CN105885839B - Red emitting phosphor based on nitride and the white light illumination source containing the phosphor - Google Patents

Red emitting phosphor based on nitride and the white light illumination source containing the phosphor Download PDF

Info

Publication number
CN105885839B
CN105885839B CN201610243773.1A CN201610243773A CN105885839B CN 105885839 B CN105885839 B CN 105885839B CN 201610243773 A CN201610243773 A CN 201610243773A CN 105885839 B CN105885839 B CN 105885839B
Authority
CN
China
Prior art keywords
phosphor
sample
red emitting
emitting phosphor
red
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.)
Active
Application number
CN201610243773.1A
Other languages
Chinese (zh)
Other versions
CN105885839A (en
Inventor
陶德节
李依群
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.)
Intel Mandix Co
Original Assignee
Intel Mandix Co
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=49949232&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN105885839(B) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from US13/871,961 external-priority patent/US8663502B2/en
Application filed by Intel Mandix Co filed Critical Intel Mandix Co
Publication of CN105885839A publication Critical patent/CN105885839A/en
Application granted granted Critical
Publication of CN105885839B publication Critical patent/CN105885839B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7729—Chalcogenides
    • C09K11/7731—Chalcogenides with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77347—Silicon Nitrides or Silicon Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/774—Borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
    • H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/507—Wavelength conversion elements the elements being in intimate contact with parts other than the semiconductor body or integrated with parts other than the semiconductor body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • H01L2224/491—Disposition
    • H01L2224/49105—Connecting at different heights
    • H01L2224/49107—Connecting at different heights on the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H01L33/504—Elements with two or more wavelength conversion materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

The present invention relates to the red emitting phosphor based on nitride and containing the white light illumination source of the phosphor.The phosphor includes by chemical formula M(xv)M′2Si5‑xAlxN8: the composition based on nitride that RE is indicated, in which: M is at least one unit price, divalent or trivalent metal with chemical valence v；M ' is at least one of Mg, Ca, Sr, Ba and Zn；And RE is at least one of Eu, Ce, Tb, Pr and Mn；Wherein x meets 0.1≤x≤0.4, and wherein the phosphor has general crystalline texture M '2Si5N8: RE, Al replace the Si in the crystalline texture, and M is positioned essentially at gap site.In addition, the phosphor is configured such that deviation the CIE Δ x and Δ y of aging 1, the 000 hour chromaticity coordinate generated under 85 DEG C and 85% humidity are less than about 0.03.

Description

Red emitting phosphor based on nitride and the white light illumination source containing the phosphor
The application is the applying date on 07 7th, 2013, and application number 201380044345.0 is entitled " based on nitride The divisional application of the application for a patent for invention of red emitting phosphor ".
Technical field
The embodiment of the present invention is related to the composition of the red emitting phosphor based on nitride and the white-light illuminating containing the phosphor Source.
Background technique
Many red emitting phosphors are derived from silicon nitride (Si3N4).The structure of silicon nitride includes in the SiN slightly distorted4Four The Si layer that is combined in the body skeleton of face and N layers.SiN4Tetrahedron is to be coupled so that each nitrogen is three four by shared nitrogen angle Face body shares.For example, with reference to hampshire (S.Hampshire), " silicon nitride ceramics-structure, processing and characteristic summary (Silicon nitride ceramics-review of structure, processing, and properties) ", material Material and manufacturing engineering achieve magazine (Journal of Achievements in Materials and Manufacturing Engineering), volume 24, the 1st phase, September (2007), the 43-50 pages.The composition of red emitting phosphor based on silicon nitride It is usually directed to and replaces SiN by elements such as Al4Si at tetrahedron center；The optics that this is mainly used for improveing phosphor is special Property, such as emissive porwer and peak emission wavelength.
However, the result that aluminium replaces is, due to Si4+By Al3+Instead of, therefore be substituted compound and lose a positive electricity Lotus.Charge balance is substantially usually realized using two ways: in an arrangement, Al3+Replace Si4+With O2-Replace N3-, It is balanced so that the negative electrical charge of the positive charge and loss lost is fought.This makes tetrahedral network have Al3+Or Si4+As four sides The cation at body center, and O in structure2-Or N3-Anion is located at tetrahedral angle.Since which kind of tetrahedron not yet accurately learnt With which kind of substitution, be accordingly used in description such case is named as (Al, Si)3-(N,O)4.Clearly, flat for realization charge Weighing apparatus replaces Si to there is an O every Al and replaces N.
In addition, these replacement mechanisms (O replaces N) for charge balance are inserted into combination with the gap of cation to use. In other words, by between the existing atom in modification cation insertion lattice sites, hole, gap or the channel of " natural " are inserted into In.This mechanism does not need to change anion structure (in other words, O replaces N), but this does not imply that O replaces N can not be same Shi Fasheng.Replacement mechanism for charge balance is inserted into combination with the gap of modifier cation to be occurred.
Will Bao Jing (K.Shioi) et al. is in " Sr- α-SiAlON:Eu2+Synthesis, crystal structure and luminescence generated by light (Synthesis,crystal structure,and photoluminescence of Sr-α-SiAlON:Eu2+) ", the U.S. Ceramic association journal (J.Am.Ceram Soc) has been discussed in 93 [2] 465-469 (2010) in-SiAlON of α containing Sr using changing Matter cation.Will Bao Jing et al. provides the formula of the total composition of this kind of phosphor: Mm/vSi12-m-nAlm+nOnN16-n:Eu2+, wherein M be Li, Mg, Ca, Y and rare earth (in addition to La, Ce, Pr and Eu) etc. " modification cation ", and ν is the chemical valence of M cation.Such as Will Bao Jing et al. is taught, and the crystal structure of α-SiAlON is derived from compound α-Si3N4.In order to from α-Si3N4Generate α- SiAlON passes through Al3+Ionic portions replace Si4+Ion, and in order to compensate for because of Al3+Replace Si4+The charge unbalance of generation, uses O Replace some N and by the way that M cation is trapped (Si, Al)-(O, N)4Added in gap in tetrahedral network it is some just Charge (will Bao Jing et al. is referred to as " stabilization ").
Research has formula M extensively in the industry2Si5N8The alkaline-earth metal nitrogen of the europium doped of (wherein M is Ca, Sr or Ba) SiClx phosphor, for example, see model crith Wei Er in Technische Universiteit Eindhoven (Technical University Eindhoven), the PhD paper in January, 2000, United States Patent (USP) 6,649,946 and He Pei et al., solid-state physics and Solid-state Chemistry Magazine (J.Phys.Chem.Solids.) 2000,61:2001-2006.This phosphor family is the wave in 600nm to 650nm Emitted under length with high-quantum efficiency.Wherein, pure Sr2Si5N8It is issued with highest quantum efficiency and in the peak wavelength of about 620nm It penetrates.Known in the industry, this feux rouges nitride phosphors are in the temperature within the scope of 60 DEG C to 120 DEG C and between 40% to 90% There is bad stability under the LED operating condition of envionmental humidity in range.
Multiple groups have used based on oxygen-containing M2Si5N8Material tested, these materials can also contain other gold Belong to.For example, with reference to United States Patent (USP) 7,671,529 and 6,956247 and U.S. Published Application 2010/0288972,2008/ 0081011 and 2008/0001126.It is well known, however, that these oxygen-containing materials high temperature and high relative humidity (RH) (such as 85 DEG C and Show bad stability under combination condition 85%RH).
It is believed that the charge compensation form reported in the industry will not weaken influence of the heat humidity aging to phosphor, seemingly It will not generate the beneficial outcomes for improving peak emission wavelength and not changing light emitting intensity seldom or substantially.
The stable silicon phosphor based on nitride is needed in the industry and is based on M2Si5N8Stabilization phosphor, in which: peak value hair Ejected wave is grown in the wider range of red and other colors；And the physical characteristic (such as temperature and humidity stability) of phosphor Enhancing.
Summary of the invention
The embodiment of the present invention provides the phosphor based on nitride, has and is based on M2Si5N8Chemical composition, wherein Replace Si with Section III B row element (especially Al), and cation is substantially included in phosphor crystal structure in a manner of substitution and is used In charge balance.These phosphor materials can be configured so that peak emission wavelength to be expanded to red more long wavelength, and enhance The physical characteristic of phosphor especially significantly improves temperature and humidity stability.
At least one embodiment of the present invention is related to by formula M 'xM”2A5-yDyE8: the phosphorescence based on nitride that RE is indicated Body composition.Herein, M ' is at least one of 1+ cation, 2+ cation and 3+ cation, and M " is Mg, Ca, Sr, Ba and Zn At least one of.A is at least one of Si, C and Ge.Element D replaces component A in a manner of replacing, and wherein D is selected from by week The group of the Section III B row element composition of phase table.In one embodiment, at least one of D B, Al and Ga.In order to D Replace A to carry out charge compensation, modifier cation M ' is added in phosphor.M ' is Li1+、Na1+、K1+、Sc3+、Ca2+、Mg2 +、Sr2+、Ba2+And Y3+At least one of, and substantially will be in the gap of this modifier cation insertion phosphor.E is 3- At least one of anion, 2- anion and 1- anion, and can be O2-、N3-、F1-、Cl1-、Br1-And I1-In at least one Person.Rare earths activator RE is at least one of Eu, Ce, Tb, Pr and Mn；And given y is 0.01≤y < 4, and x is multiplied by M's ' Chemical valence is equal to y.
Herein, RE indicates that phosphor activator and symbol ": RE " are indicated doped with rare earth, is usually with substitution side Formula doping, but can also reside in the crystalline texture of phosphor material grain boundaries, adulterate on particle surface and in gap site. In general, the crystalline texture of the 2-5-8 compound based on nitride can have selected from Pmn2 as described herein1, Cc, its derivative The space group of or mixtures thereof object.In some instances, space group Pmn21.Moreover, it is noted that in material science theory, The vacancy concentration of pure crystalline material can be existing lattice sites every about 1,000,100 parts according to the thermal balance condition of crystal.Cause This, the charge balance ion of small percentage can actually end in sky metal ion site rather than in gap site, i.e., electric Lotus ion balance first fills vacancy and refills gap site.
In alternative embodiments, the modifier cation M ' resided in gaps between crystals is selected from the group being made up of Group: including Ca2+Alkaline earth and element Li inside1+、Y3+、Mn2+、Zn2+With one or more rare earths (RE), each is placed in gap Modifier cation can be individually or to be applied in combination.Condition is that the summation of the chemical valence of modifier cation is equal to because of the IIIB row element replaces charge unbalance caused by A.
Since the stoichiometric subscript of cation will be greater than 2, it is substantial can to promptly appreciate that checked phosphor has The modifier cation being added in phosphorescence body space of the present invention.Traditional M2Si5N8The subscript of red emitting phosphor is equal to 2.When When this numerical value is greater than 2, occupied in lattice sites it can be inferred that excess cations do not reside at；But change added Matter agent cation insertion " natural " is present in the gap in the crystalline texture of host phosphor, hole or channel.These gaps It can be not occupy lattice sites.
According to the present invention by being included in the modifier cation being substantially placed in gap come to Si4+Replace progress charge flat Weighing apparatus generates unexpected benefit, that is, increases peak emission wavelength towards the red end of spectrum.According to some embodiments, this increase etc. In or greater than about 6nm.The afterclap occurred together with launch wavelength increase is substantial maintenance light emitting intensity.According to some Embodiment, with replace modification and gap modify visible intensity relative to modify before intensity decrease less than 10%.
According to the present invention by being included in the modifier cation being substantially placed in gap come to Si4+Replace progress charge flat Weighing apparatus generates unexpected benefit, that is, stability enhancing of the phosphor under high temperature and the aging condition of high humility.The composition of phosphor passes through It is configured so that the deviation of the photoluminescence intensity after aging 1,000 hours under 85 DEG C and 85% humidity no more than about 30%.Phosphorus The composition of body of light is further configured so that under 85 DEG C and 85% humidity after aging 1,000 hour, each chromaticity coordinate Grid deviation CIE Δ x and CIE Δ y is less than or equal to about 0.03.
In another embodiment of the present invention, gap modifier cation is to Si4+Replace the charge balance carried out adjoint A degree of O2-Replace N3-.In other words, in this embodiment, substantially it is placed in the modifier cation in gap The imbalance of charge balance mechanism only partially balancing charge, and remainder is by O2-Replace N3-It completes." incomplete " charge is flat The reason of weighing apparatus, may is that the chemical valence of modifier cation is lower than the chemical valence that should have originally, such as is using Li+And Ca2 +Rather than Ca2+And Y3+When.It is another to be selected as, the selection of modifier cation should make chemical valence it is higher (2+, 3+ or even 5+ sun from Son), and because places modification it is cationic less due to keep charge balance incomplete.
Lower transmitted wave is excited to grow up in the light of about 600nm according to an embodiment of the invention, phosphor is configured to blue light, Wherein blue light may be defined as light of the wavelength within the scope of about 420nm to about 470nm.Phosphor of the present invention can also by wavelength compared with It is short that (for example, about 250nm is excited to the radiation of about 420nm), but when exciting radiation is in x-ray or UV form, provides independent hair Blue phosphor is with to the required white light contributing blue light component of white light source.Common blue light excitation source is emission peak about InGaN LED or the GaN LED of 460nm.
The embodiment of the present invention also includes white light illumination source comprising the InGaN light emitting diode (LED) and sheet of blue light-emitting Any red emitting phosphor described in text.It also may include jaundice light phosphor and/or green-emitting phosphors.Implement at one In example, green-emitting phosphors have formula Ce:Lu3Al5O12.Two kinds of illustrative red emitting phosphors of the embodiment of the present invention are Eu0.05Ca0.1Sr1.95Si4.8Al0.2N8And Eu0.05Ca0.1Sr1.95Si4.8B0.2N8。
At least one embodiment of the present invention is based on M2Si5N8The modification form of (so-called " 258 " compound), wherein M For alkaline earth.Modification to 258 compounds includes to replace Si with periodic table Section III B row element B, Al, Ga and/or In, especially Al, Wherein charge compensation can be by the way that so-called modifier cation substance gap to be inserted into phosphor body crystal structure come complete At.Modifier cation has a variety of chemical valences, and includes Li+、Ca2+And Y3+.The advantages of to 258 modification, is comprising towards spectrum Dark red end increases the stability of peak emission wavelength and enhancing under a high temperature and high humidity condition.
Phosphor may include by chemical formula M(x/v)M′2A5-yDyN8-zEp: the composition based on nitride that RE is indicated, in which: M It is at least one unit price, divalent or trivalent metal with chemical valence v；M ' is at least one of Mg, Ca, Sr, Ba and Zn；A For at least one of Si, C and Ge；D is at least one of B, Al and Ga；E be at least one pentavalent with chemical valence w, Sexavalence or septivalency are nonmetallic；And RE is at least one of Eu, Ce, Tb, Pr and Mn；Wherein x=y-3z+p (8-w), wherein y is full Foot 0.1≤y < 1.1, and wherein phosphor has M '2A5N8: the general crystalline texture of RE, D replace in the general crystalline texture A, E replaces the N in the general crystalline texture, and M is positioned essentially at the gap site in the general crystalline texture.This Outside, red emitting phosphor can be selected from the group being made up of: Eu0.05Ca0.1Sr1.95B0.2Si4.8N8； Eu0.05Ca0.1Sr1.95Al0.2Si4.8N8；Eu0.05Ca0.1Sr1.95Ga0.2Si4.8N8；Eu0.05Sr1.95Al0.2Si4.8N8； Eu0.05Sr1.95B0.2Si4.8N7.93；Eu0.05Sr1.95Al0.2Si4.8N7.93；Eu0.05Sr1.95Ga0.2Si4.8N7.93；Added with Ca3N2's Eu0.05Sr1.95Si5N8；Eu added with BN0.05Sr1.95Si5N8；Eu added with AlN0.05Sr1.95Si5N8；Be added with GaN Eu0.05Sr1.95Si5N8。
Red emitting phosphor may include by chemical formula M '2Si5-yDyN8-z: the composition based on nitride that RE is indicated, wherein M ' For at least one of Mg, Ca, Sr, Ba and Zn；D is at least one of B, Al and Ga；And RE is in Eu, Ce, Tb, Pr and Mn At least one；Wherein y=3z, phosphor have M '2Si5N8: the general crystalline texture of RE, and Al replaces the general crystallization Si in structure.In addition, red emitting phosphor can be configured, it is Eu that wherein M ', which is Sr, D Si, and RE,.Red emitting phosphor can It is configured, wherein the red emitting phosphor is made of Sr, Si, Al, N and Eu.Red emitting phosphor can be configured, and wherein y is full Foot 0.1≤y < 0.4.Red emitting phosphor can be configured, and wherein z meets 0.05≤z < 0.09.Red emitting phosphor can be configured, Wherein radiation and transmitting photoluminescence peak emission wavelength of the phosphor absorbing wavelength within the scope of about 200nm to about 470nm Light greater than 623nm.Phosphor can be configured, and wherein phosphor is selected from the group being made up of: Eu0.05Sr1.95B0.2Si4.8N7.93；Eu0.05Sr1.95Al0.2Si4.8N7.93；And Eu0.05Sr1.95Ga0.2Si4.8N7.93。
Red emitting phosphor with the composition based on nitride can include: element M, wherein M be Li, Na, K, Sc, Ca, At least one of Mg, Sr, Ba and Y；Element M ', wherein M ' is at least one of Mg, Ca, Sr, Ba and Zn；Silicon；Aluminium；Nitrogen； And elements RE, wherein RE is at least one of Eu, Ce, Tb, Pr and Mn；Wherein the red emitting phosphor has M '2Si5N8: The general crystalline texture and M and Al of RE is included, and wherein the red emitting phosphor be configured such that at about 85 DEG C and Under about 85% relative humidity after aging 1,000 hour, the changes in coordinates CIE Δ x and CIE Δ y of each chromaticity coordinate be less than or Equal to about 0.03.
Red emitting phosphor may include by chemical formula M(x/v)M′2Si5-xAlxN8: the composition based on nitride that RE is indicated, In: M is at least one unit price, divalent or trivalent metal with chemical valence v；M ' is at least one in Mg, Ca, Sr, Ba and Zn Person；And RE is at least one of Eu, Ce, Tb, Pr and Mn；Wherein x meets 0.1≤x < 0.4, and the wherein red phosphor Body has M '2Si5N8: the general crystalline texture of RE, Al replace the Si in the general crystalline texture, and M be positioned essentially at it is described At gap site in general crystalline texture.
Detailed description of the invention
After being checked in conjunction with attached drawing to being described below of specific embodiment of the present invention, those one of ordinary skill in the art will be bright These and other aspects of the invention and feature, in which:
Fig. 1 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 1 to 4；
Fig. 2 shows according to some embodiments of the present invention, the X-ray diffraction pattern of the phosphor of sample 1 to 4；
Fig. 3 shows according to some embodiments of the present invention, compound Eu0.05Ca0.1Sr1.95Si4.8Al0.2N8(sample 2) Excitation spectrum, the spectrum illustrates phosphor can be by the UV between electromagnetic spectrum to the radiation between blue region come effectively Excitation；
Fig. 4 shows according to some embodiments of the present invention, compound Eu0.05Ca0.1Sr1.95Si4.8B0.2N8(sample 3) swashs Luminous spectrum, the spectrum, which illustrates phosphor, effectively to be swashed by the UV between electromagnetic spectrum to the radiation between blue region Hair；
Fig. 5 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 5-8；
Fig. 6 shows according to some embodiments of the present invention, the X-ray diffraction pattern of the phosphor of sample 5-8；
Fig. 7 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 9-12；
Fig. 8 shows according to some embodiments of the present invention, the X-ray diffraction pattern of the phosphor of sample 9 to 12；
Fig. 9 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 13 to 16；
Figure 10 shows according to some embodiments of the present invention, the X-ray diffraction pattern of the phosphor of sample 13 to 16；
Figure 11 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 17 to 21；
Figure 12 shows according to some embodiments of the present invention, the X-ray diffraction pattern of the phosphor of sample 17 to 21；
Figure 13 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 22 to 27；
Figure 14 shows according to some embodiments of the present invention, the X-ray diffraction pattern of the phosphor of sample 22 to 27；
Figure 15 shows according to some embodiments of the present invention, the emission spectrum of white light LEDs (3000K), the white light LEDs (3000K) includes blue light InGaN LED, has formula Eu0.05Ca0.1Sr1.95Si4.8Al0.2N8Red phosphor (sample 2) and tool There is formula Ce:Lu3Al5O12Green phosphor；
Figure 16 shows according to some embodiments of the present invention, the emission spectrum of white light LEDs (3000K), the white light LEDs (3000K) includes blue light InGaN LED, has formula Eu0.05Ca0.1Sr1.95Si4.8B0.2N8Red phosphor (sample 3) and tool There is formula Ce:Lu3Al5O12Green phosphor；
Figure 17 A-17C shows that according to some embodiments of the present invention the phosphor of sample 1 to 3 and 6 is in 85 DEG C and 85% phase To the reliability test under damp condition as a result, wherein Figure 17 A is that photoluminescence intensity (brightness) changes with time, figure 17B is that CIE x chromaticity coordinate changes with time, and Figure 17 C is that CIE y chromaticity coordinate changes with time；
Figure 18 A-18C shows according to some embodiments of the present invention, not coated and through Al2O3/SiO2The sample 33 of coating The knot of reliability test of the phosphor of (it has composition identical with sample 2) under 85 DEG C and 85% relative humidities Fruit, wherein Figure 18 A is that photoluminescence intensity (brightness) changes with time, and Figure 18 B is the change of CIE x chromaticity coordinate at any time Change, and Figure 18 C is that CIE y chromaticity coordinate changes with time；
Figure 19 shows (650nm) feux rouges phosphorescence of the yellow light YAG phosphor of prior art doping Ce, prior art doping Eu Body CaAlSiN3With the red phosphor Ca of the 630nm doping Eu of the embodiment of the present invention0.1Sr2Si4.8Al0.2N8Emission spectrum；
Figure 20 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 28 to 32；And
Figure 21 shows according to some embodiments of the present invention, the X-ray diffraction pattern of the phosphor of sample 28 to 32；
Figure 22 shows the light emitting device of some embodiments of the present invention；And
Figure 23 A and Figure 23 B show the solid luminous device of some embodiments of the present invention.
Specific embodiment
Now with reference to schema detailed description of the present invention embodiment, the embodiment is as illustrative example of the invention It provides, so that those one of ordinary skill in the art can practice the present invention.It is worth noting that, lower texts and pictures and example are not beaten Calculation scope of the invention is limited to single embodiment, and can by exchanging some or all of described or illustrated elements There are other embodiments.In addition, if certain elements of the invention can be practiced partially or even wholly using known tip assemblies, then only It describes to understanding those parts essential to the invention in these known tip assemblies, and by omission to other portions of these known tip assemblies The detailed description divided, with the anti-blur present invention.In the present specification, embodiments showing a single component should not be construed as limiting； But unless explicitly stated otherwise herein, otherwise it is intended that cover the other embodiments comprising multiple same components, and it is anti- ?.In addition, otherwise applicant is not intended to return the either term in specification or claims except non-clearly illustrating For unusual or special meaning.In addition, the present invention covers the current of the known tip assemblies mentioned by way of illustration herein and future Known equivalent.
Some embodiments of the present invention are related to by formula M 'xM”2A5-yDyE8: the phosphor group based on nitride that RE is indicated At.Herein, M ' is at least one of 1+ cation, 2+ cation and 3+ cation, and M " is in Mg, Ca, Sr, Ba and Zn At least one, is individual or to be applied in combination.A is at least one of C, Si and Ge individual or to be applied in combination.Element D Component A is replaced in a manner of replacing, wherein D is selected from the group being made of the Section III B row element of the periodic table of elements.In the present invention The label of each row of periodic table be those book " optical characteristics (Optical Properties of of solid in mark Fox Solids) " used in the inside front cover in (Oxford University Press (Oxford University Press), New York, 2001) Person follows old IUPAC (International Federation of Pure Chemical and Applied Chemistry (International Union of Pure and Applied Chemistry)) system.Referring to http://en.wikipedia.org/wiki/Group_ (periodic_ Table), newest browsing on January 15th, 2013.In one embodiment, D is individual or in B, Al and Ga for being applied in combination At least one.
Modifier cation M ' is added in phosphor to replace A to carry out charge compensation D.In particular, M ' is a The other or Li to be applied in combination1+、Na1+、K1+、Sc3+、Ca2+And Y3+At least one of.M ' is formula M2Si5N8In remove stoichiometry The additional cation used outside the divalent metal M of " 2 " is measured, and this modifier cation is therefore claimed to be substantially inserted phosphor In gap.Property about this site will further describe in nomenclature part below.
E in the general formula of phosphor of the present invention is at least one of 3- anion, 2- anion and 1- anion.It is specific For, E can be the individual or O to be applied in combination2-、N3-、F1-、Cl1-、Br-And I-At least one of.Rare earth RE be Eu, Ce, At least one of Tb, Pr and Mn；And given y is 0.01≤y≤1.0.The value of parameter y can be defined as simultaneously the value of x multiplied by The chemical valence of M '；This is the condition for realizing charge balance.
As discussed above, M ' cation be " modification agent " cation, be used to indicate that substantially be introduced into gap and The technical term of the non-charge balance introduced by replacement mechanism to realize crystal structure and/or the cation of stabilization.Between Gap site is to be present in cavity, hole or channel in lattice according to the arrangement mode (accumulation or stacking) of main body constituting atom. The atoms of dopant for occupying gaps between crystals and these atoms introduced in a manner of substitution are distinguished；In the latter mechanism In, atoms of dopant replaces the main body atom resided in lattice sites.Described two mechanism realize that charge is flat in the phosphor The difference of the mode of weighing apparatus will be showed by the stoichiometric equation of main body.
In content disclosed below, by (Sr known to discussion1-xCax)2Si5N8:Eu2+Composition, then to the embodiment of the present invention The property of gap site carry out certain brief comment.Then, the present invention will be presented based on M ' of the inventionxM”2A5-yDyE8:RE The phosphor of embodiment provides the difference of its advantage and characteristic and these phosphors and the prior art.It will provide specific Example, comprising wherein replacing Si4+Section III B row element be Al3+And wherein modification cation is Ca2+Phosphor.Finally, will Discuss the nitride phosphors that glow of the invention for being used to form white light LEDs, and the heat and change of display phosphor of the present invention Learn the accelerated ageing result of stability.
Known (Sr1-xCax)2Si5N8:Eu2+The discussion of composition
Piao et al. is in entitled " (Sr1-xCax)2Si5N8:Eu2+The preparation of solid solution and its characteristics of luminescence (Preparation of(Sr1-xCax)2Si5N8:Eu2+solid solutions and their luminescence Properties paper) ", electrochemical society's magazine (J.of the Electrochem.Soc.) 153 (12) H232-H235 (2006) it is discussed in (" preparation paper (Preparation Paper) ") and is based on (Sr1-xCax)2Si5N8:Eu2+Composition.Such as Piao Et al. preparation paper in taught, " ... Ca2+In (Sr1-xCax)2Si5N8:Eu2+In solution be limited to the composition of x=0.5.? (Sr1-xCax)2Si5N8:Eu2+Middle group there is the first [Ca when becoming x=0.62Si5N8] phase.Two-phase is in the range of 0.5 < x < 0.75 It coexists, wherein the transformation of rectangle structure to monocline occurs ".Piao et al. illustrates Ca2+Modifier cation is in feux rouges nitride Position in phosphor: " Sr is occupied2+/Ca2+The doping Eu of the position of ion2+Ion is arranged in by Si6N6Ring is respectively along two-phase [100] and in the channel of [010] direction formation ".When in [Sr2Si5N8] in phase by Ca2+When content increases to x=0.5, formed SrCaSi5N8, " grain crystalline more preferably, and [crystal grain] size increases ".This will enhance optical characteristics.When x increases to 0.6, (60 is former Sub- %) when, " there are two phases with different shape for SEM image instruction ".Referring to Piao et al., prepared paper, the H233 pages.
Piao et al. illustrates the modifier cation in feux rouges nitride phosphors of the present invention to a certain extent in paper The property of gap site.In M2Si5N8There are two crystallize the site M for each structure cell tool in (wherein M=Sr and Ca)；This is these changes Closing object has the reason of two transmitting bands.However, in (Sr1-xCax)2Si5N8:Eu2+In series, a broadband emission is only seen.This Show that two sites have closely similar crystalline environment, or is rich in N3-Network in Eu2+Two sites of ion pair have not With coordination (around the site every M and N in connection3-The number of anion) the fact be not particularly sensitive.Referring to Piao et al., Preparation paper, the H234 pages.
Piao et al. teaching, as addition Ca2+To replace [Sr2Si5N8] Sr in phase when, transmitting is displaced to more long wavelength, until (Sr1-xCax)2Si5N8:Eu2+The point of x=0.5 in (with 2 atom %Eu) series.Eu2+Transmitting band is from Sr2Si5N8:Eu2+'s 617nm red shift is to SrCaSi5N8:Eu2+632nm, wherein Eu concentration is 2 atom % in both cases.In two kinds of situations Under, ligancy be 10 Ca2+And Sr2+The ionic radius of ion is respectivelyWithTherefore, in Ca2+Ionic compartmentation [Sr2Si5N8] Sr in phase2+When site, visible M-N bond distance and lattice parameter reduce in x-ray diffraction (XRD) experiment. Ca-N key makes Eu relative to the shorter average distance of Sr-N2+Ion undergoes stronger crystal field strength, the crystal field strength with 5 powers of chemical bond distance are inversely proportional.Referring to Piao et al., prepared paper, the H234 pages.
According to Piao et al., emissive porwer is with (Sr1-xCax)2Si5N8:Eu2+Ca in phosphor2+Content increases and reduces.This by Piao et al. makes an explanation at the H235 pages；It can not be specified in this although details is too complicated, intensity reduces certainty and Eu2+Ion Coordination mode and energy level diagram relevant to excitation state transition it is related.Referring to Piao et al., prepared paper, the H235 pages.
The property of the gap site of the embodiment of the present invention
Although being not intended to be limited to any specific of the property of the modified cationic gap site about the embodiment of the present invention Theory, but discussion well-known theory is helpful or can derive by it.It is described since term " gap site " is used in the present invention It is inserted into the site of charge balance modifier cation, therefore this relates generally to nomenclature.(reader will remember, such as Ca2+Deng modification Agent cation can be used for because of Al3+Replace Si4+The charge unbalance of generation carries out charge balance).Term " gap " is selected to come strong The fact that modifier cation is adjusted usually not replace or replace the existing ion in lattice sites.If previously emphasized, modification Agent cation is added to the cation in existing crystalline body structure.
That is, seeming in the literature and being not present excessively about the property of these gap sites (comprising it modified M2Si5N8:Eu2+Position or quantity in structure cell) information.There may be some data to indicate that it is not occupy the site M.Such as thank Et al. entitled " for white-light emitting diode based on Sr2Si5N8Eu2+Red phosphor simple and effective route of synthesis (A simple,efficient synthetic route to Sr2Si5N8Eu2+-based red phosphors for White light-emitting diodes) ", in the paper of chemical journal (Chem.Mater.) 2006,18,5578-5583 It is taught, at least one synthesis Sr2Si5N8Experiment in, it is 90.7% and for Sr2 for the site Sr1 that site, which occupies point rate, Site is 88.9%, to remind reader, there are two the sites M for each structure cell tool.It thanks et al. and this is described as to " Sr is in two sites The light defects at place ".In material science theory, the vacancy concentration of pure crystalline material is according to the thermal balance condition of produced crystal Should be existing lattice sites every about 1,000,100 parts.Therefore, the charge balance ion of small percentage can be terminated actually In the empty metal ion such as Sr/Ca/Eu lattice sites site, i.e., charge balance ion first fills vacancy and refills gap digit Point.
Based on M 'xM”2A5-yDyE8: the discussion of the phosphor of the present invention of RE
The embodiment of the present invention is related to by formula M 'xM”2A5-yDyE8: the phosphor composition based on nitride that RE is indicated. Herein, M ' is 1+ cation, 2+ cation and at least one of 3+ cation, and M " be in Mg, Ca, Sr, Ba and Zn extremely Few one.A is at least one of Si and Ge.Element D replaces component A in a manner of replacing, and wherein D is selected from by the of periodic table The group of IIIB row element composition.In one embodiment, at least one of D B, Al and Ga.
In order to replace A to carry out charge compensation D, modifier cation M ' is added in phosphor.M ' is Li1+、Na1+、 K1+、Sc3+、Ca2+And Y3+At least one of, and this modifier cation is substantially inserted in phosphorescence body space, E is 3- yin At least one of ion, 2- anion and 1- anion, and can be O2-、N3-、F-、Cl-、Br-And I-At least one of.It is dilute Native RE is at least one of Eu, Ce, Tb, Pr and Mn；And given y is 0.01≤y < 1.0, and x is multiplied by the chemical valence etc. of M ' In y.
In alternative embodiments, the modifier cation M ' substantially resided in gaps between crystals is to be selected to be made up of Group: include Ca2+Alkaline earth and element Li inside+、Zn2+、Y3+With one or more rare earths (RE), these are placed in gap Each of modifier cation is individual or to be applied in combination.
Occur when rare earths activator ion is inserted into main body the earth atoms replaced at lattice sites discussed herein above Replacement mechanism, " conventional ceramic " is thus converted into phosphor.But replace event that can carry out in other ways: for example when being in SiN4Si at tetrahedron center can also replace when being replaced by Al.This can improve optical characteristics.However, fields technology Personnel will be noted that Al/Si replaces the result presented different from the substitution of Eu/ alkaline earth: since divalent alkaline earth cation is dilute by divalent Native cation replaces, and Al3+Replace Si4+So that main body is lost a positive charge, therefore is substituted by neutral charge in the latter case Replace.This positive charge lost can further modification through phosphor material balance.In replacement mechanism, rare earths activator Doping may be additionally located in gap site；For example, as it is known that Eu is resided in the gap site of β-SiAlON phosphor.
Document has reported two kinds of modes commonly used to carry out charge balance to loss positive charge.In an arrangement, Al3+ Replace Si4+With O2-Replace N3-, balanced so that the negative electrical charge of the positive charge and loss lost is fought.This makes tetrahedral net Network changeably has Al at its center3+Or Si4+Cation, and there is O in Qi Jiaochu2-To N3-The combination of anion.Due to still Which kind of tetrahedron is not learnt accurately with which kind of substitution, be accordingly used in description such case is named as (Al, Si)-(N, O)4。 Clearly, it to realize charge balance, replaces Si to there is an O every Al and replaces N.However, the embodiment of the present invention is simultaneously O is not utilized2-Replace N3-As main charge balance mode, and it is intended to provide the modification agent sun for being positioned essentially at gap Ion, but this does not imply that not using O in combination with modifier cation2-Replace N3-。
The second way and present inventor of losing positive charge progress charge balance are utilized in the present invention main Method is substantially to be supplied to additional positive charge in gaps between crystals.Present inventor implements a series of experiments, wherein with Section III B Row element replaces Si, uses Ca2+And/or Sr2+As modifier cation.
Some embodiments of the invention comprising being replaced with realizing to Group IIIB element to the substitution of N and additional cation The general representative of the phosphor of the charge balance of Si or isovalent element may include by chemical formula M(x/v)M′2A5-yDyN8-zEp: RE is indicated The composition based on nitride, in which: M is at least one unit price, divalent or trivalent metal with chemical valence v；M ' be Mg, At least one of Ca, Sr, Ba and Zn；A is at least one of Si, C and Ge；D is at least one of B, Al and Ga；E is At least one pentavalent with chemical valence w, sexavalence or septivalency are nonmetallic；And RE is at least one of Eu, Ce, Tb, Pr and Mn； Wherein x=y-3z+p (8-w), wherein y meets 0.1≤y < 1.1, and wherein phosphor has M '2A5N8: the general crystallization knot of RE Structure, D replaces the A in the general crystalline texture, E to replace the N in the general crystalline texture, and M is positioned essentially at described one As at gap site in crystalline texture.
In First Series experiment (being expressed as sample 1-4), the of the periodic table of the potential substituent as Si is assessed IIIB row element.Starting material for synthesizing " basic compound " (being free of the phosphor of Section III B row content) is difference As europium source, the EuCl of barium source, calcium source, silicon source3、Sr3N2、Ca3N2And Si3N4Powder.Certainly, any nitride salt can provide Nitrogen.For replacing three kinds of the Si elements from periodic table Section III row to be Al, B and Ga.Experiment about this series compound Details is provided in table 2A and table 2B.Stoichiometry group comprising replacing the compound of the sample 1-4 of the Section III B row element of silicon At the atomic weight incremental order for pressing B, Al and Ga are as follows: be Eu for boron-containing compound0.05Ca0.1Sr1.95B0.2Si4.8N8；For containing Al compound is Eu0.05Ca0.1Sr1.95Al0.2Si4.8N8, and be Eu for compound containing Ga0.05Ca0.1Sr1.95Ga0.2Si4.8N8。
With reference to Fig. 1, the phosphor in this series of samples 1-4 with highest photoluminescence intensity is boron-containing compound；This A sample also shows that the phosphor with most short peak emission wavelength (emitting at about 623nm).This group phosphor containing aluminium shows Control comprising this group of compound (is free of the 2-5-8 phosphor (Eu of Section III B row substituent group0.05Sr1.95Si5N8)) it is photic Minimum photoluminescence intensity including luminous intensity.Or even control compound Eu in other words0.05Sr1.95Si5N8Also show height In the photoluminescence intensity of aluminum contained compound.In independent experiment, the photoluminescence intensity of sample containing aluminum can be by higher temperatures The lower sintering of degree further increases.It shall yet further be noted that the sample containing B and Ga does not show significant 2 θ degree offset in XRD data, This can indicate the substitution that Si may not occur in these samples.For example, B may evaporate or may be with Sr etc. Other elements form impurity phase, and 2-5-8 material (seldom or without B replacing Si) is still main phase.
In second series experiment (being expressed as sample 5-8), the of the periodic table of the potential substituent as Si is assessed IIIB row element, but the not calcic in described second group.But to realize charge balance, replace nitrogen with oxygen.Oxygen is with raw material Powder SiO2And Al2O3Form supply.Certainly, in these cases, raw material powder SiO2And Al2O3Also serve as the source of silicon and aluminium Or the source of potential source and oxygen.It is provided in table about using oxygen come the experimental detail of this series compound of charge balance In 3A and table 3B.Replace nitrogen come the chemistry for the sample 5-8 compound for replacing Si to carry out charge balance B, Al and/or Ga by oxygen Metering composition is according to the sequence are as follows: is Eu for boron-containing compound0.05Sr1.95B0.2Si4.8O0.2N7.8；It is for compound containing Al Eu0.05Sr1.95Al0.2Si4.8O0.2N7.8, and be Eu for compound containing Ga0.05Sr1.95Ga0.2Si4.8O0.2N7.8。
With reference to Fig. 5, the phosphor with highest photoluminescence intensity is control compound in this serial (sample 5-8) Eu0.05Sr1.95Si5N8.This seems to indicate, at least for this serial experiment, it is strong that addition oxygen can weaken luminescence generated by light Degree.
In third serial experiment (being expressed as sample 9-12), compare the compound pair that charge balance is carried out by clearance C a By replacing oxygen to carry out the compound of charge balance, two kinds of charge balances are that Al replaces Si institute required.Further compare these Compound with do not cause containing Al but the phosphor of intentional charge balance mechanism.Experimental detail about this series compound provides In table 4A and table 4B.The stoichiometric composition of the compound of sample 9-12 are as follows: Eu0.05Ca0.1Sr1.95Al0.2Si4.8N8, described It has used Section III B row element Al to replace Si in compound, and charge balance is realized by clearance C a； Eu0.05Sr1.95Al0.2Si4.8O0.2N7.8, also used in the compound Section III B row element Al to replace Si, but be specifically to pass through use Oxygen replaces nitrogen to realize charge balance；Eu0.05Sr1.95Al0.2Si4.8N7.93, Al is replaced using nitrogen shortage in the compound Si carries out charge balance；With finally, control be Eu0.05Sr1.95Si5N8。
With reference to Fig. 7, the phosphor with highest photoluminescence intensity is also control chemical combination in this serial (sample 9-12) Object Eu0.05Sr1.95Si5N8, but the compound replaced through Al for carrying out using clearance C a charge balance show it is about the same high Photoluminescence intensity.Data further display, this compound substitution and subsequent charge balance make peak emission intensity to It is more long wavelength shifted.This and " routine " Sr2Si5N8The wavelength shift seen when replacing Sr with Ca in compound is opposite.It is described latter Observation has multiple benefits for color rendition when generating white-light illuminating from white light LEDs.The reality implemented from present inventor Test it can be inferred that, due to Al replace Si, by Ca complete substantial intermittence charge balance be required.
In the 4th serial experiment (being expressed as sample 13-16), the of the periodic table of the potential substituent as Si is assessed IIIB row element, but intentional charge balance is not implemented in this series.The latter statement is it is meant that be not added with Ca etc. Gap cation；Unused oxygen replaces nitrogen (therefore these formulas show that the stoichiometry content of nitrogen is 8).About this series compound Experimental detail be provided in table 5A and table 5B.In this serial experiment, it is believed by the inventor that some nitrogen sites can be vacancy With balancing charge.The hypothesis of charge balance is realized using nitrogen defect based on this, it is contemplated that the chemistry of the compound of sample 13-16 Metering composition are as follows: Eu0.05Sr1.95B0.2Si4.8N7.93, Section III B row element B has replaced Si in the compound, and not further Attempt charge balance；Eu0.05Sr1.95Al0.2Si4.8N7.93, Section III B row element Al has also replaced Si in the compound, and Charge balance is not attempted；And Eu0.05Sr1.95Ga0.2Si4.8N7.93, Section III B row element Ga has replaced Si in the compound, and Also charge balance is not further attempted to.The control of this series is also Eu0.05Sr1.95Si5N8。
Some embodiments of the invention lack comprising N to realize the charge for replacing Si or isovalent element to Group IIIB element The general representative of the red emitting phosphor of balance may include by chemical formula M '2Si5-yDyN8-z: the group based on nitride that RE is indicated At wherein M ' is at least one of Mg, Ca, Sr, Ba and Zn；D is at least one of B, Al and Ga；And RE be Eu, Ce, At least one of Tb, Pr and Mn；Wherein y=3z, phosphor have M '2Si5N8: the general crystalline texture of RE, and Al replaces institute State the Si in general crystalline texture.In addition, red emitting phosphor can be configured, it is Eu that wherein M ', which is Sr, D Si, and RE,.It is rubescent Light phosphor can be configured, wherein the red emitting phosphor is made of Sr, Si, Al, N and Eu.Red emitting phosphor can be through matching It sets, wherein y meets 0.1≤y < 0.4.Red emitting phosphor can be configured, and wherein z meets 0.05≤z < 0.09.
With reference to Fig. 9, the phosphor with highest photoluminescence intensity is boracic chemical combination in this serial (sample 13-16) Object.The high person of intensity time is two kinds of compounds with substantially the same intensity: gallium-containing compound and control.Aluminum contained compound has Significantly lower photoluminescence intensity.Interestingly, it can be noted that in this series, control contains B and contains Ga The peak emission wavelength that sample (sample 15 and 16) shows is about 624nm.According to some embodiments, B and Ga may not replace Si, And it is used as fluxing agent.The statement is made according to experiment, and wherein x-ray diffraction peak is not deviated because of substitution；In addition, peak Value launch wavelength does not also deviate in these experiments.Interestingly, it can be noted that with the sample through Ca charge balance (sample 2) is compared, and it is strong compared with small wavelength offset and lower luminescence generated by light that the Al for lacking charge balance through N replaces sample to have Degree.This may indicate that being placed in the Ca in gap for charge balance keeps wavelength shift farther and improve photoluminescence intensity.
In the 5th serial experiment (being expressed as sample 17-21), assessment is as except stoichiometric equation Sr2Si5N8Member in addition The periodic table Section III B row element of element.The amount for the Section III B row element being added in raw material powder mixture is about sample 13-16 Twice of (50%) i.e. lower than the sample of those IIIB substitution silicon of middle dosage.The amount of the added Ca of sample 21 and the sample of addition IIIB Condition is same.Due to especially being difficult to accurately measure the composition of sintered compound if without using single-crystal x x ray diffraction method, because The stoichiometric equation of this this series is by the way that Ca, B, Al and Ga cation form are shown as its corresponding raw material powder salt " addition Agent " is shown.Therefore, the stoichiometric equation of the compound of sample 17-21 may be expressed as: added with Ca3N2's Eu0.05Sr1.95Si5N8；Eu added with BN0.05Sr1.95Si5N8；Eu added with AlN0.05Sr1.95Si5N8；Added with GaN's Eu0.05Sr1.95Si5N8；With control Eu0.05Sr1.95Si5N8.Experimental detail about this series compound is provided in table 6A and table In 6B.
With reference to Figure 11, each phosphor in this serial (sample 17-21) shows substantially the same luminescence generated by light Intensity and substantially similar peak emission wavelength (about 624nm), the Section III B row element that this instruction is added merely may not Replace silicon.
In the 6th serial experiment (being expressed as sample 22-27), from the Section III B row of periodic table selection boron for further Research.For example, with reference to the boron-containing sample in Fig. 1 and this group of sample 1-4.In this group experiment, boron content is with stoichiometric manner It is expressed as parameter " y ", the parameter " y " has following values: y=0；Y=0.2；Y=0.3；Y=0.4；Y=0.5 and y=1.0. Charge compensation is completed by adding gap calcium with amount incremental respectively.Experimental detail about this series compound provides In table 7A and table 7B.The emission spectrum of the phosphor of sample 22-27 is shown in Figure 13.
In the 7th serial experiment (being expressed as sample 28-32), from the Section III B row of periodic table selection aluminium for further Research.For example, with reference to the sample containing aluminum in Fig. 1 and this group of sample 1-4.In this group experiment, boron content is with stoichiometric manner It is expressed as parameter " y ", the parameter " y " has following values: y=0.15；Y=0.2；Y=0.25；Y=0.3 and y=0.4.Electricity Lotus compensation is completed by adding gap calcium with amount incremental respectively.Experimental detail about this series compound is provided in In table 8A and table 8B.The emission spectrum of the phosphor of sample 28-32 is shown in Figure 20.
Test the general introduction of concept
These are tested (may indicate that general trend), find Section III B row by experimental result instruction as described above Element al replaces Si and Ca maximum and strong with luminescence generated by light as the offset of combination to the longer emission wavelength of modification cation Degree is minimum to be weakened.The amount of used starting material, peak wavelength emission, the stoichiometry of phosphor and to substituted object/addition The general introduction of object is shown in the following table 1.
Amount, stoichiometry and the peak emission wavelength of the starting material of 1 sample 2 and 6 of table
In table 1 in institute's the first experiment outstanding, Al3+Replace Si4+Lead to charge unbalance.The phosphor of sample 2 passes through The Ca being substantially added in gap2+Modifier cation solves charge unbalance；This sends out the peak value of 2 phosphor of sample Ejected wave is long to increase 6nm relative to the control without Al or modifier cation.2 phosphor of sample has formula Eu0.05Ca0.1Sr1.95Al0.2Si4.8N8, and compareing is Eu0.05Sr1.95Si5N8。
In table 1 in institute's the second experiment outstanding, Al3+Replace Si4+Also lead to charge unbalance.However, in this experiment In, using larger amount of Al, and some Al are in Al2O3Form (source of oxygen).Here, O2-Replace N3-For charge balance machine System, and therefore there is no extra calcium or do not add calcium.It as a result is also the peak emission wavelength of 6 phosphor of sample relative to sample 5 Control increases 6nm.The formula of 6 compound of sample is Eu0.05Sr1.95Al0.2Si4.8N7.8O0.2, and control is also Eu0.05Sr1.95Si5N8。
However, as discussed below, Reliability Test Data is shown, mentions the phosphor of the present invention of charge balance according to calcium For or very close Lighting Industry required for the extent of stability of humidity and temperature, and make the phosphorescence of charge balance according to oxygen Body has relatively poor stability.
Figure 19 shows the comparison of the emission spectrum to following phosphor: the yellow light YAG phosphor of the doping Ce of the prior art； Adulterate (650nm) the red phosphor CaAlSiN of Eu3With the red phosphor of the 630nm doping Eu of the embodiment of the present invention Ca0.1Sr2Si4.8Al0.2N8(sample 2).Each spectrum is measured under 450nm blue-ray LED excitaton source.
Feux rouges nitride of the present invention as white light LEDs a part
Figure 15 shows the spectrum of white light LEDs (3000K), and the white light LEDs (3000K) include blue light InGaN LED, have Formula Eu0.05Ca0.1Sr1.95Si4.8Al0.2N8Red phosphor (come from sample 2) and there is formula Ce:Lu3Al5O12Green light phosphorescence Body；And Figure 16 shows the spectrum of white light LEDs (3000K), the white light LEDs (3000K) include blue light InGaN LED, have formula Eu0.05Ca0.1Sr1.95Si4.8B0.2N8Red phosphor (come from sample 3) and there is formula Ce:Lu3Al5O12Green phosphor.
Reliability test
In comprising many areas including the U.S., regulatory agency is to set performance standard instead of LED light.For example, the U.S. Bureau for Environmental Protection (US Environmental Protection Agency, EPA) combines U.S. Department of Energy (US Department of Energy, DOE) disclose such as identification power supply requirement, minimum light output requirement, luminous intensity point The specification of cloth requirement, luminous efficacy requirement, life expectancy etc., the lamp for meeting the specification can be described as " " qualified products." to requirements of plan of integral LED lamp " requirement, owns " in minimum lumen depreciation test phase (6000 hours), the coloration variation on CIE 1976 (u ', v ') figure should not for LED light More than 0.007 ", and depending on lamp type, the lamp must be " when working 15,000 or 25,000 hour with >=70% Lumen depreciation (L70) ".It is required that being directed to lamp behaviour and including all components of lamp, such as LED, phosphorus Body of light, electronic drive circuit, optical module and mechanical component.In principle, the brightness of white light LEDs weakens with aging and can be not only Due to phosphor, and still due to blue-light LED chip.The other sources weakened may be from packaging material (such as substrate), engagement Line and other components being encapsulated through silicone.In contrast, the principal element for influencing hue coordinate variation is that phosphor degrades.About Phosphor performance, it is believed that in order to meetIt is required that need it is in 85 DEG C and 85% relative humidity plus Under speed test, the coloration of phosphor each coordinate in 1000 hours changes (CIE Δ x, CIE Δ y)≤0.01.To following system The standby LED through phosphor-coating carries out accelerated test: the combination adhesives such as phosphor particles and epoxy resin or silicone, And it is then applied to LED chip.It will continuously be grasped in baking oven that coated LED is placed under assigned temperature and humidity and within the test phase Make.
Figure 17 A-17C shows that reliability of the phosphor of sample 1 to 3 and 6 under 85 DEG C and 85% relative humidities is surveyed The result of examination.Figure 17 A-17C is shown under the acceleration environment of 85 DEG C and 85% relative humidity, 3000K white light LEDs (such as Figure 15 and It is shown in the spectrum of Figure 16) photoluminescence intensity (brightness) change with time and change with time with cie color coordinate. Sr with LED conversion2Si5N8Phosphor (the Eu of control sample and sample 60.05Sr1.95Si4.8Al0.2N7.8O0.2) the two display Industrial usually unacceptable result.As most significantly improved out people's will by stability defined in maintenance intensity and coloration Material ground is to replace Si (referring to table 2A) Lai Shixian by the gap the Ca charge balance as illustrated by sample 2 and Al.Sample 3 is shown surely Qualitatively smaller opposite improvement；Sample 3 is sample containing B.
It is further improved performance to meetIt is required that (for example) one or more SiO can be used2、 Al2O3And/or TiO2Coating is coated with the phosphor particles of the composition with sample 2, if co-pending patent application is for using In the US application case of the coating (COATINGS FOR PHOTOLUMINESCENT MATERIALS) of embedded photoluminescent material No. 13/671,501 and for the highly reliable embedded photoluminescent material (HIGHLY with thick and uniform coating of titanium dioxide RELIABLE PHOTOLUMINESCENT MATERIALS HAVING A THICK AND UNIFORM TITANIUM DIOXIDE COATING) US application case the 13/273rd, 166 in taught, the content in these application cases each Full text is incorporated herein by reference.Figure 18 A-18C is shown with Al2O3/SiO2Phosphor (its of the sample 33 of coating With composition identical with sample 2).Such as from these schemas as it can be seen that coated phosphor meets for establishingThe accelerated test standard of qualification.
The synthesis of phosphor of the present invention
For each example described herein and comparative example, starting material includes at least one in following compound Person: Si3N4、AlN、Ca3N2、Sr3N2、BN、GaN、SiO2、Al2O3And EuCl3。
Sample 1 to 4
For the required composition for obtaining illustrated phosphor in sample 1 to 4, weighed according to the composition listed in table 2A solid Body powder.Then the mixture of raw material is loaded into plastics grind bottle together with grinding bead, is sealed in glove box, Then about 2 hours ball-milling technologies are executed.Then mixed-powder is loaded into the molybdenum crucible that internal diameter is 30mm and height is 30mm In；By loaded crucible molybdenum lid covering and it is placed in the gas sintered furnace equipped with graphite heater.
After loading crucible, furnace is evacuated to 10-2Pa, and sample is heated to 150 DEG C under these vacuum conditions.150 At a temperature of DEG C, by high purity N2Gas is introduced into room；Then by the temperature of furnace with the virtually constant rate of heat addition of 4 DEG C/min It is increased to about 1700 DEG C.Sample is maintained at 1700 DEG C about 7 hours.
After roasting, cuts off the power and keep sample cooling in furnace.Be lightly ground sintering after original sample phosphor, ball milling to certain Then program is washed, dried and sieved to one particle size.It is divided using marine optics (Ocean Optics) USB4000 It counts to test the photoluminescence intensity (PL) and coloration (CIE coordinate x and y) of final product.Use the K of Cu targetαLine measures X-ray diffraction (XRD) figure of the phosphor of sample 1 to 4.
The test result of the phosphor of sample 1 to 4 is shown in table 2B.Fig. 1 shows emission spectrum result.Fig. 2 shows XRD Figure.It should be noted that phosphor sample 33 is manufactured using method identical with sample 2.
The composition of the raw starting material of table 2A sample 1 to 4
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 1 2.5833 37.8131 - 46.7629 - - - - -
Sample 2 2.5833 37.8131 0.987 44.8915 1.6396 - - - -
Sample 3 2.5833 37.8131 0.987 44.8915 - 0.9928 - - -
Sample 4 2.5833 37.8131 0.987 44.8915 - - 3.3492 - -
The composition and peak emission wavelength, intensity and CIE. of table 2B sample 1 to 4
Sample 5 to 8
For the design composition for obtaining phosphor, solid powder is weighed according to the mixture composition listed in table 3A, is made With with identical synthesis program described in sample 1 to 4.Test result is shown in table 3B.
Fig. 5 is the emission spectrum of the phosphor of sample 5 to 8.Use the K of Cu targetαLine to the phosphor of sample 5 to 8 into Capable xray diffraction measurement is shown in Fig. 6.
The composition of the raw starting material of table 3A sample 5 to 8
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 5 2.5833 37.8131 - 46.7629 - - - - -
Sample 6 2.5833 37.8131 - 44.8915 0.5468 - - - 1.3602
Sample 7 2.5833 37.8131 - 43.9572 - 0.9928 - 1.2017 -
Sample 8 2.5833 37.8131 - 43.9572 - - 3.3492 1.2017 -
The composition and peak emission wavelength, intensity and CIE. of table 3B sample 5 to 8
Sample 9 to 12
For the design composition for obtaining phosphor, solid powder is weighed according to the mixture composition listed in table 4A, is made With with identical synthesis program described in sample 1 to 4.Test result is shown in table 4B.
Fig. 7 is the emission spectrum of the phosphor of sample 9 to 12.Use the K of Cu targetαPhosphor of the line to sample 9 to 12 The xray diffraction measurement of progress is shown in Fig. 8.
The composition of the raw starting material of table 4A sample 9 to 12
The composition and peak emission wavelength, intensity and CIE. of table 4B sample 9 to 12
Sample 13 to 16
For the design composition for obtaining phosphor, solid powder is weighed according to the mixture composition listed in table 5A, is made With with identical synthesis program described in sample 1 to 4.Test result is shown in table 5B.
Fig. 9 is the emission spectrum of the phosphor of sample 13 to 16.Use the K of Cu targetαPhosphorescence of the line to sample 13 to 16 The xray diffraction measurement that body carries out is shown in Figure 10.
The composition of the raw starting material of table 5A sample 13 to 16
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 13 2.5833 37.8131 - 46.7629 - - - - -
Sample 14 2.5833 37.8131 - 44.8915 1.6396 - - - -
Sample 15 2.5833 37.8131 - 44.8915 - 0.9928 - - -
Sample 16 2.5833 37.8131 - 44.8915 - - 3.3492 - -
The composition and peak emission wavelength, intensity and CIE. of table 5B sample 13 to 16
Sample 17 to 21
For the required composition for obtaining this group of phosphor, solid powder is weighed according to the mixture composition listed in table 6A End, using with identical synthesis program described in sample 1 to 4.Test result is shown in table 6B.
Figure 11 is the emission spectrum of the phosphor of sample 17 to 21.Use the K of Cu targetαPhosphorescence of the line to sample 17 to 21 The xray diffraction measurement that body carries out is shown in Figure 12.
The composition of the raw starting material of table 6A sample 17 to 21
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 17 2.5833 37.8131 - 46.7629 - - - - -
Sample 18 2.5833 37.8131 - 46.7629 0.8198 - - - -
Sample 19 2.5833 37.8131 - 46.7629 - 0.4064 - - -
Sample 20 2.5833 37.8131 - 46.7629 - - 1.6746 - -
Sample 21 2.5833 37.8131 0.494 46.7629
The composition and peak emission wavelength, intensity and CIE. of table 6B sample 17 to 21
Sample 22 to 27
For the required composition of the phosphor of acquisition sample 22 to 27, solid powder is weighed according to the composition listed in table 7A End.Using with identical synthesis program used in sample 1 to 4.Test result is shown in table 7B.
Figure 13 is the emission spectrum of the phosphor of sample 22 to 27.Use the K of Cu targetαLine obtains X-ray diffraction measurement, And the XRD diagram of sample 22 to 27 is shown in Figure 14.
The composition of the raw starting material of table 7A sample 22 to 27
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 22 2.5833 37.8131 - 46.7629 - - - - -
Sample 23 2.5833 37.8131 0.987- 44.8915 - 0.9928 - - -
Sample 24 2.5833 37.8131 1.4825 43.9572 - 1.4892 - - -
Sample 25 2.5833 37.8131 1.9776 43.0201 - 1.9856 - - -
Sample 26 2.5833 37.8131 2.4698 42.0858 - 2.482 - - -
Sample 27 2.5833 37.8131 4.9426 37.4087 - 4.964 - - -
The composition and peak emission wavelength, intensity and CIE. of table 7B sample 22 to 27
Sample 28 to 32
For the required composition of the phosphor of acquisition sample 28 to 32, solid powder is weighed according to the composition listed in table 8A End.Using with identical synthesis program used in sample 1 to 4.Test result is shown in table 8B.It should be noted that in table 8B Ionization meter is carried out using the equipment different from used in the ionization meter of sample product listed in other tables；Use the difference The absolute intensity measurement of equipment is measured lower than the absolute intensity of the used equipment of other samples.
Figure 20 is the emission spectrum of the phosphor of sample 28 to 32.Use the K of Cu targetαLine obtains X-ray diffraction measurement, And the XRD diagram of sample 28 to 32 is shown in Figure 21.
The composition of the raw starting material of table 8A sample 28 to 32
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN
Sample 28 2.5833 37.8131 0.7412 45.3600 1.2296
Sample 29 2.5833 37.8131 0.987 44.8915 1.6396
Sample 30 2.5833 37.8131 1.2356 44.4228 2.0496
Sample 31 2.5833 37.8131 1.4824 43.9572 2.4596
Sample 32 2.5833 37.8131 1.9768 43.0200 3.2792
The composition and peak emission wavelength, intensity and CIE. of table 8B sample 28 to 32
Those one of ordinary skill in the art will be appreciated that some different choosings that method as described above can be used according to element It selects to prepare the composition for exceeding the composition being explicitly described above.For example, can prepare by chemical formula M(x/v)M′2A5-yDyN8-zEp: RE table The composition shown, in which: M is at least one unit price, divalent or trivalent metal with chemical valence v, such as Li, Na, K, Sc, Ca, Mg, Sr, Ba and Y；M ' is at least one of Mg, Ca, Sr, Ba and Zn；A is at least one of Si, C and Ge；D be B, Al and At least one of Ga；E is that at least one pentavalent with chemical valence w, sexavalence or septivalency are nonmetallic, such as O, N, F, Cl, Br And I；And RE is at least one of Eu, Ce, Tb, Pr and Mn；Wherein x=y-3z+p (8-w), and wherein phosphor has M '2A5N8: the general crystalline texture of RE.
Figure 22 illustrates light emitting device in accordance with some embodiments.Device 10 may include being contained in (for example) packaging Blue light-emitting (in 450nm to 470nm range) GaN (gallium nitride) LED chip 12.It may include that (for example) low temperature concurrent roasting is ceramic (LTCC) or the packaging of high temperature polymer includes upper and lower part body part 16,18.Upper body component 16, which defines, is usually in Circular concave portion 20 is configured to receive LED chip 12.The packaging further comprises electric connector 22 and 24, also Define the respective electrode engagement pad 26 and 28 on the bottom plate of concave portion 20.Adhesive agent or solder can be used that LED chip 12 is installed Heat conductive pad on the bottom plate for being located at concave portion 20.The electronic pads of LED chip are electrically connected to packaging using closing line 30 and 32 Respective electrode engagement pad 26 and 28 on bottom plate, and filled out concave portion 20 completely with transparent polymer material 34 (usually silicone) Full, the transparent polymer material 34 is mounted with the mixed of yellow light and/or green phosphor and red phosphor material of the invention Object is closed so that the exposed surface of LED chip 12 is covered by phosphor/polymer material mixture.For the hair for enhancing described device Brightness is penetrated, the wall of concave portion is tilted and there is light reflective surface.
Figure 23 A and 23B illustrate solid luminous device in accordance with some embodiments.Device 100 is configured to generate CCT (correlated colour temperature) is about 3000K and luminous flux is the warm white of about 1000 lumens, and can be used as lower illuminator or other luminaires A part.Device 100 includes hollow o cylindrical body 102, is by circular plate-shaped substrate 104, hollow cylindrical wall part 106 It is constituted with detachable annular top 108.For help radiate, substrate 104 preferably from aluminium, aluminium alloy or it is any have high thermal conductivity The material of rate manufactures.Substrate 104 can be attached to wall portion by screw or bolt or by other fasteners or according to adhesive agent Divide 106.
Device 100 further comprises multiple 112 (blue lights of (being in the illustrated example 4) blue light-emitting LED LED), these blue light-emittings LED 112 is through installation and circle MCPCB (metallic core printed circuit board) 114 thermal communications.Blue-ray LED 112 may include the ceramic package array of 12 0.4W blue-light LED chips based on GaN (based on gallium nitride), and the array is through matching Set the rectangular array in 3 × 4 rows of column.
To maximize the transmitting of light, device 100 can further comprise the face and top 108 for being covered each by MCPCB 114 Inner curved surfaces light reflective surface 116 and 118.Device 100 further comprises photoluminescence wavelength transition components 120, It includes the mixtures of yellow light and/or green phosphor and red phosphor material of the invention, can operate to absorb LED The 112 a part of blue lights generated and the light that different wave length is converted thereof by photoluminescent process.The transmitting product of device 100 Including the group light combination generated by LED 112 and photoluminescence wavelength transition components 120.The wavelength conversion component is located remotely from LED 112 is simultaneously spatially opened with LED points.In the specification, " remotely " mean in interval or divide with " remote " Open relation.Wavelength conversion component 120 is configured to that shell aperture is completely covered, so that all light of lamp transmitting both pass through component 120.As illustrated, the usable top 108 of wavelength conversion component 120 is removably installed on the top of wall part 106, So that being easily changed the transmitting color of component and lamp.
Although the present invention has been described in detail with reference to certain embodiments of the present invention, one of ordinary skill in the art will be easy Understand, change and modification can be made to form and details without departing from the spirit and scope of the present invention.

Claims (18)

1. a kind of red emitting phosphor comprising by chemical formula M(x/v)M′2A5-xDxE8: the combination based on nitride that RE is indicated Object, in which:
M is at least one unit price, divalent or trivalent metal with chemical valence v；
M ' is at least one of Mg, Ca, Sr, Ba and Zn；
A is Si；
D is at least one of B, Al and Ga；
E is N；And
RE is at least one of Eu, Ce, Tb, Pr and Mn,
Wherein x meets 0.01≤x≤1, and wherein the red emitting phosphor has M '2A5E8: the general crystalline texture of RE, D take For the A in the general crystalline texture, and M is positioned essentially at the gap site in the general crystalline texture.
2. red emitting phosphor according to claim 1, wherein A further includes at least one of C and Ge.
3. red emitting phosphor according to claim 1, wherein E further includes at least one in O, F, Cl, Br and I Person.
4. red emitting phosphor according to claim 1, wherein M be in Li, Na, K, Sc, Ca, Mg, Sr, Ba and Y extremely Few one.
5. red emitting phosphor according to claim 1, wherein M is Ca, M ' is Sr, and A Si, E are N and RE is Eu.
6. red emitting phosphor according to claim 3, wherein D is Ga.
7. red emitting phosphor according to claim 1, wherein the red emitting phosphor include Ca, Sr, Si, Ga, N and Eu。
8. red emitting phosphor according to claim 1, wherein the red emitting phosphor is by Ca, Sr, Si, Ga, N and Eu Composition.
9. red emitting phosphor according to claim 8, wherein the red emitting phosphor is Ca0.1Sr2.0Ga0.20Si4.80N8:Eu。
10. red emitting phosphor according to claim 1, wherein the red emitting phosphor is Eu0.05Ca0.1Sr1.95Ga0.20Si4.80N8。
11. a kind of white light illumination source comprising:
Excitaton source has the launch wavelength in 200nm to 480nm range；
Red emitting phosphor according to claim 1, the red emitting phosphor are configured to absorb from the excitation The exciting radiation in source simultaneously emits the light with the peak emission wavelength greater than 600nm；And
Turn to be yellow at least one of light phosphor and green-emitting phosphors.
12. white light illumination source according to claim 11, wherein the red emitting phosphor has formula Ca0.1Sr2.0Ga0.20Si4.80N8:Eu。
13. white light illumination source according to claim 11, wherein in the Yellow light-emitting low temperature phosphor and green-emitting phosphors At least one is with formula Ce:Lu3Al5O12。
14. white light illumination source according to claim 11, wherein the excitaton source has in 420nm to 470nm range Launch wavelength.
15. a kind of red emitting phosphor comprising by chemical formula Eu0.05Ca0.1Sr1.95Ga0.20Si4.80N8Indicate based on nitridation The composition of object, wherein the red emitting phosphor has Sr2Si5N8: the general crystalline texture of Eu, Ga replace the general knot Si in crystal structure, and Ca is positioned essentially at the gap site in the general crystalline texture.
16. a kind of white light illumination source comprising:
Excitaton source has the launch wavelength in 200nm to 480nm range；
Red emitting phosphor according to claim 15, the red emitting phosphor are configured to absorb from the excitation The exciting radiation in source simultaneously emits the light with the peak emission wavelength greater than 600nm；And
Turn to be yellow at least one of light phosphor and green-emitting phosphors.
17. white light illumination source according to claim 16, wherein in the Yellow light-emitting low temperature phosphor and green-emitting phosphors At least one is with formula Ce:Lu3Al5O12。
18. white light illumination source according to claim 16, wherein the excitaton source has in 420nm to 470nm range Launch wavelength.
CN201610243773.1A 2012-07-18 2013-07-17 Red emitting phosphor based on nitride and the white light illumination source containing the phosphor Active CN105885839B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US201261673191P 2012-07-18 2012-07-18
US61/673,191 2012-07-18
US13/871,961 US8663502B2 (en) 2011-12-30 2013-04-26 Red-emitting nitride-based phosphors
US13/871,961 2013-04-26
CN201380044345.0A CN104583365B (en) 2012-07-18 2013-07-17 Based on the red emitting phosphor of nitride

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201380044345.0A Division CN104583365B (en) 2012-07-18 2013-07-17 Based on the red emitting phosphor of nitride

Publications (2)

Publication Number Publication Date
CN105885839A CN105885839A (en) 2016-08-24
CN105885839B true CN105885839B (en) 2019-10-11

Family

ID=49949232

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201380044345.0A Active CN104583365B (en) 2012-07-18 2013-07-17 Based on the red emitting phosphor of nitride
CN201610243773.1A Active CN105885839B (en) 2012-07-18 2013-07-17 Red emitting phosphor based on nitride and the white light illumination source containing the phosphor

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201380044345.0A Active CN104583365B (en) 2012-07-18 2013-07-17 Based on the red emitting phosphor of nitride

Country Status (5)

Country Link
JP (1) JP6060259B2 (en)
KR (1) KR101546510B1 (en)
CN (2) CN104583365B (en)
TW (1) TWI530549B (en)
WO (1) WO2014015038A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104583365B (en) * 2012-07-18 2016-05-11 英特曼帝克司公司 Based on the red emitting phosphor of nitride
US8597545B1 (en) 2012-07-18 2013-12-03 Intematix Corporation Red-emitting nitride-based calcium-stabilized phosphors
US10066160B2 (en) 2015-05-01 2018-09-04 Intematix Corporation Solid-state white light generating lighting arrangements including photoluminescence wavelength conversion components
KR102553495B1 (en) 2015-07-02 2023-07-10 루미리즈 홀딩 비.브이. Wavelength conversion light emitting device
TR201711917A2 (en) * 2017-08-11 2019-02-21 Dokuz Eyluel Ueniversitesi Rektoerluegue PHOSPHORUS-BASED SUN PROTECTION, WHICH TURNS UV LIGHT INTO RED LIGHT
CN108419307B (en) * 2018-04-17 2021-02-05 北京强度环境研究所 Control method of graphite heater
JP7428869B2 (en) * 2019-09-27 2024-02-07 日亜化学工業株式会社 light emitting device

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003321675A (en) * 2002-04-26 2003-11-14 Nichia Chem Ind Ltd Nitride fluorophor and method for producing the same
JP4244653B2 (en) * 2003-02-17 2009-03-25 日亜化学工業株式会社 Silicon nitride phosphor and light emitting device using the same
JP4128564B2 (en) * 2004-04-27 2008-07-30 松下電器産業株式会社 Light emitting device
JP4543251B2 (en) * 2004-08-31 2010-09-15 Ｄｏｗａエレクトロニクス株式会社 Phosphor and light source
JP5013374B2 (en) 2005-03-22 2012-08-29 独立行政法人物質・材料研究機構 Phosphor, method for producing the same, and light emitting device
TWI317756B (en) * 2006-02-07 2009-12-01 Coretronic Corp Phosphor, fluorescent gel, and light emitting diode device
US7648650B2 (en) * 2006-11-10 2010-01-19 Intematix Corporation Aluminum-silicate based orange-red phosphors with mixed divalent and trivalent cations
CN101631843B (en) * 2007-02-06 2015-04-08 皇家飞利浦电子股份有限公司 Red emitting luminescent materials
EP2009077A1 (en) 2007-06-29 2008-12-31 Leuchtstoffwerk Breitungen GmbH Manganese-doped metal-silicon-nitrides phosphors
CN101157854B (en) * 2007-07-02 2010-10-13 北京宇极科技发展有限公司 Oxynitrides luminescent material, preparation method and uses thereof
JP5183128B2 (en) 2007-08-30 2013-04-17 凸版印刷株式会社 Liquid crystal display
US20090283721A1 (en) * 2008-05-19 2009-11-19 Intematix Corporation Nitride-based red phosphors
US20100289044A1 (en) * 2009-05-12 2010-11-18 Koninklijke Philips Electronics N.V. Wavelength conversion for producing white light from high power blue led
CN101798510A (en) * 2010-03-15 2010-08-11 彩虹集团公司 Nitride phosphor material and preparation method thereof
US8329484B2 (en) * 2010-11-02 2012-12-11 Tsmc Solid State Lighting Ltd. Phosphor with Ce3+/Ce3+, Li+ doped luminescent materials
KR101641378B1 (en) * 2011-12-30 2016-07-20 인터매틱스 코포레이션 Nitride phosphors with interstitial cations for charge balance
CN104583365B (en) * 2012-07-18 2016-05-11 英特曼帝克司公司 Based on the red emitting phosphor of nitride

Also Published As

Publication number Publication date
CN104583365B (en) 2016-05-11
CN105885839A (en) 2016-08-24
TW201406927A (en) 2014-02-16
TWI530549B (en) 2016-04-21
WO2014015038A1 (en) 2014-01-23
KR101546510B1 (en) 2015-08-21
CN104583365A (en) 2015-04-29
JP2015529707A (en) 2015-10-08
JP6060259B2 (en) 2017-01-11
KR20150030774A (en) 2015-03-20

Similar Documents

Publication Publication Date Title
CN105154079B (en) Based on the red emitting phosphor through calcium stable for the nitride
CN105885839B (en) Red emitting phosphor based on nitride and the white light illumination source containing the phosphor
US8663502B2 (en) Red-emitting nitride-based phosphors
Jin et al. A deep red phosphor Li2MgTiO4: Mn4+ exhibiting abnormal emission: potential application as color converter for warm w-LEDs
KR101772352B1 (en) Luminescent material, method for producing a luminescent material and use of a luminescent material
Fu et al. A promising blue-emitting phosphor CaYGaO 4: Bi 3+ for near-ultraviolet (NUV) pumped white LED application and the emission improvement by Li+ ions
US20110248303A1 (en) METHOD FOR PREPARING A B-SiAION PHOSPHOR
KR102352032B1 (en) Supertetrahedron phosphor for solid-state lighting
Huang et al. Tunable concentration/excitation-dependent deep-red and white light emission in single-phase Eu 2+-activated Sc-based oxide phosphors for blue/UV-LEDs
Chen et al. The site occupation and valence of Mn ions in the crystal lattice of Sr4Al14O25 and its deep red emission for high color-rendering white light-emitting diodes
CN105131951B (en) Red light LED fluorescent powder and preparation method and application thereof
Chang et al. Intense broad-band absorption and efficient blue-emitting SrCa2MgSi2O8: Eu2+ phosphor for high color-rendering white LED applications
US9475986B2 (en) Red phosphor and light-emitting device comprising the same
Chen et al. Effect of alkali metal ions on structure and luminescent properties of red emitting β-Ca3 (PO4) 2: Eu3+ phosphor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant