WO2014015038A1 - Luminophores à base de nitrure émettant dans le rouge - Google Patents

Luminophores à base de nitrure émettant dans le rouge Download PDF

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WO2014015038A1
WO2014015038A1 PCT/US2013/050885 US2013050885W WO2014015038A1 WO 2014015038 A1 WO2014015038 A1 WO 2014015038A1 US 2013050885 W US2013050885 W US 2013050885W WO 2014015038 A1 WO2014015038 A1 WO 2014015038A1
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red
emitting phosphor
phosphor
samples
emission wavelength
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Dejie Tao
Yi-Qun Li
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Intematix Corporation
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Priority claimed from US13/871,961 external-priority patent/US8663502B2/en
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Priority to CN201380044345.0A priority Critical patent/CN104583365B/zh
Priority to KR1020157004239A priority patent/KR101546510B1/ko
Priority to JP2015523223A priority patent/JP6060259B2/ja
Publication of WO2014015038A1 publication Critical patent/WO2014015038A1/fr

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    • H01L33/26—Materials of the light emitting region
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Definitions

  • Embodiments of the present invention are directed to red-emitting nitride -based phosphor compositions.
  • silicon nitride Si 3 N 4
  • the structure of silicon nitride comprises layers of Si and N bonded in a framework of slightly distorted SiN 4 tetrahedra.
  • the SiN 4 tetrahedra are joined by a sharing of nitrogen corners such that each nitrogen is common to three tetrahedra. See, for example, S. Hampshire in "Silicon nitride ceramics - review of structure, processing, and properties," Journal of Achievements in Materials and Manufacturing Engineering, Volume 24, Issue 1, September (2007), pp. 43-50.
  • compositions of red-emitting phosphors based on silicon nitride often involve substitution of the Si at the center of the SiN 4 tetrahedra by elements such as Al; this is done primarily to modify the optical properties of the phosphors, such as the intensity of the emission, and the peak emission wavelength.
  • substitutional mechanisms for charge balance - O for N - may be employed in conjunction with an interstitial insertion of a cation.
  • the modifying cation is inserted between atoms preexisting on crystal lattice sites, into "naturally occurring" holes, interstices, or channels.
  • This mechanism does not require an altering of the anionic structure (in other words, a substitution of O for N), but this is not to say that an O for N substitution may not simultaneously occur.
  • Substitutional mechanisms for charge balance may occur in conjunction with an interstitial insertion of a modifier cation.
  • modifying cation such as Li, Mg, Ca, Y, and rare earths (excluding La, Ce, Pr, and Eu), and v is the valence of the M cation.
  • the crystal structure of an a-SiA10N is derived from the compound a-Si 3 N 4 .
  • a partial replacement of Si 4+ ions by Al 3+ ions takes place, and to compensate for the charge imbalance created by Al 3+ substituting for Si 4+ , some O substitutes N and some positive charges are added (what Shioi et al. refer to as "stabilization") by trapping the M cations into the interstices within the network of (Si,Al)-(0,N) 4 tetrahedra.
  • this red nitride phosphor has poor stability under the conditions wherein the LED is operated at a temperature ranging from 60 C to 120 C and an ambient relative humidity ranging from 40% to 90%.
  • Embodiments of the present invention provide nitride-based phosphors with chemical composition based on M 2 Si 5 N g with column IIIB elements, particularly Al, substituting for Si, and cations substantially substitutionally incorporated into the phosphor crystal structure for charge balance.
  • These phosphor materials may be configured to extend the peak emission wavelength to longer wavelengths in the red, and to enhance physical properties of the phosphor - notably, significant improvement of the temperature and humidity stability.
  • At least one embodiment of the present invention is directed to a nitride-based phosphor composition represented by the general formula ⁇ ' ⁇ ⁇ " 2 ⁇ 5 y D y E g :RE.
  • M' is at least one of a 1+ cation, a 2+ cation, and a 3+ cation
  • M" is at least one of Mg, Ca, Sr, Ba, and Zn.
  • A is at least one of Si, C and Ge.
  • the element D replaces the A component substitutionally, where D is elected from the group consisting of column IIIB elements of the periodic table.
  • D is at least one of B, Al, and Ga.
  • a modifier cation M' is added to the phosphor.
  • M' is at least one of Li 1+ , Na 1+ , K 1+ , Sc 3+ , Ca 2+ , Mg 2+ , Sr 2+ , Ba 2+ and Y 3+ , and this modifier cation is inserted into the phosphor substantially interstitially.
  • E is at least one of a 3- anion, a 2- anion, and a 1- anion, and may be at least one of O 2" , N 3" , F 1" , CI 1" , Br 1" , and I 1" .
  • the rare earth activator RE is at least one of Eu, Ce, Tb, Pr, and Mn; and y is given by 0.01 ⁇ y ⁇ 4, and x times the valence of M' is equal to y.
  • RE represents a phosphor activator and the notation ":RE" represents doping by a rare earth which is generally substitutional, but may also include doping at grain boundaries, on particle surfaces and in interstitial sites within the crystalline structure of the phosphor material.
  • the crystalline structures of the 2-5-8 nitride-based compounds as described herein may have a space group selected from Pmn2], Cc, derivatives thereof, or mixtures thereof. In some examples, the space group is Pmn2i.
  • the vacancy density of a pure crystalline material may be on the order of a hundred parts per million of the existing lattice sites depending on the thermal equilibrium conditions of the crystal. As such, a small percentage of the charge balance ions may actually end up in vacant metal ion sites, rather than the interstitial sites - the charge balance ions filling the vacancies before the interstitial sites.
  • the modifier cation M' residing in the crystal interstitially is selected from the group consisting of an alkaline earth, including Ca 2+ , and the elements Li 1+ , Y 3+ , Mn 2+ , Zn 2+ , and one or more rare earths (RE), each of the interstitially placed modifier cations may be used either individually or in combinations. This is the case as long as the sum of the modifier cations valencies equals the charge imbalance caused by the column IIIB element substitution for A.
  • an alkaline earth including Ca 2+
  • the elements Li 1+ , Y 3+ , Mn 2+ , Zn 2+ , and one or more rare earths (RE) each of the interstitially placed modifier cations may be used either individually or in combinations. This is the case as long as the sum of the modifier cations valencies equals the charge imbalance caused by the column IIIB element substitution for A.
  • a phosphor under examination has modifier cations added substantially interstitially in the present phosphors because the stoichiometric subscript on the cations will be greater than 2.
  • a traditional M 2 Si 5 N g red-emitting phosphor has a subscript that is equal to 2. When this number is greater than 2, it may be concluded that the excess cations do not reside on occupied crystalline lattice sites; rather, the added modifier cations are inserted into the interstices, holes, or channels that exist "naturally" in the crystalline structure of the host phosphor. These interstices may be unoccupied lattice sites.
  • the Si 4+ substitution being charge balanced by the inclusion of a substantially interstitially placed modifier cation as per the present invention has the unexpected benefit that the peak emission wavelength is increased, towards the red end of the spectrum. According to some embodiments, this increase is equal to or greater than about 6 nm.
  • An unexpected result that occurs in conjunction with the emission wavelength increase is a substantial maintaining of the photoemission intensity. According to some embodiments, the decrease in intensity seen with the substitutional and interstitial modifications is less than 10%, relative to the intensity prior to the modifications being made.
  • the Si 4+ substitution being charge balanced by the inclusion of a substantially interstitially placed modifier cation as per the present invention has the unexpected benefit that the stability of the phosphor is enhanced under conditions of aging at elevated temperature and humidity.
  • the phosphor is compositionally configured such that the deviation in photoluminescent intensity after 1,000 hours of aging at 85 C and 85% humidity is no greater than about 30%.
  • the phosphor is further compositionally configured such that the deviation in chromaticity coordinates CIE ⁇ and CIE Ay after 1,000 hours of aging at 85 C and 85% humidity is less than or equal to about 0.03 for each coordinate.
  • the interstitial modifier cation charge balancing for the Si 4+ substitution is accompanied by some degree of a substitution of O 2" for N 3" .
  • the charge balancing mechanism of a substantially interstitially placed modifier cation only partially balances the charge imbalance, and the O 2' for N 3" accomplishes the remainder.
  • the reason for the "incomplete" charge balance may be that the modifier cations have a lower valence than otherwise would be the case, such as when Li + and Ca 2+ are used instead of Ca 2+ and Y 3+ .
  • the choice of modifier cations are such that the valence is high (2+, 3+, or even 5+ cations), and the charge balance is incomplete because fewer modifying cations are placed.
  • the phosphor is configured to emit light having a wavelength greater than about 600 nm under blue excitation, where blue may be defined as light having a wavelength ranging from about 420 nm to about 470 nm.
  • the present phosphors may also be excited by radiation having shorter wavelengths; e.g., from about 250 nm to about 420 nm, but when the excitation radiation is in the x-ray or UV, a separate blue- emitting phosphor is provided to contribute a blue component to the desired white light for a white light source.
  • a common blue excitation source is an InGaN LED, or GaN LED, emitting with a peak at about 460 nm.
  • Embodiments of the present invention also include white light illumination sources comprising a blue-emitting InGaN light emitting diode (LED) and any of the red-emitting phosphors described herein. It may also include a yellow-emitting phosphor and/or a green- emitting phosphor. In one embodiment a green emitting phosphor has the formula Ce:Lu 3 Al 5 0 12 .
  • At least one embodiment of the invention is based on a modified version of M 2 Si 5 N g (a so-called "258" compound), where M is an alkaline earth.
  • the modification to the 258 compound includes substitution of a periodic table column IIIB element B, Al, Ga, and/or In for Si, particularly Al, where charge compensation may be accomplished by the substantially interstitial insertion of a so-called modifier cation into the phosphor's host crystal structure.
  • Modifier cations have a range of valencies, and include Li + , Ca 2+ , and Y 3+ .
  • Advantages of the modification to 258 include an increase in peak emission wavelength towards the deep red end of the spectrum, and an enhanced stability in elevated thermal and humidity conditions.
  • the phosphor has the general crystalline structure of M ' 2 A 5 N g :RE, D substitutes for A within said general crystalline structure, E substitutes for N within said general crystalline structure, and M is located within said general crystalline structure substantially at the interstitial sites.
  • the red-emitting phosphor may be selected from the group consisting of: Eu 0 05 Ca A Sr 95 B Q 2 Si 4 g N g ;
  • a red-emitting phosphor may comprise a nitride-based composition represented by the chemical formula M ' 2 Si 5.-y D y N réelle 8-z :RE, ' wherein M ' is at least one of Mg °,' Ca, ' Sr, ' Ba, ' and Zn; '
  • the red-emitting phosphor may be configured wherein M ' is Sr, D is Si, and RE is Eu.
  • the red-emitting phosphor may be configured wherein said red-emitting phosphor consists of Sr, Si, Al, N and Eu.
  • the red- emitting phosphor may be configured wherein y satisfies 0.1 ⁇ y ⁇ 0.4.
  • the red-emitting phosphor may be configured wherein z satisfies 0.05 ⁇ z ⁇ 0.09.
  • the red-emitting phosphor may be configured wherein the phosphor absorbs radiation at a wavelength ranging from about 200 nm to about 470 nm and emits light with a photoluminescence peak emission wavelength greater than 623 nm.
  • the phosphor may be configured wherein the phosphor is selected from the group consisting of: Eu Q ⁇ 95 B Q 2 Si 4 g N 7 93 ; Eu Q ⁇ 95 A1 Q 2 Si 4 g N ? 93 ; and Eu Q ⁇ S ⁇ 95 Ga Q 2 Si 4 g N ? 93 .
  • a red-emitting phosphor with a nitride-based composition may comprise: an element M, wherein M is at least one of Li, Na, K, Sc, Ca, Mg, Sr, Ba and Y; an element M', wherein M' is at least one of Mg, Ca, Sr, Ba, and Zn; silicon; aluminum; nitrogen; and an element RE, wherein RE is at least one of Eu, Ce, Tb, Pr and Mn; wherein said red-emitting phosphor has the general crystalline structure of M' 2 Si 5 N g :RE with M and Al incorporated therein, and wherein said red-emitting phosphor is configured such that the change in chromaticity coordinates CIE
  • ⁇ and CIE Ay after 1,000 hours of aging at about 85 C and about 85% relative humidity is less than or equal to about 0.03 for each coordinate.
  • a red-emitting phosphor may comprise a nitride-based composition represented by the chemical formula M (,x/ .v ,) ⁇ ' 2 Si 5-x Al x N 8 'RE, ' wherein: M is at least one monovalent, ' divalent or trivalent metal with 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 satisfies 0.1 ⁇ x ⁇ 0.4, and wherein said red-emitting phosphor has the general crystalline structure of M ' 2 Si 5 N g :RE, Al substitutes for Si within said general crystalline structure, and M is located within said general crystalline structure substantially at the interstitial sites.
  • M is at least one monovalent, ' divalent or trivalent metal with valence v
  • M' is at least one of Mg, Ca, Sr, Ba, and Zn
  • RE is at least one of
  • FIG. 1 shows emission spectra of the phosphors from Samples 1 through 4, according to some embodiments of the present invention
  • FIG. 2 shows x-ray diffraction patterns for the phosphors from Samples 1 through 4, according to some embodiments of the present invention
  • FIG. 3 shows an excitation spectrum of the compound Eu Q 05 Ca 0 Sr 95 Si 4 Al 2 N g (Sample 2) illustrating that the phosphors may be efficiently excited by radiation ranging from the UV to the blue regions of the electromagnetic spectrum, according to some embodiments of the present invention
  • FIG. 4 shows an excitation spectrum of the compound Eu 0 05 Ca Q 1 Sr 1 95 Si 4 8 B 0 2 N 8 (Sample 3) illustrating that the phosphors may be efficiently excited by radiation ranging from the UV to the blue regions of the electromagnetic spectrum, according to some embodiments of the present invention
  • FIG. 5 shows emission spectra from the phosphors of Samples 5-8, according to some embodiments of the present invention.
  • FIG. 6 shows x-ray diffraction patterns of the phosphors from Samples 5-8, according to some embodiments of the present invention
  • FIG. 7 shows emission spectra of the phosphors from Samples 9-12, according to some embodiments of the present invention.
  • FIG. 8 shows x-ray diffraction patterns of the phosphors from Samples 9 through 12, according to some embodiments of the present invention
  • FIG. 9 shows emission spectra of the phosphors from Samples 13 through 16, according to some embodiments of the present invention.
  • FIG. 10 shows x-ray diffraction patterns of the phosphors from Samples 13 through 16, according to some embodiments of the present invention
  • FIG. 11 shows emission spectra of the phosphors from Samples 17 through 21, according to some embodiments of the present invention.
  • FIG. 12 shows x-ray diffraction patterns of the phosphors from Samples 17 through 21, according to some embodiments of the present invention
  • FIG. 13 shows emission spectra of the phosphors from Samples 22 through 27, according to some embodiments of the present invention.
  • FIG. 14 shows x-ray diffraction patterns of the phosphors from Samples 22 through 27, according to some embodiments of the present invention.
  • FIG. 15 shows the emission spectrum of a white LED (3000K) comprising a blue InGaN LED, a red phosphor having the formula Eu 0 05 Ca Q ⁇ r ⁇ Si ⁇ A1 Q 2 N 8 (Sample 2), and a green phosphor having the formula Ce:Lu 3 Al 5 0 12 , according to some embodiments of the present invention;
  • FIG. 16 shows the emission spectrum from a white LED (3000K) comprising a blue InGaN LED, a red phosphor having the formula Eu 0 05 Ca 0 1 Sr 1 95 Si 4 g B 0 2 N 8 (Sample 3) and a green phosphor having the formula Ce:Lu 3 Al 5 0 12 , according to some embodiments of the present invention;
  • FIGS. 17A-17C show the results of reliability testing under the conditions of 85 C and 85% relative humidity of the phosphor of Samples 1 through 3 and 6, where FIG. 17A is the change in photoluminescent intensity (brightness) with time, FIG. 17B is the change in CIE x chromaticity coordinate with time, and FIG. 17C is the change in CIE y chromaticity coordinate with time, according to some embodiments of the present invention;
  • FIGS. 18A-18C show the results of reliability testing under the conditions of 85 C and 85% relative humidity of the phosphor of Sample 33 (which has the same composition as Sample 2) uncoated and coated with Al 2 0 3 /Si0 2 , where FIG. 18A is the change in photoluminescent intensity (brightness) with time, FIG. 18B is the change in CIE x chromaticity coordinate with time, and FIG. 18C is the change in CIE y chromaticity coordinate with time, according to some embodiments of the present invention;
  • FIG. 19 shows emission spectra for a prior art yellow Ce doped YAG phosphor, a prior art Eu doped (650 nm) red phosphor CaAlSiN 3 , and a 630 nm Eu doped red phosphor Ca Q 1 Sr 2 Si 4 8 A1 Q 2 N g in accordance with an embodiment of the present invention
  • FIG. 20 shows emission spectra of the phosphors from Samples 28 through 32, according to some embodiments of the present invention.
  • FIG. 21 shows x-ray diffraction patterns of the phosphors from Samples 28 through 32, according to some embodiments of the present invention.
  • FIG. 22 shows a light emitting device, according to some embodiments of the present invention.
  • FIGS. 23 A and 24B show a solid-state light emitting device, according to some embodiments of the present invention.
  • Some embodiments of the present invention are directed to a nitride -based phosphor composition represented by the general formula ⁇ ' ⁇ ⁇ " 2 ⁇ 5 y D y E g :RE.
  • M' is at least one of a 1+ cation, a 2+ cation, and a 3+ cation
  • M" is at least one of Mg, Ca, Sr, Ba, and Zn, used either individually or in combinations.
  • A is at least one of C, Si and Ge, used either individually or in combinations.
  • the element D replaces the A component substitutionally, where D is selected from the group consisting of column IIIB elements of the periodic table of elements.
  • D is at least one of B, Al, and Ga, used either individually or in combinations.
  • the modifier cation M' is added to the phosphor to charge compensate for the substitution of D for A.
  • M' is at least one of Li , Na , K , Sc , Ca , and Y , used either individually or in combinations.
  • M' is an extra cation, utilized in addition to the stoichiometric amount "2" of the divalent metal M in the formula M L,Si NL, and as such, this modifier cation is said to have been inserted into the phosphor substantially interstitially . More will be said about the nature of this site in a nomenclature section to follow.
  • E in the general formula of the present phosphor is at least one of a 3- anion, a 2- anion, and a 1- anion.
  • E may be at least one of O 2" , N 3" , F 1" , CI 1" , Br “ , and I " , used either individually or in combinations.
  • the rare earth RE is at least one of Eu, Ce, Tb, Pr, and Mn; and y is given by 0.01 ⁇ y ⁇ 1.0.
  • the value of the parameter y may simultaneously be defined as the value of x times the valence of M'; this is the condition that achieves the charge balance.
  • the M' cation is a "modifier" cation, a term of art used to denote cations introduced substantially interstitially to achieve charge balance and/or stabilization of the crystal structure, rather than by a substitutional mechanism.
  • Interstitial sites are cavities, holes, or channels that exist in the crystalline lattice by virtue of the manner in which the host's constituent atoms are arranged (packed, or stacked).
  • Dopant atoms that occupy the interstices of a crystal are to be distinguished from such atoms introduced substitutionally; in this latter mechanism, the dopant atoms replace host atoms residing on crystal lattice sites. The difference in the ways that these two mechanisms achieve charge balance in the phosphor will be manifested by the host's stoichiometric formula.
  • Two phases coexist in the range of 0.5 ⁇ x ⁇ 0.75 where transformation from orthorhombic to monoclinic structure occurs." Piao et al.
  • interstitial site is used in this disclosure to describe the sites where the charge-balancing modifier-cations are inserted.
  • modifier-cations such as Ca 2+
  • interstitial was chosen to emphasize the fact that the modifier cations generally do not replace, or substitute for, existing ions on crystalline lattice sites.
  • modifier cations are cations that are added to the existing crystalline host structure.
  • Embodiments of the present invention are directed to a nitride-based phosphor composition represented by the general formula ⁇ ' ⁇ ⁇ " 2 ⁇ 5 y D y E g :RE.
  • M' is at least one of a 1+ cation, a 2+ cation, and a 3+ cation
  • M" is at least one of Mg, Ca, Sr, Ba, and Zn.
  • A is at least one of Si and Ge.
  • the element D replaces the A component substitutionally, where D is elected from the group consisting of column IIIB elements of the periodic table.
  • D is at least one of B, Al, and Ga.
  • a modifier cation M' is added to the phosphor.
  • M' is at least one of Li , Na , K , Sc , Ca , and Y , and this modifier cation is inserted into the phosphor substantially inter stitially
  • E is at least one of a 3- anion, a 2- anion, and a 1- anion, and may be at least one of O 2" , N 3" , F " , CI " , Br " , and T.
  • the rare earth RE is at least one of Eu, Ce, Tb, Pr, and Mn; and y is given by 0.01 ⁇ y ⁇ 1.0, and x times the valence of M' is equal to y.
  • the modifier cations M' residing in the crystal substantially interstitially are selected from the group consisting of the alkaline earths, including Ca 2+ , and the elements Li + , Zn 2+ , Y 3+ , and one or more rare earths (RE), each of these interstitially placed modifier cations used either individually or in combinations.
  • the alkaline earths including Ca 2+
  • the elements Li + , Zn 2+ , Y 3+ , and one or more rare earths (RE), each of these interstitially placed modifier cations used either individually or in combinations.
  • RE rare earths
  • substitutional mechanisms discussed above occur when a rare earth activator ion is inserted into the host replacing an alkaline earth atom at its lattice site, thereby converting an "ordinary ceramic" into a phosphor. But there are other ways in which a substitutional event may occur: substitution may also come into play, for example, when the Si at the center of a SiN 4 tetrahedron is replaced by Al. This may be done to modify optical properties.
  • the present embodiments do not, however, utilize 0 2 ⁇ for N 3" substitution as a primary means of charge balance, preferring instead to provide substantially interstitial modifier cations, but this is not to say that the 0 2 ⁇ for N 3" substitution may not be used in conjunction with modifier cations.
  • a second way to charge balance the missing positive charge, and the primary method utilized by the present inventors in this disclosure, is to supply additional positive charges substantially interstitially to the crystal.
  • a series of experiments was conducted by the present inventors wherein column IIIB elements were substituted for Si, Ca 2+ and/or Sr 2+ was employed as a modifier cation.
  • a generalized representation of a phosphor according to some embodiments of the present invention which includes substitution for N in combination with additional cations to achieve charge balance for a Group IIIB element substitution for the Si, or equivalent element, may comprise a nitride-based composition represented by the chemical formula M, .
  • the stoichiometric compositions of the compounds from Samples 1-4 that include column IIIB elements substituting for silicon are, in the increasing order of atomic weight B, Al, and Ga: Eu 0 05 Ca Q 1 Sr 1 95 B 0 2 Si 4 8 N 8 for the boron containing compound; Eu 0 05 Ca 0 1 Sr 1 95 Al 0 2 Si 4 g N g for the Al containing compound, and Eu Q 05 Ca 0 Sr 95 Ga Q 2 Si 4 g N g for the Ga containing compound.
  • the phosphor of this series from Samples 1-4 with the highest photoluminescent intensity was the boron containing compound; this sample also demonstrated the phosphor with the shortest emission peak wavelength (emitting at about 623 nm).
  • the aluminum containing phosphor of this group displayed the lowest photoluminescent intensity, including that of the control for this group of compound, the 2-5-8 phosphor containing no column IIIB substituent (Eu Q 05 Sr 1 95 Si 5 N g ). In other words, even the control compound
  • EU Q QJ S ⁇ 95 Si 5 N g displayed a higher photoluminescent intensity than did the aluminum containing compound.
  • the photoluminescent intensity of aluminum containing samples can be further increased by sintering at a higher temperature. It was also noticed that the samples containing B and Ga did not show a substantial 2 ⁇ degrees shift in the XRD data which may indicate that the substitution of Si might not have occurred in these samples.
  • the B may have evaporated or may have formed an impurity phase with other elements such as Sr, and the 2-5-8 material (with little or no substitution of B for Si) is still the majority phase.
  • the stoichiometric compositions of the compounds from Samples 5-8 that charge balance B, Al, and/or Ga for Si substitutions via the substitution of oxygen for nitrogen are, in that order: Eu 0 05 Sr 1 95 B 0 2 Si 4 g O 0 2 N 7 g for the boron containing compound; Eu 0 05 Sr 1 95 Al 0 2 Si 4 g O 0 2 N 7 g for the Al containing compound, and Eu Q ⁇ S ⁇ 95 Ga Q 2 Si 4 g O Q 2 N ? g for the Ga containing compound.
  • the stoichiometric compositions of the compounds from Samples 9-12 were: Eu 0 05 Ca 0 Sr j 95 A1 Q 2 Si 4 g N g , a compound where the column IIIB element Al has been substituted for Si, and charge balance is effected by interstitial Ca, Eu Q 05 Sr 1 95 Al 0 2 Si 4 8 O 0 2 N 7 8 , a compound where the column IIIB element Al has again been substituted for Si, but this time charge balance is effected by oxygen substituting for nitrogen, Eu Q 05 Sr Al Si 4 g N 7 93 , a compound where a nitrogen deficit is used for charge balance for the substitution of Si by Al, and finally the control,
  • the phosphor of this series (Samples 9-12) with the highest photoluminescent intensity was again the control compound, Eu Q 05 Sr Si N g , although the Al substituted compound using interstitial Ca for charge balance displayed a photoluminescent intensity that was almost as high.
  • the data further shows that the substitution and subsequent charge balance of this compound shifted the peak emission intensity towards longer wavelengths. This is opposite to the wavelength shift that is seen when Ca is substituted for Sr in a "conventional" Sr 2 Si 5 N g compound. This latter observation has many advantages with regard to color rendition when producing white light illumination from a white LED. From the experiments conducted by the present inventors, it may be concluded that a substantially interstitial charge balance accomplished by Ca in light of an Al substitution of Si is necessary.
  • the stoichiometric compositions of the compounds from Samples 13-16 are expected to be: Eu Q 05 Sr 1 95 B Q 2 Si 4 g N ? , a compound where the column IIIB element B has been substituted for Si, with no further attempt at charge balance; Eu Q Sr 95 A1 A 2 Si 4 g N ? , a compound where the column IIIB element Al has again been substituted for Si, with again no further attempt to charge balance; and Eu 0 05 Sr 1 95 Ga Q 2 Si 4 8 N 7 93 , a compound where the column
  • IIIB element Ga has been substituted for Si, and again, with no further attempt at charge balance.
  • the control for this series was again Eu A Ai Sr, _.Si JNL.
  • a generalized representation of a red-emitting phosphor according to some embodiments of the present invention which includes a N deficit to achieve charge balance for a Group IIIB element substitution for the Si, or equivalent element, may comprise a nitride-based the chemical formula M' 2 Si 5-y D y N 0 8-z :RE, 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 is at least one of Eu, Ce, Tb,
  • the phosphor has the general crystalline structure of M' 2 Si 5 N g :RE, and Al substitutes for Si within said general crystalline structure.
  • the red-emitting phosphor may be configured wherein M' is Sr, D is Si, and RE is Eu.
  • the red-emitting phosphor may be configured wherein said red-emitting phosphor consists of Sr, Si, Al, N and Eu.
  • the red- emitting phosphor may be configured wherein y satisfies 0.1 ⁇ y ⁇ 0.4.
  • the red-emitting phosphor may be configured wherein z satisfies 0.05 ⁇ z ⁇ 0.09.
  • the phosphor of this series (Samples 13-16) with the highest photoluminescent intensity was the boron containing compound.
  • the gallium containing compound was the control.
  • the aluminum containing compound had significantly lower photoluminescent intensity.
  • the peak emission wavelength exhibited by the control, the B containing and Ga containing samples (Samples 15 and 16), is at about 624 nm. It is possible, according to some embodiments, that B and Ga may not substitute for Si, instead serving as a flux.
  • Samples 17-21 elements from column IIIB of the periodic table were evaluated as elements in addition to the stoichiometric S ⁇ SisNs formula.
  • the amounts of the column IIIB elements added to the raw powder mix were roughly twice that used in Samples 13-16 (i.e. 50% less than those IIIB substitution of silicon samples).
  • the Sample 21 has Ca added in the same amount as the IIIB added samples. Since the compositions of sintered compounds can be difficult to determine accurately, especially if single crystal x-ray diffraction is not the method used, the stoichiometric formulas for this series are shown by representing the Ca, B, Al, and Ga cations as "additives" of their respective raw powder salts.
  • the stoichiometric formulas of the compounds from Samples 17-21 may be represented as: Eu ⁇ S ⁇ 95 Si 5 N g with Ca 3 N 2 addition; Eu ⁇ S ⁇ 95 Si 5 N g with BN addition;
  • each of the phosphors of this series displayed substantially the same photoluminescent intensity, as well as a substantially similar peak emission wavelength, at about 624 nm, which indicates that the simple additions of column IIIB elements might not substitute for silicon.
  • boron was selected from column IIIB of the periodic table for further investigation. See, for example, FIG. 1, and the boron containing sample in that set of Samples 1-4.
  • Charge compensation was accomplished by interstitial calcium addition, in respectively increasing amounts.
  • Tables 7A and 7B The emission spectra of the phosphors from Samples 22-27 are shown in FIG. 13.
  • FIG. 19 shows a comparison of emission spectra for: a state of the art yellow Ce doped YAG phosphor; a Eu doped (650 nm) red phosphor CaAlSiN 3 and a 630 nm Eu doped red phosphor Ca Q j S ⁇ S ⁇ g Al 0 2 N g (Sample 2) in accordance with an embodiment of the invention.
  • FIG. 15 shows the spectrum from a white LED (3000K) comprising a blue InGaN LED; a red phosphor having the formula Eu 0 05 Ca A Sr 95 Si 4 g Al 0 2 N g (from Sample 2); and a green phosphor having the formula Ce:Lu 3 Al 5 0 12 ; and FIG. 16 shows the spectrum from a white LED (3000K) comprising a blue InGaN LED; a red phosphor having the formula Eu 0 05 Ca A Sr 95 Si 4 g Al 0 2 N g (from Sample 2); and a green phosphor having the formula Ce:Lu 3 Al 5 0 12 ; and FIG. 16 shows the spectrum from a white LED (3000K) comprising a blue InGaN LED; a red phosphor having the formula Eu 0 05 Ca A Sr 95 Si 4 g Al 0 2 N g (from Sample 2); and a green phosphor having the formula Ce:Lu 3 Al 5 0 12 ; and FIG.
  • LED (3000K) comprising a blue InGaN LED; a red phosphor having the formula Eu 0 05 Ca 0 1 Sr 1 95 Si 4 g B 0 2 N g (from Sample 3); and a green phosphor having the formula
  • the ENERGY STAR ® "Program Requirements for Integral LED Lamps" requires that for all LED lamps "the change of chromaticity over the minimum lumen maintenance test period (6000 hours) shall be within 0.007 on the CIE 1976 (u',v') diagram” and depending on lamp type, the lamp must have ">70% lumen maintenance (L70) at 15,000 or 25,000 hours of operation”.
  • the ENERGY STAR ® requirements are for the lamp performance and include all components of the lamp such as the LEDs, phosphor, electronic driver circuitry, optics and mechanical components. In principal, the degradation in brightness of a white LED with aging can be due not only to the phosphor, but also to the blue LED chip.
  • CIE ⁇ , CIE Ay change in chromaticity
  • the accelerated testing is done on phosphor coated LEDs prepared as follows: phosphor particles are combined with a binder, such as epoxy or silicone, and then applied to the LED chip. The coated LED is placed in an oven at the specified temperature and humidity and operated continuously for the testing period.
  • FIGS. 17A-17C show the results of reliability testing under the conditions of 85°C and 85% relative humidity of the phosphor of Samples 1 through 3 and 6.
  • FIGS. 17A-17C show the change in photoluminescent intensity (brightness) and the change in CIE chromaticity coordinates of 3000K white LEDs (as shown in the spectra of FIGS. 15 and 16) with time under the accelerated conditions of 85 C and 85% relative humidity.
  • Both the S ⁇ SisNs control sample and the phosphor of Sample 6 (Eu Q Sr 95 Si 4 8 A1 Q 2 N ? g O 0 ) with LED conversion showed results that would typically be unacceptable to the industry.
  • the particles of the phosphor with the composition of Sample 2 can be coated with one or more coatings of, for example, Si0 2 , A1 2 0 3 and/or Ti0 2 , as taught in copending patent applications U.S. Appl. No. 13/671,501 for COATINGS FOR PHOTOLUMINESCENT MATERIALS and U.S. Appl. No. 13/273,166 for HIGHLY RELIABLE PHOTOLUMINESCENT MATERIALS HAVING A THICK AND UNIFORM TITANIUM DIOXIDE COATING, the content of each of which is incorporated in its entirety by way of reference thereto.
  • the starting materials included at least one of the compounds Si 3 N 4 , A1N, Ca 3 N 2 , Sr 3 N 2 , BN, GaN, Si0 2 ,
  • the furnace was evacuated to 10 "2 Pa, and the sample heated to 150 C under these vacuum conditions. At the 150 C temperature, a high purity N 2 gas was introduced into the chamber; the temperature of the furnace was then increased to about
  • FIG. 1 shows the emission spectra results.
  • Fig. 2 shows the XRD patterns. Note that the phosphor Sample 33 was made using the same method as for Sample 2.
  • Table 2B Composition and Emission Peak Wavelength, Intensity and CIE of Samples 1 through 4.
  • FIG. 5 is the emission spectra of the phosphors from Samples 5 through 8. Powder x- ray diffraction measurements using the K a line of a Cu target are shown in FIG. 6 for the phosphors of Samples 5 through 8.
  • Table 3 A Composition of starting raw materials for Samples 5 through 8.
  • FIG. 7 is the emission spectra of the phosphors from Samples 9 through 12. Powder x-ray diffraction measurements using the K a line of a Cu target are shown in FIG. 8 for the phosphors of Samples 9 through 12.
  • FIG. 9 is the emission spectra of the phosphors from Samples 13 through 16. Powder x-ray diffraction measurements using the K a line of a Cu target are shown in FIG. 10 for the phosphors of Samples 13 through 16.
  • FIG. 11 is the emission spectra of the phosphors from Samples 17 through 21. Powder x-ray diffraction measurements using the K a line of a Cu target are shown in FIG. 12 for the phosphors of Samples 17 through 21. [00124] Table 6A Composition of starting raw materials for Samples 17 through 21.
  • Table 6B Composition and Emission Peak wavelength, Intensity and CIE of Samples 17 through 21.
  • FIG. 13 is the emission spectra of the phosphors from Samples 22 through 27. X-ray diffraction measurements using the Ka line of a Cu target were obtained, and the XRD patterns of Samples 22 through 27 are shown in FIG. 14.
  • FIG. 20 is the emission spectra of the phosphors from Samples 28 through 32. X-ray diffraction measurements using the K Monomer line of a Cu target were obtained, and the XRD patterns of Samples 28 through 32 are shown in FIG. 21. [00134] Table 8A Composition of starting raw materials for Samples 28 through 32.
  • compositions beyond those specifically described above may be made using the methods described above with some different choices of elements.
  • M is at least one monovalent, divalent or trivalent metal with 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 is at least one of B, Al, and Ga;
  • E is at least one pentavalent, hexavalent or heptavalent non-metal with valence w, such as O, N, F, CI, Br and I; and
  • FIG. 22 illustrates a light emitting device, according to some embodiments.
  • the device 10 can comprise a blue light emitting, within the range of 450 nm to 470 nm, GaN (gallium nitride) LED chip 12, for example, housed within a package.
  • the package which can for example comprise a low temperature co-fired ceramic (LTCC) or high temperature polymer, comprises upper and lower body parts 16, 18.
  • the upper body part 16 defines a recess 20, often circular in shape, which is configured to receive the LED chips 12.
  • the package further comprises electrical connectors 22 and 24 that also define corresponding electrode contact pads 26 and 28 on the floor of the recess 20.
  • LTCC low temperature co-fired ceramic
  • the LED chip 12 can be mounted to a thermally conductive pad located on the floor of the recess 20.
  • the LED chip's electrode pads are electrically connected to corresponding electrode contact pads 26 and 28 on the floor of the package using bond wires 30 and 32 and the recess 20 is completely filled with a transparent polymer material 34, typically a silicone, which is loaded with a mixture of a yellow and/or green phosphor and a red phosphor material of the present invention such that the exposed surfaces of the LED chip 12 are covered by the phosphor/polymer material mixture.
  • a transparent polymer material 34 typically a silicone
  • the walls of the recess are inclined and have a light reflective surface.
  • FIGS. 23A and 23B illustrate a solid-state light emitting device, according to some embodiments.
  • the device 100 is configured to generate warm white light with a CCT (Correlated Color Temperature) of approximately 3000K and a luminous flux of approximately 1000 lumens and can be used as a part of a downlight or other lighting fixture.
  • the device 100 comprises a hollow cylindrical body 102 composed of a circular disc-shaped base 104, a hollow cylindrical wall portion 106 and a detachable annular top 108.
  • the base 104 is preferably fabricated from aluminum, an alloy of aluminum or any material with a high thermal conductivity.
  • the base 104 can be attached to the wall portion 106 by screws or bolts or by other fasteners or by means of an adhesive.
  • the device 100 further comprises a plurality (four in the example illustrated) of blue light emitting LEDs 112 (blue LEDs) that are mounted in thermal communication with a circular-shaped MCPCB (metal core printed circuit board) 114.
  • the blue LEDs 112 can comprise a ceramic packaged array of twelve 0.4W GaN-based (gallium nitride -based) blue LED chips that are configured as a rectangular array 3 rows by 4 columns.
  • the device 100 can further comprise light reflective surfaces 116 and 118 that respectively cover the face of the MCPCB 114 and the inner curved surface of the top 108.
  • the device 100 further comprises a photo luminescent wavelength conversion component 120 including a mixture of a yellow and/or green phosphor and a red phosphor material of the present invention that is operable to absorb a proportion of the blue light generated by the LEDs 112 and convert it to light of a different wavelength by a process of photoluminescence.
  • the emission product of the device 100 comprises the combined light generated by the LEDs 112 and the photoluminescent wavelength conversion component 120.
  • the wavelength conversion component is positioned remotely to the LEDs 112 and is spatially separated from the LEDs.
  • the wavelength conversion component 120 is configured to completely cover the housing opening such that all light emitted by the lamp passes through the component 120. As shown the wavelength conversion component 120 can be detachably mounted to the top of the wall portion 106 using the top 108 enabling the component and emission color of the lamp to be readily changed.

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Abstract

L'invention concerne un luminophore émettant dans le rouge qui comporte une composition à base de nitrure représentée par la formule chimique M(xv)M'2Si5-xAlxN8:RE, dans laquelle M représente au moins un métal monovalent, divalent ou trivalent avec une valence v ; M' représente au moins l'un parmi Mg, Ca, Sr, Ba et Zn ; RE représente au moins l'un parmi Eu, Ce, Tb, Pr et Mn ; x satisfaisant 0,1≤x≤0,4 et le luminophore ayant la structure cristalline générale M'2Si5N8:RE, Al remplaçant Si dans la structure cristalline et M étant situé sensiblement aux sites interstitiels. De plus, le luminophore est configuré de telle sorte que 1000 heures de vieillissement à 85°C et à 85 % d'humidité entraînent une déviation des coordonnées trichromatiques CIE Δx et Δy de moins d'environ 0,03. En outre, le luminophore absorbe le rayonnement dans l'UV et le bleu et émet une lumière ayant une longueur d'onde de pic de photoluminescence dans les limites de la plage d'environ 620 à 650 nm.
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US11742463B2 (en) 2015-07-02 2023-08-29 Lumileds Llc Wavelength converted light emitting device

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JP6060259B2 (ja) 2017-01-11
TWI530549B (zh) 2016-04-21
KR101546510B1 (ko) 2015-08-21
CN105885839B (zh) 2019-10-11
KR20150030774A (ko) 2015-03-20
JP2015529707A (ja) 2015-10-08
TW201406927A (zh) 2014-02-16
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