-11|Priority to JP2001142024A
    2001-05-11|Priority to JPJP-P-2001-00142024
    2001-07-06|Application filed by 사토 히로시, 티디케이가부시기가이샤
    2002-01-17|Publication of KR20020005477A
    2003-11-12|Application granted
    2003-11-12|Publication of KR100405184B1
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP-P-2000-00206652|2000-07-07|
    JP2000206652|2000-07-07|
    JP2000303719|2000-10-03|
    JPJP-P-2000-00303718|2000-10-03|
    JPJP-P-2000-00303719|2000-10-03|
    JP2000303718A|JP3501742B2|2000-10-03|2000-10-03|Multilayer phosphor and EL panel|
    JP2001142024A|JP3704057B2|2000-07-07|2001-05-11|Phosphor thin film and method for manufacturing the same, and EL panel|
    JPJP-P-2001-00142024|2001-05-11|
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