[go: up one dir, main page]

WO2014092165A1 - Elément à émission de lumière de surface utilisant un substrat en oxyde de zinc - Google Patents

Elément à émission de lumière de surface utilisant un substrat en oxyde de zinc Download PDF

Info

Publication number
WO2014092165A1
WO2014092165A1 PCT/JP2013/083376 JP2013083376W WO2014092165A1 WO 2014092165 A1 WO2014092165 A1 WO 2014092165A1 JP 2013083376 W JP2013083376 W JP 2013083376W WO 2014092165 A1 WO2014092165 A1 WO 2014092165A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc oxide
light emitting
sintered body
layer
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/083376
Other languages
English (en)
Japanese (ja)
Inventor
守道 渡邊
克宏 今井
吉川　潤
七瀧　努
隆史 吉野
武内　幸久
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to JP2014552091A priority Critical patent/JPWO2014092165A1/ja
Publication of WO2014092165A1 publication Critical patent/WO2014092165A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/817—Bodies characterised by the crystal structures or orientations, e.g. polycrystalline, amorphous or porous
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/822—Materials of the light-emitting regions
    • H10H20/823—Materials of the light-emitting regions comprising only Group II-VI materials, e.g. ZnO
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/83—Electrodes
    • H10H20/832—Electrodes characterised by their material
    • H10H20/835—Reflective materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8514—Wavelength conversion means characterised by their shape, e.g. plate or foil

Definitions

  • the present invention relates to a surface light emitting device using a zinc oxide substrate.
  • surface-emitting EL lighting has attracted attention as next-generation lighting.
  • the surface-emitting EL illumination has advantages such as high brightness uniformity, thin and space-saving, high designability, and eye-friendlyness.
  • surface-emitting EL lighting is partially commercialized using organic EL, there are still many issues for widespread use in terms of cost and durability.
  • a light emitting diode (LED) is used, there is a problem that it is difficult to increase the area of the element because it is necessary to use an expensive substrate.
  • zinc oxide (ZnO) is a safe and inexpensive compound semiconductor, and is known as a material that is chemically stable and excellent in transparency. It is mainly used in the form of sintered bodies and powders, and is used for sputtering targets, varistors, additives to rubber, cosmetics and the like. When used as a sintered body, it is known that the characteristics change by orienting the crystal orientation. For example, Patent Document 1 discloses a crystal orientation property in which the orientation ratio of (101) crystal orientation is within a predetermined range. A zinc oxide sintered body is disclosed as a sputtering target.
  • Non-Patent Document 1 an Mg x Zn 1-x O film doped with N is formed on a Zn-polar ZnO single crystal substrate. It was reported that ultraviolet light emission was observed in the LED fabricated in this manner.
  • the present inventors have now obtained the knowledge that a surface-emitting element with high luminous efficiency can be provided at low cost by using a plate-like oriented polycrystalline zinc oxide sintered body as a substrate.
  • an object of the present invention is to provide a surface light emitting device having high luminous efficiency at a low cost.
  • a substrate composed of a plate-like oriented polycrystalline zinc oxide sintered body; A light emitting functional layer provided on the substrate; An electrode provided on the light emitting functional layer; There is provided a surface light emitting device comprising:
  • FIG. 6 is a schematic cross-sectional view showing an AD film forming apparatus used in Example 2.
  • FIG. 6 is a schematic cross-sectional view showing a heating device used in Example 2.
  • FIG. 6 is a schematic cross-sectional view showing an AD film forming apparatus used in Example 2.
  • FIG. 1 schematically shows the structure of a surface light emitting element according to one embodiment of the present invention.
  • the surface light emitting device 10 shown in FIG. 1 includes a substrate 12, a light emitting functional layer 14 provided on the substrate, and an electrode 16 provided on the light emitting functional layer.
  • the substrate 12 is composed of a plate-like oriented polycrystalline zinc oxide sintered body.
  • the zinc oxide crystal has a hexagonal wurtzite structure
  • the oriented polycrystalline zinc oxide sintered body is a solid formed by bonding innumerable zinc oxide crystal particles to each other by sintering.
  • the zinc oxide crystal particles are particles composed of zinc oxide, and may include a dopant and inevitable impurities as other elements, or may be composed of zinc oxide and inevitable impurities.
  • Such other elements may be substituted with hexagonal wurtzite structure Zn sites or O sites, may be included as additive elements that do not constitute a crystal structure, or exist at grain boundaries. It may be a thing.
  • the zinc oxide sintered body may also contain other phases or other elements as described above in addition to the zinc oxide crystal particles, but preferably comprises zinc oxide crystal particles and inevitable impurities.
  • the oriented polycrystalline zinc oxide sintered body may be composed of ZnO mixed with one or more kinds of crystals selected from the group consisting of MgO, CdO, ZnS, ZnSe, and ZnTe, and The oriented polycrystalline zinc oxide sintered body may be doped with an n-type dopant so that the substrate 12 functions as an n-type zinc oxide layer.
  • n-type dopant examples include aluminum (Al), gallium (Ga), indium (In), boron (B) fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and silicon ( 1 or more types selected from the group consisting of Si).
  • the oriented polycrystalline zinc oxide sintered body is composed of a zinc oxide sintered body including a large number of zinc oxide single crystal particles, and the single crystal particles are oriented to some extent or highly in a certain direction. It is a thing.
  • the polycrystalline zinc oxide sintered body thus oriented is higher in strength and cheaper than a zinc oxide single crystal, and therefore has a large area while being much cheaper than using a single crystal substrate. Enables production of light emitting elements.
  • high luminous efficiency can be realized by using an oriented polycrystalline zinc oxide sintered body.
  • the constituent layer of the light emitting functional layer 14 is formed on the oriented substrate 12 by epitaxial growth, a state in which the crystal orientation is aligned in the normal direction is realized, so that it is as high as when a single crystal substrate is used. Luminous efficiency can be obtained.
  • the oriented polycrystalline zinc oxide sintered body has low light transmittance due to the presence of grain boundaries, and incident light is easily scattered and reflected. For this reason, in the case of a structure in which light is extracted from the light emitting functional layer 14 on the side opposite to the substrate 12 (that is, on the electrode 16 side), it is easy to emit scattered light and reflected light from the substrate 12 to increase the light emission efficiency. Can do. Due to these various factors, according to the present invention using a plate-like oriented polycrystalline zinc oxide sintered body as a substrate, it is possible to provide a surface emitting device with high luminous efficiency and a large area at low cost.
  • the substrate 12 preferably has an area of 25 cm 2 or more, more preferably 100 cm 2 or more, and further preferably 400 cm 2 or more.
  • the substrate 12 preferably has a size of 5 ⁇ 5 cm or more, more preferably 10 ⁇ 10 cm or more, and further preferably 20 ⁇ 20 cm or more.
  • the average particle diameter of the zinc oxide single crystal particles constituting the oriented polycrystalline zinc oxide sintered body is preferably 1 to 100 ⁇ m, more preferably 10 to 80 ⁇ m, and still more preferably 20 to 50 ⁇ m. Within these ranges, the light emission efficiency, mechanical strength, light scattering properties, reflectivity, etc. are excellent.
  • the average particle size of the sintered particles in the present invention is measured by the following method. That is, a sample of an appropriate size is cut out from the plate-shaped sintered body, the surface perpendicular to the plate surface is polished, etched with nitric acid having a concentration of 0.3 M for 10 seconds, and then an image is obtained with a scanning electron microscope. Take a picture.
  • the visual field range is a visual field range in which straight lines intersecting 10 to 30 particles can be drawn when straight lines parallel and perpendicular to the plate surface are drawn.
  • a value obtained by multiplying the average length of the line segments inside the individual particles by 1.5 for all the particles intersecting the straight line is a 1
  • a value obtained by multiplying the average length of the inner line segment of each particle by 1.5 for all the particles intersecting with each other is a 2 and (a 1 + a 2 ) / 2 is the average particle size.
  • the orientation plane orientation of the oriented polycrystalline zinc oxide sintered body is not particularly limited, and may be a (002) plane, a (100) plane, or another plane. Good.
  • the degree of orientation for example, the degree of orientation on the substrate surface is preferably 50% or more, more preferably 65% or more, and further preferably 75% or more. This degree of orientation was measured using an XRD apparatus (for example, product name “RINT-TTR III” manufactured by Rigaku Corporation) and measuring the XRD profile when the surface of the plate-like zinc oxide was irradiated with X-rays. It is obtained by calculating by the following formula.
  • the light emitting functional layer 14 is provided on the substrate.
  • the light-emitting functional layer 14 may be any layer that has a light-emitting function in the light-emitting element. As long as a desired light-emitting function can be secured on the oriented polycrystalline zinc oxide sintered body that is a constituent material of the substrate 12, The method is not limited. Therefore, the light emitting functional layer 12 may emit blue or red visible light, or may emit ultraviolet light without visible light or together with visible light. In this regard, since the light emitting functional layer 14 shown in FIG. 1 is configured to emit ultraviolet light, a phosphor layer 17 is separately provided to convert the ultraviolet light into visible light.
  • the light-emitting functional layer 14 preferably constitutes at least a part of a light-emitting element using a pn junction, and the pn junction may include a light-emitting layer between the p-type layer and the n-type layer. . Further, as one form of the p-type layer-the light-emitting layer-the n-type layer, a quantum well structure in which the light-emitting layer is thin can be adopted. In the case of a pn junction, each of the p-type layer, the n-type layer, and the light-emitting layer (when the light-emitting layer is included) can be made of a zinc oxide-based material, which is also made of zinc oxide. Therefore, it is easy to align the orientation or crystal orientation with the substrate, thereby increasing the light emission efficiency.
  • the light emitting functional layer 14 preferably includes at least a p-type zinc oxide layer 14a made of ZnO doped with a p-type dopant.
  • a light-emitting element with a pn junction can be formed by combination with the n-type zinc oxide layer 14b, while the substrate 12 is made to be n-type even when a configuration without the n-type zinc oxide layer 14b is adopted.
  • a light emitting element with a pn junction can be configured in combination with the substrate 12.
  • the p-type dopant include nitrogen (N), phosphorus (P), arsenic (As) carbon (C) lithium (Li), sodium (Na), potassium (K), silver (Ag), and copper (Cu). 1) or more selected from the group consisting of
  • the p-type zinc oxide layer may be made of ZnO mixed with one or more kinds of crystals selected from the group consisting of MgO, CdO, ZnS, ZnSe, and ZnTe. ZnO may be doped with a p-type dopant.
  • a compound in which Mg x Zn 1-x O (0.1 ⁇ x ⁇ 0.4), which is a mixed crystal of ZnO and MgO, is doped with N is particularly preferable.
  • ZnO mixed with MgO the band gap is widened, and the emission wavelength can be shifted to a higher energy side.
  • ZnO may be a mixed crystal with CdO, ZnS, ZnTe, or ZnSe, thereby narrowing the band gap and shifting the emission wavelength to the lower energy side.
  • the light emitting functional layer 14 may further include an n-type zinc oxide layer 14b doped with an n-type dopant between the p-type zinc oxide layer 14a and the substrate 12.
  • the n-type dopant include aluminum (Al), gallium (Ga), indium (In), boron (B) fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and silicon ( 1 or more types selected from the group consisting of Si).
  • the n-type zinc oxide layer may be made of ZnO mixed with one or more kinds of crystals selected from the group consisting of MgO, CdO, ZnS, ZnSe, and ZnTe.
  • ZnO may be doped with an n-type dopant.
  • a compound in which Mg x Zn 1-x O (0.1 ⁇ x ⁇ 0.4), which is a mixed crystal of ZnO and MgO, is doped with Al or Ga is particularly preferable.
  • the n-type zinc oxide layer 14b can be omitted.
  • the light emitting functional layer 14 includes ZnO or MgO having a smaller band gap than the p-type zinc oxide layer 14a and the n-type zinc oxide layer 14b between the p-type zinc oxide layer 14a and the n-type zinc oxide layer 14b.
  • You may have at least the light emitting layer which consists of a mixed crystal of ZnO with 1 or more types selected from the group which consists of CdO, ZnS, ZnSe, and ZnTe, and does not contain a p-type dopant and an n-type dopant.
  • the structure in which the light emitting layer is thin corresponds to a light emitting element having a quantum well structure which is an embodiment of a pn junction, and the light emission efficiency can be further improved.
  • the light emitting functional layer 14 is formed between the p-type zinc oxide layer 14a and the oriented polycrystalline zinc oxide sintered body 12, One or more selected from the group consisting of ZnO or MgO, CdO, ZnS, ZnSe, and ZnTe having a smaller band gap than any of the p-type zinc oxide layer 14a and the oriented polycrystalline zinc oxide sintered body 12, and ZnO What is necessary is just to comprise so that it may consist of a mixed crystal and may have at least the light emitting layer which does not contain a p-type dopant and an n-type dopant.
  • the light emitting functional layer 14 has a structure that is epitaxially grown following the orientation of the oriented polycrystalline zinc oxide sintered body, and thereby has a crystal orientation aligned in the normal direction. Since the polycrystalline zinc oxide sintered body, which is a constituent material of the substrate 12, is oriented, the crystal orientation of the light emitting functional layer 14 also grows in accordance with the orientation, so that the orientation is constant, so that the light emitting functional layer is a polycrystalline light emitting functional layer. Even so, it is possible to obtain excellent light emission characteristics close to a single crystal.
  • the method for forming the light emitting functional layer 14 having such a structure is not particularly limited as long as it is a method for promoting growth according to the orientation of the substrate, but sputtering, molecular beam epitaxy (MBE), solid epitaxial growth, etc. Is preferably exemplified.
  • the solid epitaxial growth method can be preferably performed by, for example, forming a film on a substrate by an aerosol deposition method (AD method) and making a single crystal by heating a film. In this way, since the functional layer is grown in line with the sintered grain size of the polycrystalline zinc oxide sintered body, the normal direction is aligned in a single orientation (single crystal), and there is a grain boundary in the xy direction.
  • the light emitting functional layer has a grain boundary in the xy direction
  • the light in the horizontal direction is scattered and reflected by the grain boundary, and as a result, the light in the normal direction has high intensity.
  • the directivity of light is increased, and further high intensity and high efficiency can be obtained.
  • the light emitting functional layer 14 is capable of emitting ultraviolet light
  • the phosphor layer 17 is not particularly limited as long as it includes a known fluorescent component capable of converting ultraviolet light into visible light.
  • a fluorescent component that emits blue light when excited by ultraviolet light, a fluorescent component that emits blue to green light when excited by ultraviolet light, and a fluorescent component that emits red light when excited by ultraviolet light are mixed. It is preferable that white light is obtained as a mixed color.
  • Preferred combinations of such fluorescent components include (Ca, Sr) 5 (PO 4 ) 3 Cl: Eu, BaMgAl 10 O 17 : Eu, and Mn, Y 2 O 3 S: Eu, and these components Is preferably dispersed in a resin such as a silicone resin to form the phosphor layer 17.
  • a fluorescent component is not limited to the above-exemplified substances, and may be a combination of other ultraviolet light-excited phosphors such as yttrium aluminum garnet (YAG), silicate phosphors, and oxynitride phosphors. .
  • a phosphor layer 17 for converting blue light into yellow light is further provided outside the electrode 16.
  • the phosphor layer 17 is not particularly limited as long as it includes a known fluorescent component capable of converting blue light into yellow light. For example, it may be combined with a phosphor emitting yellow light such as YAG. By doing in this way, since blue light emission which permeate
  • the phosphor layer 17 includes both a fluorescent component for converting blue to yellow and a fluorescent component for converting ultraviolet light to visible light, thereby converting ultraviolet light into visible light and blue light. It is good also as a structure which performs both conversion to yellow light.
  • the electrode 16 is provided on the light emitting functional layer 14.
  • the electrode 16 may be made of a known electrode material, but if a transparent conductive film such as ITO or a metal electrode having a high aperture ratio such as a lattice structure or a moth-eye structure is used, the light extraction efficiency generated in the light emitting functional layer 14 is extracted. Is preferable in that it can be increased.
  • the substrate 12 is configured to function as a counter electrode. However, if this is not the case, a counter electrode may be separately provided on the side of the substrate 12 opposite to the light emitting functional layer 14.
  • the n-type layer included in the light emitting functional layer 14 may be used as an electrode, or an electrode may be provided on the n-type layer.
  • a method for producing an oriented polycrystalline zinc oxide sintered body An oriented polycrystalline zinc oxide sintered body used as the substrate 12 is formed and sintered by using a plate-like zinc oxide powder as a raw material as described below. Can be manufactured.
  • the plate-like zinc oxide powder as a raw material may be produced by any method as long as an oriented sintered body is obtained by the molding and firing steps described later.
  • a plate-like zinc oxide powder produced according to the method described in Patent Document 1 may be used as a raw material.
  • a plate-like zinc oxide powder produced by the following production method may be used as a raw material.
  • the plate-like zinc oxide powder includes a step of producing zinc oxide precursor plate-like particles by a solution method using a zinc ion-containing raw material solution, and calcining the precursor plate-like particles at a heating rate of 150 ° C./h or less. And calcining by raising the temperature to a temperature and producing a zinc oxide powder composed of a plurality of zinc oxide plate-like particles.
  • zinc oxide precursor plate-like particles are produced by a solution method using a zinc ion-containing raw material solution.
  • the zinc ion supply source include organic acid salts such as zinc sulfate, zinc nitrate, zinc chloride, and zinc acetate, zinc alkoxide, and the like, but zinc sulfate is preferable because sulfate ions described later can also be supplied.
  • the production method of the zinc oxide precursor plate-like particles by the solution method is not particularly limited, and can be performed according to a known method.
  • the raw material solution preferably contains a water-soluble organic substance and sulfate ions because it is porous and can increase the specific surface area.
  • water-soluble organic substances include alcohols, polyols, ketones, polyethers, esters, carboxylic acids, polycarboxylic acids, celluloses, saccharides, sulfonic acids, amino acids, and amines, and more Specifically, aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol and hexanol, aliphatic polyhydric alcohols such as ethylene glycol, propanediol, butanediol, glycerol, polyethylene glycol and polypropylene glycol, phenol and catechol , Aromatic alcohols such as cresol, alcohols having a heterocyclic ring such as furfuryl alcohol, ketones such as acetone, methyl ethyl ketone, acetylacetone, ethyl ether
  • water-soluble organic substances those having at least one functional group among hydroxyl group, carboxyl group, and amino group are preferable, hydroxycarboxylic acid having a hydroxyl group and a carboxyl group and salts thereof are particularly preferable, for example, sodium gluconate, Examples include tartaric acid.
  • the water-soluble organic substance is preferably allowed to coexist in a raw material solution to which ammonia water described later is added in a range of about 0.001 wt% to about 10 wt%.
  • a preferred sulfate ion source is zinc sulfate as described above.
  • the raw material solution may further contain an additive substance such as the dopant described above.
  • the raw material solution is preferably heated to a precursor reaction temperature of 70 to 100 ° C., more preferably 80 to 100 ° C. Further, it is preferable that ammonia water is added to the raw material solution after or during this heating, and the raw material solution to which the ammonia water is added is preferably held at 70 to 100 ° C. for 0.5 to 10 hours, more preferably. Is 80 to 100 ° C. for 2 to 8 hours.
  • the precursor plate-like particles are heated to the calcination temperature at a heating rate of 150 ° C./h or less and calcined to generate zinc oxide powder composed of a plurality of zinc oxide plate-like particles.
  • a heating rate of 150 ° C./h or less By slowing the heating rate to 150 ° C / h or less, the crystal surface of the precursor is easily transferred to zinc oxide when changing from precursor to zinc oxide, and the degree of orientation of plate-like particles in the compact is improved. It is thought to do. It is also considered that the connectivity between the primary particles increases and the plate-like particles are less likely to collapse.
  • a preferable temperature increase rate is 120 ° C./h or less, more preferably 100 ° C./h or less, further preferably 50 ° C./h or less, particularly preferably 30 ° C./h or less, and most preferably 15 It is below °C / h.
  • the zinc oxide precursor particles Prior to calcination, the zinc oxide precursor particles are preferably washed, filtered and dried.
  • the calcination temperature is not particularly limited as long as the precursor compound such as zinc hydroxide can be changed to zinc oxide, but is preferably 800 to 1100 ° C, more preferably 850 to 1000 ° C.
  • the precursor plate-like particles are preferably held for 0 to 3 hours, more preferably 0 to 1 hour. Under such temperature holding conditions, a precursor compound such as zinc hydroxide can be reliably changed by zinc oxide. By such a calcination step, the precursor plate-like particles are changed to plate-like zinc oxide particles having many pores.
  • an additive substance may be mixed in the zinc oxide powder.
  • additive substances include various additives that impart desired characteristics (for example, conductivity and insulation) according to the use and specifications of the molded body, and dopants as described above as the second component. it can.
  • dopant elements may be added to the zinc oxide powder in the form of compounds or ions containing these elements.
  • the addition method of the additive substance is not particularly limited, but in order to spread the additive substance even inside the fine pores of the zinc oxide powder, (1) a method of adding the additive substance to the zinc oxide powder in the form of fine powder such as nanoparticles (2) A method of adding the zinc oxide powder after dissolving the additive substance in the solvent and drying the solution is preferably exemplified.
  • a plate-like zinc oxide powder produced by the following production method may be used as a raw material.
  • the plate-like zinc oxide powder is prepared by adding an aqueous alkaline salt solution to an aqueous zinc salt solution and stirring at 60 to 95 ° C. for 2 to 10 hours to precipitate a precipitate, washing and drying the precipitate, and further pulverizing the precipitate.
  • the aqueous zinc salt solution may be an aqueous solution containing zinc ions, and is preferably an aqueous solution of a zinc salt such as zinc nitrate, zinc chloride, or zinc acetate.
  • the alkaline aqueous solution is preferably an aqueous solution of sodium hydroxide, potassium hydroxide or the like.
  • concentration and mixing ratio of the zinc salt aqueous solution and the alkaline aqueous solution are not particularly limited, but it is preferable to mix the zinc salt aqueous solution and the alkaline aqueous solution having the same molar concentration in the same volume ratio. It is preferable to wash the precipitate with ion exchange water a plurality of times.
  • the washed precipitate is preferably dried at 100 to 300 ° C. Since the dried precipitate is a spherical secondary particle in which plate-like zinc oxide primary particles are aggregated, it is preferably subjected to a pulverization step.
  • This pulverization is preferably carried out by adding a solvent such as ethanol to the washed precipitate in a ball mill for 1 to 10 hours.
  • a solvent such as ethanol
  • plate-like zinc oxide powder as primary particles is obtained.
  • the plate-like zinc oxide powder thus obtained preferably has a volume-based D50 average particle diameter of 0.1 to 1.0 ⁇ m, more preferably 0.3 to 0.8 ⁇ m. This volume standard D50 average particle diameter can be measured by a laser diffraction particle size distribution measuring apparatus.
  • the plate-like zinc oxide powder produced by the above method is oriented by a technique using shearing force to obtain an oriented molded body.
  • another element or component such as a metal oxide powder for dopant (for example, ⁇ -Al 2 O 3 powder) may be added to the plate-like zinc oxide powder.
  • the technique using shearing force include tape molding, extrusion molding, doctor blade method, and any combination thereof.
  • the orientation method using the shearing force is made into a slurry by appropriately adding additives such as a binder, a plasticizer, a dispersant, and a dispersion medium to the plate-like zinc oxide powder.
  • the slit width of the discharge port is preferably 10 to 400 ⁇ m.
  • the amount of the dispersion medium is preferably such that the slurry viscosity is 5000 to 100,000 cP, more preferably 20000 to 60000 cP.
  • the thickness of the oriented molded body formed into a sheet is preferably 5 to 500 ⁇ m, more preferably 10 to 200 ⁇ m. It is preferable to stack a large number of oriented molded bodies formed in this sheet shape to form a precursor laminate having a desired thickness, and press-mold the precursor laminate.
  • This press molding can be preferably performed by isostatic pressing at a pressure of 10 to 2000 kgf / cm 2 in warm water at 50 to 95 ° C. by packaging the precursor laminate with a vacuum pack or the like.
  • the sheet-shaped molded body is integrated and laminated in the mold after passing through a narrow discharge port in the mold due to the design of the flow path in the mold.
  • the molded body may be discharged.
  • the obtained molded body is preferably degreased according to known conditions.
  • the oriented molded body obtained as described above is fired at a firing temperature of 1000 to 1500 ° C., preferably 1100 to 1400 ° C., to form a zinc oxide sintered body comprising oriented zinc oxide crystal particles.
  • the firing time at the above-mentioned firing temperature is not particularly limited, but is preferably 1 to 10 hours, and more preferably 2 to 5 hours.
  • the zinc oxide sintered body thus obtained becomes an oriented sintered body oriented on the (101) plane, the (100) plane, the (002) plane, etc., depending on the type of the plate-like zinc oxide powder as the raw material.
  • the degree of orientation is high, and the degree of orientation on the substrate surface is preferably 50% or more, more preferably 65% or more, and further preferably 75% or more.
  • Example 1 Using a non-doped ZnO oriented sintered body substrate, a surface light emitting device provided with a light emitting functional layer by pn junction was produced as follows.
  • Non-doped (002) plane oriented ZnO powder was produced as follows. 173 parts by weight of zinc sulfate heptahydrate (manufactured by High Purity Chemical Laboratory) and 0.45 part by weight of sodium gluconate (manufactured by Wako Pure Chemical Industries) were dissolved in 300 parts by weight of ion-exchanged water. The solution thus obtained was placed in a beaker and dissolved by heating to 90 ° C. while stirring with a magnetic stirrer. This solution was kept at 90 ° C., and 49 parts by weight of 25% ammonium water was added dropwise with a microtube pump while stirring.
  • the solution was kept at 90 ° C. with stirring for 4 hours, and then the solution was poured into a large amount of ion-exchanged water and allowed to stand.
  • the precipitate deposited on the bottom of the container was separated by filtration, further washed with ion-exchanged water three times, and dried to obtain a white powdered zinc oxide precursor.
  • the obtained zinc oxide precursor was placed on a zirconia setter and calcined in the air in an electric furnace to obtain a zinc oxide plate-like porous powder.
  • the temperature schedule at the time of calcination was raised from room temperature to 900 ° C. at a rate of temperature increase of 100 ° C./h, and then kept at 900 ° C. for 30 minutes to allow natural cooling.
  • the slurry thus prepared was formed into a sheet shape on a PET film by a doctor blade method so that the thickness after drying was 20 ⁇ m.
  • the obtained tape was cut into a sheet of 20 ⁇ 20 cm, 500 pieces of cutting tape were stacked, placed on an aluminum plate having a thickness of 10 mm, and then vacuum packed. This vacuum pack was hydrostatically pressed at a pressure of 100 kgf / cm 2 in 85 ° C. warm water to produce a plate-like molded body.
  • the obtained molded body was placed in a degreasing furnace and degreased at 600 ° C. for 20 hours.
  • the obtained degreased body was fired at 1400 ° C. for 5 hours under normal pressure in nitrogen to prepare a plate-like ZnO oriented sintered body substrate.
  • the (002) orientation degree F (002) of the obtained sintered body was measured by XRD.
  • an XRD apparatus product name “RINT-TTR III” manufactured by Rigaku Corporation
  • RINT-TTR III manufactured by Rigaku Corporation
  • the average particle size of the sintered particles was measured by the following method. A 5 ⁇ 5 ⁇ 3 mm sample was cut out from the obtained plate-like sintered body, the surface perpendicular to the plate surface was polished, etched with nitric acid having a concentration of 0.3 M for 10 seconds, and then subjected to a scanning electron microscope. I took a picture. The visual field range was such that when straight lines parallel to and perpendicular to the plate surface were drawn, straight lines intersecting 10 to 30 particles could be drawn.
  • volume resistivity (Evaluation of volume resistivity) Using a resistivity meter (Loresta AX MCP-T370 type, manufactured by Mitsubishi Chemical Corporation), the volume resistivity of the sintered body was measured by the four-probe method in the vicinity of the center of the plate-like sintered body plate surface.
  • the (002) orientation degree of the sintered substrate was 80%
  • the average particle size of the sintered particles was 38 ⁇ m
  • the volume resistivity was 1 ⁇ 10 ⁇ 1 ⁇ ⁇ cm.
  • the light emitting functional layer 14, the electrode 16, and the phosphor layer 17 are formed on the obtained ZnO oriented sintered body substrate, and the surface light emitting element 10 shown in FIG. Produced.
  • the formation method of each layer was as follows.
  • n-type ZnO layer 14b was formed to a thickness of 100 nm on the ZnO oriented sintered body substrate 12 by an RF magnetron sputtering apparatus.
  • a ZnO target added with 2 parts by weight of Al was used for the film formation, and the film formation conditions were a pure Ar atmosphere, a pressure of 0.5 Pa, an input power of 150 W, and a film formation time of 5 minutes.
  • the substrate is heated to 700 ° C. using a resistance heater, and an N-doped ZnO layer having a thickness of 100 nm is formed while controlling the flux of various gas sources so that the nitrogen concentration in the film becomes 1 ⁇ 10 20 cm ⁇ 3. Filmed.
  • Electrode Formation Au 30 nm was formed on the p-type ZnO layer 14a by the electron beam evaporation method to form the electrode 16.
  • the electrode of this example is an Au thin film
  • an electrode having a high aperture ratio such as a lattice shape or a transparent conductive film such as ITO may be used instead of the Au thin film in order to increase the emission intensity.
  • Example 2 Using a Al-doped n-type ZnO oriented sintered body substrate, a surface light emitting device including a light emitting functional layer using a pn junction was manufactured as follows. In this example, since the substrate itself becomes an n-type semiconductor by Al doping and has a sufficiently low resistance, the formation of the n-type layer is omitted unlike Example 1.
  • a light emitting functional layer, an electrode, and a phosphor layer are formed on the obtained ZnO oriented sintered body substrate and shown in FIG. 1 except that there is no n-type ZnO layer.
  • a surface light emitting device having the same configuration as the above was fabricated. That is, in this example, since the substrate itself becomes an n-type semiconductor by Al doping and has a sufficiently low resistance, the formation of the n-type ZnO layer is omitted.
  • the formation method of each layer was as follows.
  • the film forming apparatus 120 includes an aerosol generating unit 122 that generates an aerosol of a raw material powder containing a raw material component, and a film forming unit 130 that sprays the film forming powder onto the seed substrate 121 to form a film containing the raw material component. ing.
  • the aerosol generating unit 122 contains the film forming powder 112 and receives the supply of the carrier gas 111 from a gas cylinder (not shown) to generate an aerosol, and supplies the generated aerosol to the film forming unit 130.
  • a raw material supply pipe 124, an aerosol generation chamber 123, and a vibrator 125 for applying vibration to the aerosol therein at a frequency of 10 to 100 Hz are provided.
  • the film forming unit 130 includes a film forming chamber 132 for injecting aerosol onto the seed substrate 121, a seed substrate holder 134 that is disposed inside the film forming chamber 132 and fixes the seed substrate 121, and the seed substrate holder 134 is X-axis- And an XY stage 133 that moves in the Y-axis direction.
  • the film forming unit 130 includes a spray nozzle 136 that has a slit 137 formed at the tip thereof and sprays aerosol onto the seed substrate 121, and a vacuum pump 138 that decompresses the film forming
  • nitrogen (N 2 ) gas is flowed as a carrier gas 111 at a flow rate of 10 L / min, the pressure in the aerosol generation chamber 123 is 50 kPa, and the pressure in the film forming chamber 132 is 0.1 kPa or less.
  • the opening size of the slit 137 provided in the film-forming powder injection nozzle 136 was 10 mm ⁇ 0.4 mm.
  • the nozzle scanning method at the time of film formation one scan is performed with a scanning distance of 200 mm and a scanning speed of 1 mm / second. Went as. This film formation was performed for a total of 60 cycles to obtain an AD film made of N-doped ZnO having a thickness of about 2.5 ⁇ m.
  • the obtained ZnO film was subjected to solid phase epitaxial growth using the heating apparatus of FIG.
  • a near-infrared lamp 206 is used as a light source for light heating.
  • a platinum plate 203 is disposed on the ZnO oriented sintered body substrate 202 and irradiated with near infrared rays from the ZnO oriented sintered body substrate 202 side. By absorbing the platinum plate 203, the film 201 was heated from the ZnO oriented sintered body substrate 202 side.
  • the ZnO oriented sintered body substrate 202 and the platinum plate 203 were placed on a quartz pedestal 204 and a quartz sample holder 207, and the temperature of the film 201 was measured with a thermocouple 205.
  • the heat treatment was performed in nitrogen, heated at a heating rate of 400 ° C./min, and held at 1100 ° C. for 10 minutes.
  • the ZnO film produced solid-phase epitaxial growth that grew following the surface atomic arrangement of the ZnO oriented sintered body substrate, and became an N-doped ZnO layer oriented in the c-axis.
  • the degree of orientation was found to be 78%.
  • the solid phase epitaxial growth method was used for forming the p-type layer, but the manufacturing method is not particularly limited, and the p-type ZnO powder is applied by a MOCVD method or a solution method such as spin coating or dipping, A heat treatment method at 200 to 700 ° C. may be used.

Landscapes

  • Led Devices (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Physical Vapour Deposition (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne un élément à émission de lumière de surface qui comprend : un substrat configuré à partir d'un corps fritté en oxyde de zinc polycristallin orienté qui est en forme de plaque ; une couche fonctionnelle d'émission de lumière disposée sur le substrat ; et une électrode disposée sur la couche fonctionnelle d'émission de lumière. Selon la présente invention, un élément à émission de lumière de surface présentant une efficacité d'émission de lumière élevée peut être fourni à un faible coût.
PCT/JP2013/083376 2012-12-14 2013-12-12 Elément à émission de lumière de surface utilisant un substrat en oxyde de zinc Ceased WO2014092165A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014552091A JPWO2014092165A1 (ja) 2012-12-14 2013-12-12 酸化亜鉛基板を用いた面発光素子

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2012273932 2012-12-14
JP2012-273932 2012-12-14
JP2013115752 2013-05-31
JP2013-115752 2013-05-31

Publications (1)

Publication Number Publication Date
WO2014092165A1 true WO2014092165A1 (fr) 2014-06-19

Family

ID=50934448

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/083376 Ceased WO2014092165A1 (fr) 2012-12-14 2013-12-12 Elément à émission de lumière de surface utilisant un substrat en oxyde de zinc

Country Status (2)

Country Link
JP (1) JPWO2014092165A1 (fr)
WO (1) WO2014092165A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE112015004076B4 (de) 2014-09-04 2018-06-28 Ngk Insulators, Ltd. Mg-enthaltender Zinkoxid-Sinterkörper und Verfahren zur Herstellung desselben
CN110563457A (zh) * 2019-09-05 2019-12-13 华南理工大学 一种氮离子掺杂的氧化锌基压敏电阻器及其制备方法
US10717679B2 (en) 2014-09-04 2020-07-21 Ngk Insulators, Ltd. Zinc oxide sintered body and method for producing same
JPWO2021029421A1 (ja) * 2019-08-15 2021-09-13 Ｊｆｅミネラル株式会社 酸化亜鉛焼結体作製用酸化亜鉛粉末および酸化亜鉛焼結体、ならびに、これらの製造方法
CN118108506A (zh) * 2024-03-05 2024-05-31 中山智隆新材料科技有限公司 一种碲化锌靶材及其制备方法与应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5116316A (fr) * 1974-07-31 1976-02-09 Matsushita Electric Industrial Co Ltd
JP2004359495A (ja) * 2003-06-04 2004-12-24 Ngk Insulators Ltd エピタキシャル膜用アルミナ基板
JP2011108859A (ja) * 2009-11-18 2011-06-02 Toyoda Gosei Co Ltd Ｉｉｉ族窒化物化合物半導体発光素子
JP2011521477A (ja) * 2008-05-21 2011-07-21 ルーメンズ， インコーポレイテッド 酸化亜鉛系エピタキシャルの層およびデバイス
JP2011252965A (ja) * 2010-05-31 2011-12-15 Meijo University 屈折率変調構造及びｌｅｄ素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5116316A (fr) * 1974-07-31 1976-02-09 Matsushita Electric Industrial Co Ltd
JP2004359495A (ja) * 2003-06-04 2004-12-24 Ngk Insulators Ltd エピタキシャル膜用アルミナ基板
JP2011521477A (ja) * 2008-05-21 2011-07-21 ルーメンズ， インコーポレイテッド 酸化亜鉛系エピタキシャルの層およびデバイス
JP2011108859A (ja) * 2009-11-18 2011-06-02 Toyoda Gosei Co Ltd Ｉｉｉ族窒化物化合物半導体発光素子
JP2011252965A (ja) * 2010-05-31 2011-12-15 Meijo University 屈折率変調構造及びｌｅｄ素子

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE112015004076B4 (de) 2014-09-04 2018-06-28 Ngk Insulators, Ltd. Mg-enthaltender Zinkoxid-Sinterkörper und Verfahren zur Herstellung desselben
US10442736B2 (en) 2014-09-04 2019-10-15 Ngk Insulators, Ltd. Mg-containing zinc oxide sintered body and method for producing same
US10717679B2 (en) 2014-09-04 2020-07-21 Ngk Insulators, Ltd. Zinc oxide sintered body and method for producing same
JPWO2021029421A1 (ja) * 2019-08-15 2021-09-13 Ｊｆｅミネラル株式会社 酸化亜鉛焼結体作製用酸化亜鉛粉末および酸化亜鉛焼結体、ならびに、これらの製造方法
JP2022185054A (ja) * 2019-08-15 2022-12-13 Ｊｆｅミネラル株式会社 酸化亜鉛焼結体作製用酸化亜鉛粉末および酸化亜鉛焼結体、ならびに、これらの製造方法
JP7197808B2 (ja) 2019-08-15 2022-12-28 Ｊｆｅミネラル株式会社 酸化亜鉛焼結体作製用酸化亜鉛粉末および酸化亜鉛焼結体、ならびに、これらの製造方法
JP7573807B2 (ja) 2019-08-15 2024-10-28 Koa株式会社 酸化亜鉛焼結体作製用酸化亜鉛粉末および酸化亜鉛焼結体、ならびに、これらの製造方法
CN110563457A (zh) * 2019-09-05 2019-12-13 华南理工大学 一种氮离子掺杂的氧化锌基压敏电阻器及其制备方法
CN118108506A (zh) * 2024-03-05 2024-05-31 中山智隆新材料科技有限公司 一种碲化锌靶材及其制备方法与应用

Also Published As

Publication number Publication date
JPWO2014092165A1 (ja) 2017-01-12

Similar Documents

Publication Publication Date Title
JP6112626B2 (ja) 酸化亜鉛基板を用いた面発光素子
JP5770905B1 (ja) 窒化ガリウム自立基板、発光素子及びそれらの製造方法
JP6480398B2 (ja) 多結晶窒化ガリウム自立基板及びそれを用いた発光素子
JPWO2016035721A1 (ja) 酸化亜鉛焼結体及びその製造方法
CN105830237A (zh) 发光元件用复合基板及其制造方法
JP6890117B2 (ja) 多結晶１３族元素窒化物からなる自立基板及びそれを用いた発光素子
WO2014092165A1 (fr) Elément à émission de lumière de surface utilisant un substrat en oxyde de zinc
JP6138781B2 (ja) 酸化亜鉛粉末及びその製造方法
JP6307071B2 (ja) 光起電力素子
JP6648253B2 (ja) 多結晶窒化ガリウム自立基板及びそれを用いた発光素子
JPWO2014192911A1 (ja) 窒化ガリウム自立基板、発光素子及びそれらの製造方法
CN105658849B (zh) 氮化镓自立基板、发光元件及它们的制造方法
JPWO2016035720A1 (ja) Ｍｇ含有酸化亜鉛焼結体及びその製造方法
JP6092015B2 (ja) 単結晶体の製造方法
JP2015003837A (ja) ドープされた酸化亜鉛単結晶体の製造方法
JP6489621B2 (ja) 酸化亜鉛基板及びそれを用いた第１３族窒化物結晶の製造方法
JPWO2014092168A1 (ja) 酸化亜鉛基板を用いた面発光素子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13862931

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014552091

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13862931

Country of ref document: EP

Kind code of ref document: A1