Stable phosphors for lighting applications

Abstract

Compositions are generally provided that include an oxyfluoride compound. In one embodiment, the oxyfluoride compound has the formula: NaCa.sub.2xA.sub.xGeO.sub.4zF.sub.1yN.sub.z where A is Ba, Sr, or a mixture thereof; 0.01x0.1; 0y0.2; and 0z0.1. Methods of forming such compounds are also generally provided.

Claims

1. A composition comprising an oxyfluoride compound having the formula:
NaCa.sub.2xA.sub.xGeO.sub.4zF.sub.1yN.sub.z where A is Ba, Sr, or a mixture thereof; 0.01x0.1; 0y0.2; and 0z0.1.

2. The composition as in claim 1, wherein z is 0.

3. The composition as in claim 1, wherein y is 0.

4. The composition as in claim 1, wherein the oxyfluoride compound has the formula:
NaCa.sub.2xA.sub.xGeO.sub.4F wherein A is Ba, Sr, or a mixture thereof; and wherein 0.01x0.1.

5. The composition as in claim 1, wherein A is Ba.

6. The composition as in claim 1, wherein A is Sr.

7. The composition as in claim 1, wherein 0.01x0.06.

8. The composition as in claim 1, further comprising: an activator ion coupled with the compound.

9. A composition comprising an oxyfluoride compound having the formula:
NaCa.sub.2xA.sub.xGeO.sub.4zF.sub.1yN.sub.z where A is Ba, Sr, or a mixture thereof; 0x0.1; 0y0.2; and 0z0.1; and an activator ion coupled with the compound.

10. The composition as in claim 9, wherein x is 0.

11. The composition as in claim 9, wherein z is 0 and y is 0.

12. The composition as in claim 9, wherein the activator ion comprises an ion of an element selected from the group consisting of La, Ac, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, U, Cr, Mn, Tc, Re, Cu, Ag, Au, Zn, Cd, Hg, As, Sb, Bi, Ge, Sn, Pb, In, Tl, and mixtures thereof.

13. The composition as in claim 9, wherein the activator ion comprises an ion of Eu, Ce, Tb, or a mixture thereof.

14. The composition as in claim 9, wherein the activator ion comprises Eu.sup.3+, Ce.sup.3+, Tb.sup.3+, or a mixture thereof.

15. A method of doping a compound having the formula: NaCa.sub.2GeO.sub.4zF.sub.1yN.sub.z where 0y0.2; and 0z0.1, the method comprising: introducing defects into the compound by substituting a portion of the Ca ions with ions of Ba, Sr, or a mixture thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) A full and enabling disclosure of the present invention, including the best mode thereof to one skilled in the art, is set forth more particularly in the remainder of the specification, which includes reference to the accompanying figures, in which:

(2) FIG. 1a the arrangement in NaCa.sub.2GeO.sub.4F of GeO.sub.4 tetrahedra (10, with oxygen atoms 11) and FM.sub.6 octahedra (M=Na/Ca) (12), with different M sites shown as M1 (14) and M2 (16), along with the CaO bonds;

(3) FIG. 1b shows the arrangement in NaCa.sub.2GeO.sub.4F in a view of the face-shared fluorine-centered octahedra in the a-c plane;

(4) FIGS. 1c and 1d show the structure of Sr.sub.3XO.sub.4F (X=Al, Ga) along a-c plane and b-c plane, respectively, as a comparison to the structure of NaCa.sub.2GeO.sub.4F and showing the XO.sub.4 tetrahedra (20), FSr.sub.6 octahedra (22); oxygen atoms (11), and different Sr sites shown as 24 and 26 along with CaO bonds.

(5) FIG. 2 shows the XRD peaks of NaCa.sub.1.955Ba.sub.0.045GeO.sub.4F (bottom line) and NaCa.sub.1.945Ba.sub.0.055GeO.sub.4F (top line) with Ba.sub.2Ge.sub.5O.sub.12 impurity peaks shown by asterisks;

(6) FIG. 3 shows the XRD peaks for different mol fractions of Ba.sup.2+ substitution;

(7) FIG. 4a shows a plot of lattice parameter a against various Ba.sup.2+ concentrations in NaCa.sub.2xBa.sub.xGeO.sub.4F (x=0.01, 0.015, 0.02, 0.025, 0.035, 0.04, 0.045), with R.sup.2 being the coefficient indicating how close the lattice parameter data scatter about a linear function of the Ba.sup.2+ concentration;

(8) FIG. 4b shows the plot of lattice parameter b against various Ba.sup.2+ concentrations in NaCa.sub.2xBa.sub.xGeO.sub.4F (x=0.01, 0.015, 0.02, 0.025, 0.035, 0.04, 0.045);

(9) FIG. 4c shows the plot of lattice parameter c against various Ba.sup.2+ concentrations in NaCa.sub.2xBa.sub.xGeO.sub.4F (x=0.01, 0.015, 0.02, 0.025, 0.035, 0.04, 0.045);

(10) FIG. 4d shows the plot of the unit cell volume against Ba.sup.2+ concentrations in NaCa.sub.2xBa.sub.xGeO.sub.4F (x=0.01, 0.015, 0.02, 0.025, 0.035, 0.04, 0.045);

(11) FIG. 4e shows the plot of lattice parameters a and b against various Ba.sup.2+ concentrations in NaCa.sub.2xBa.sub.xGeO.sub.4F (x=0.01, 0.015, 0.02, 0.025, 0.035, 0.04, 0.045);

(12) FIG. 4f shows the plot of lattice parameters a and c against various Ba.sup.2+ concentrations in NaCa.sub.2xBa.sub.xGeO.sub.4F (x=0.01, 0.015, 0.02, 0.025, 0.035, 0.04, 0.045);

(13) FIG. 5a shows a plot of lattice parameter a against y in NaCa.sub.2ySr.sub.yGeO.sub.4F;

(14) FIG. 5b shows a plot of lattice parameter b against y in NaCa.sub.2y Sr.sub.y GeO.sub.4F;

(15) FIG. 5c shows a plot of lattice parameter c against y in NaCa.sub.2ySr.sub.yGeO.sub.4F;

(16) FIG. 6 shows the emission and excitation spectra of NaCa.sub.2GeO.sub.4F at 254 nm excitation and 422 nm emission;

(17) FIG. 7 shows the emission spectra of NaCa.sub.1.985Ba.sub.0.015GeO.sub.4F (72) and NaCa.sub.2GeO.sub.4F (70) under 254 nm excitation;

(18) FIG. 8 shows the emission spectra of NaCa.sub.1.985Ba.sub.0.02GeO.sub.4F under 365 nm excitation;

(19) FIG. 9 shows excitation and emission spectra of Na.sub.1.01Ca.sub.1.98Ce.sub.0.01GeO.sub.4F at 415 nm excitation and 555 nm emission;

(20) FIG. 10a shows the Gaussian fitted emission spectra (30) of Na.sub.1.02Ca.sub.1.98Ce.sub.0.02GeO.sub.4F at 465 nm excitation and three Gaussian components (31, 32, 33);

(21) FIG. 10b shows the Gaussian-fitted emission spectra of Ca.sub.2GeO.sub.4:Ce.sup.3+,Li.sup.+ and its two Gaussian components;

(22) FIG. 11 shows (a) Plot of emission spectra of Na.sub.1+xCa.sub.22xCe.sub.xGeO.sub.4F (x=0.01, 0.02, 0.03, 0.04, 0.05) at 465 nm excitation and (b) Emission spectra of Na.sub.1+xCa.sub.22xCe.sub.xGeO.sub.4F (x=0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07) at 430 nm excitation;

(23) FIG. 12 shows a CIE chromaticity diagram showing the corresponding CIE coordinates for various phosphors studied;

(24) FIG. 13 shows excitation and emission spectra of Na.sub.1.05Ca.sub.1.9Eu.sub.0.05GeO.sub.4F at 260 nm excitation;

(25) FIG. 14 shows emission spectra of NaCa.sub.1.9Li.sub.0.05Tb.sub.0.03Ce.sub.0.02GeO.sub.4F, at 254 nm excitation;

(26) FIG. 15 shows emission spectra of NaCa1.93Tb0.07Ge0.93Al0.07O4F at 254 nm excitation;

(27) FIG. 16 shows Emission spectra of Na1.07Ca1.86Tb0.07GeO4F at 270 nm excitation;

(28) FIG. 17 shows emission spectra of Na.sub.0.1Ca.sub.1.8Mn.sub.0.1Ce.sub.0.04GeO.sub.4F at (a) 220 nm excitation, (b) 365 nm and (c) 318 nm excitation;

(29) FIG. 18a and FIG. 18b show[[s]] emission spectra of Na.sub.1.02Ca.sub.1.95Ba.sub.0.02Ce.sub.0.02GeO.sub.4F and Na.sub.1.02Ca.sub.1.96Ba.sub.0.01Ce.sub.0.02GeO.sub.4F at 365 nm excitation (FIG. 18a) and Na.sub.1.02Ca.sub.1.96Ba.sub.0.01Ce.sub.0.02GeO.sub.4F at 254 nm excitation (FIG. 18b);

(30) FIG. 19 shows excitation and emission spectra of Na.sub.1.01Ca.sub.1.97Ba.sub.0.01Eu.sub.0.01GeO.sub.4F under 254 nm excitation;

(31) FIG. 20 shows excitation and emission spectra of Na.sub.1.02Ca.sub.1.94Ba.sub.0.02Eu.sub.0.02GeO.sub.4F at 610 nm emission exhibiting peak at 378 nm;

(32) FIG. 21 shows emission spectra of Na.sub.1.02Ca.sub.1.94Ba.sub.0.02Eu.sub.0.02GeO.sub.4F at 365 nm and 420 nm excitation;

(33) FIG. 22 shows excitation and emission spectra of Na.sub.1.02Ca.sub.1.94Ba.sub.0.02Eu.sub.0.02GeO.sub.4F at 615 nm emission and 420 nm excitation;

(34) FIG. 23 shows emission spectra of Na.sub.1.01Ca.sub.1.97Ba.sub.0.01Eu.sub.0.01GeO.sub.4F at the excitation wavelengths of 365 nm, 378 nm and 412 nm;

(35) Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention.

DETAILED DESCRIPTION

(36) Reference now will be made to the embodiments of the invention, one or more examples of which are set forth below. Each example is provided by way of an explanation of the invention, not as a limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as one embodiment can be used on another embodiment to yield still a further embodiment. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the appended claims and their equivalents. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied exemplary constructions.

(37) Chemical elements are discussed in the present disclosure using their common chemical abbreviation, such as commonly found on a periodic table of elements. For example, hydrogen is represented by its common chemical abbreviation H; helium is represented by its common chemical abbreviation He; and so forth.

(38) In general, the present disclosure is directed to phosphors for use in light emitting devices.

(39) I. Substituted Oxyfluoride Compounds

(40) In one embodiment, an ordered oxyfluoride compound is generally provided that has the formula:
NaCa.sub.2xA.sub.xGeO.sub.4zF.sub.1yN.sub.z
where A is Ba, Sr, ora mixture thereof; 0.01x0.1 (e.g., 0.01x0.06); 0y0.2; and 0z0.1. In particular embodiments, z can be 0 (i.e., no nitrogen is present in the compound), and/or y can be 0. For example, in one particular embodiment, the oxyfluoride compound can have the formula:
NaCa.sub.2xA.sub.xGeO.sub.4F
wherein A is Ba, Sr, or a mixture thereof; and wherein 0.01x0.1 (e.g., 0.01x0.06). Such a oxyfluoride compound is generally a compound formed from a base compound NaCa.sub.2GeO.sub.4F, substituted with Ba.sup.2+ and/or Sr.sup.2+ for Ca.sup.2+.

(41) In one embodiment, A consists essentially of Ba (e.g., A consists of Ba). In an alternatively embodiment, A consists essentially of Sr (e.g., A consists of Sr).

(42) II. Doped Oxyfluoride Compounds

(43) Doped ordered oxyfluoride compounds are also generally provided. In one embodiment, any of the substituted oxyfluoride compounds discussed above can be doped with an activator ion. Alternatively, in one embodiment, the base oxyfluoride compound NaCa.sub.2GeO.sub.4F can be doped with an activator ion.

(44) Suitable activator ions for doping the oxyfluoride compounds (either of the substituted or base compounds) include ions of La, Ac, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, U, Cr, Mn, Tc, Re, Cu, Ag, Au, Zn, Cd, Hg, As, Sb, Bi, Ge, Sn, Pb, In, Tl, or mixtures thereof. Particularly suitable activator ions for doping the oxyfluoride compounds are ions of Eu (e.g., Eu.sup.3+), Ce (e.g., Ce.sup.3+), Tb (e.g., Tb.sup.3+), or mixtures thereof.

(45) Doping with rare earth elements allows white light emitting LEDs to be prepared by mixing green, blue and red light or yellow and blue light emitted from phosphors. Introducing suitable dopants in the oxyfluoride host lattice can result in the formation of novel down-conversion phosphors with desired emissions in the visible spectrum. Being a white powder, NaCa.sub.2GeO.sub.4F has a large optical band gap (>3 eV) due to the energy difference between the oxygen 2p state and the Ca 3d and Ge 4s states. Having a large band gap is favorable for photoluminescence as both the ground and excited states of the activator ions can be accommodated within the electronic band gap of the host structure.

(46) In particular embodiments, Eu.sup.3+ and Ce.sup.3+ can be chosen for doping. For example, the Eu.sup.3+ ion is very efficient red light emitter mainly due to its .sup.5D.sub.0.fwdarw..sup.7F.sub.0, .sup.7F.sub.1, .sup.7F.sub.2 transitions. Alternatively, Ce.sup.3+ doping can be used for its yellow emission due to its electronic transition from 5d.sup.1 to .sup.2F.sub.5/2 and .sup.2F.sub.7/2 and its role as a sensitizer.

(47) Finding the optimum dopant concentration is important to avoid concentration quenching, which decreases the luminescence due to energy transfers via multipole-multipole interactions between emitting species. Germanates have good physical and chemical stability and some germanates, for example, Ca.sub.2GeO.sub.4 has already been shown to be good phosphor. Ca.sub.2GeO.sub.4:Ce.sup.3+,Li.sup.+ exhibits a broad yellow emission band in the wavelength range of 480-750 nm under 465 nm excitation due to electronic transitions from 5d to 4f (.sup.2F.sub.5/2 and .sup.2F.sub.7/2).

(48) Ce.sup.3+ can act as a sensitizer when co-doped with Eu.sup.2+. A study done by Sivakumar et. al. on Sr.sub.2LiSiO.sub.4F has shown that, the co-doping of Ce.sup.3+ increases the probability of the absorption of Eu.sup.2+ in the UV to near-UV region as excitation spectra shows peaks at 830 and 330 nm. One observes broad-band emission from 360 to 620 nm (blue to green-yellowish) due to partial energy transfer from Ce.sup.3+ to Eu.sup.2+.

(49) Bond valence sum (BVS) calculation is a method of determining bond strengths. The bond valence provides a metric to assess the stability of a structure.

(50) $\underset{j}{\overset{}{.Math.}}{v}_{i,j}=V_i$

(51) According to Pauling's electrostatic valence rule, the atomic valence of an atom is equal to the sum of valences of all its bonds.

(52) $v_{i,j}=\exp \left[\frac{R_{i,j}-d_{i,j}}{b}\right]$

(53) where R.sub.ij is tabulated bond distance, d.sub.ij is the observed bond distance and b is an empirical constant can be calculated as 0.37 from well refined structures. The M1 and M2 (Ca/Na) sites have the same coordination environment. The formal valence of M1 is 1.7 (0.72+0.31) and the one for M2 is 1.76 (0.732+0.271). The M1 site has a BVS value of 1.87, and BVS of M2 is 1.91. These two sites can be partially substituted with Ba.sup.2+ and Sr.sup.2+. As the Sr.sup.2+ ion size is smaller (ionic radius 1.44 ) than the Ba.sup.2+ ion (ionic radius 1.61 ), Sr.sup.2+ can substitute slightly more of Ca.sup.2+ (ionic radius 1.34 ) (>0.06 mol %) than Ba.sup.2+ (<0.05 mol %). The NaCa.sub.2xBa.sub.xGeO.sub.4F samples prepared under reducing atmosphere are self-activating and shows yellow luminescence when excited with 254 nm UV light.

EXAMPLES

(54) Research on NaCa.sub.2GeO.sub.4F and related compounds was done to investigate whether this oxyfluoride material can be a phosphor when doped with lanthanides and/or rare earth elements. This oxyfluoride is chemically very stable and in its structure distinct crystallographic sites for metal ions are present which can be occupied with suitable dopants taking into consideration the charge and cation size of the host lattice metal and dopant element.

Experimental: Synthesis of Na2CaGeO4F

(55) NaCa.sub.2GeO.sub.4F was synthesized by combining stoichiometric amounts of CaCO.sub.3 (99.95%), GeO.sub.2 (99.99%), NaF (99.9%) in a mortar and pestle. The ground mixture was heated in a furnace from at 850 C. for 12 h in a flowing nitrogen atmosphere. The resulting powder was reground, pressed into a pellet, and again heated to 850 C. for 12 hours.

Experimental: Substitution of Ca Ions in Na2CaGeO4F

(56) Ba.sup.2+ substituted materials, NaCa.sub.2xBa.sub.xGeO.sub.4F (x=0.01, 0.015, 0.02, 0.025, 0.035, 0.04, 0.045) were prepared by heating appropriate amounts of CaCO.sub.3 (99.95%), GeO.sub.2 (99.99%), NaF (99.9%), BaCO.sub.3 (99.5%) under reducing gas (5% H.sub.2/95% Ar) flow at 800 C. and 900 C. for 12 hrs respectively.

(57) Sr.sup.2+ substituted materials, NaCa.sub.2xSr.sub.xGeO.sub.4F (x=0.01, 0.02, 0.05, 0.06) were prepared by heating appropriate amounts of CaCO.sub.3 (99.95%), GeO.sub.2 (99.99%), NaF (99.9%), SrCO.sub.3 (99.5%).

Experimental: Rare Earth Doping of Na2CaGeO4F

(58) Rare earth doping using Ce.sup.3+, Eu.sup.3+, and Tb.sup.3+ was performed by mixed appropriate amounts of Ce.sub.2O.sub.3, Eu.sub.2O.sub.3 and Tb.sub.4O.sub.7 with the above mentioned starting materials and heated at 950 C.

(59) Characterization

(60) The structures formed were refined based upon X-ray powder diffraction data recorded on a Rigaku Miniflex X-ray diffractometer with a Cu-K radiation source emitting a wavelength of 1.5406 . The 2 data were recorded from 3.0 to 149 degree in 2 with a step size of 0.02. The X-ray data were analyzed by Rietveld refinement using the GSAS software package. Lattice parameters and atomic sites for NaCa.sub.2GeO.sub.4F in the orthorhombic Pnma space group were used as a starting model for the refinements. The atomic coordinates and isotropic displacement parameters of different atoms occupying the same site and the oxygen displacement parameters were constrained. The fractional occupancies were fixed to the nominal composition.

(61) Results and Discussions

(62) The lattice parameters from refinement are a=5.3665(2) , b=7.3270(5) , c=12.6871(6) , V=498.72(8) .sup.3 which are in reasonable agreement within the given error values. The bond valence sum values calculated from the Schneemeyer data and our data are listed in Table 1. The BVS for M1 are almost equal, however, we observe a higher BVS value for M2 from our data due to a lower average Ca.sub.2O bond distances than that found by Schneemeyer et. al. in their single crystal refinement. The GeO bond distances are higher in our case as indicated by a lower BVS for Ge.

(63) TABLE-US-00001 TABLE 1 BVS values for various atoms in NaCa.sub.2GeO.sub.4F calculated from Schneemeyer data and this experimental data Schneemeyer Mitra, Atoms BVS Vogt BVS Ge 4.38 3.84 M1 1.66 1.87 M2 1.74 1.91 F 1.30 1.24 O1 2.27 2.14 O2 2.14 2.25 O3 2.12 1.93

(64) NaCa.sub.2GeO.sub.4F is quite stable in air and moisture, as the comparison of X-ray diffraction data of a freshly prepared NaCa.sub.2GeO.sub.4F and that of a 45 days old sample shows no significant change, but only a slight shrinkage of the lattice parameters of the aged sample. The lattice parameters obtained from a Rietvled refinement of the 45 days old sample were, a=5.3658(2) , b=7.3216(4) , c=12.6863(6) , V=498.40(8) .sup.3 compared to the fresh sample lattice parameters a=5.3665(2) , b=7.3270(5) , c=12.6871(6) , V=498.72(8) .sup.3. This chemical stability is in marked contrast to that observed for Sr.sub.3AlO.sub.4F which degrade over days when in contact with moisture and air.

(65) Structural characterization of NaCa.sub.2xA.sub.xGeO.sub.4F (A=Ba, Sr and x=0.01, 0.015, 0.02, 0.025, 0.035, 0.04, 0.045)

(66) The formal valence of M1 is 1.7 (0.72+0.31) and the one for M2 is 1.76 (0.732+0.271). The M1 site has a BVS value of 1.87, and BVS of M2 is 1.91. These two sites can be partially substituted with Ba.sup.2+ and Sr.sup.2+. As the Sr.sup.2+ ion size is smaller (ionic radius 1.44 ) than the Ba.sup.2+ ion (ionic radius 1.61 ), Sr.sup.2+ can substitute slightly more of Ca.sup.2+ (ionic radius 1.34 ) (>0.06 mol %) than Ba.sup.2+ (<0.05 mol %). The structural properties of materials from the series of NaCa.sub.2xBa.sub.xGeO.sub.4F (x=0.01, 0.015, 0.02, 0.025, 0.035, 0.04, 0.045) were investigated. At higher concentrations a second phase, hexagonal Ba.sub.2Ge.sub.5O.sub.12 started to form as an impurity, as shown in the X-ray diffraction pattern (FIGS. 2 and 3).

(67) As seen, there is a shift of the peaks towards lower 2 angles with increasing barium concentration, indicating a lattice expansion. As the two M (Ca/Na) sites in the structure have the same octahedral coordination environment, the refinements assumed that Ba.sup.2+ substitutes into the Ca1 and Ca2 sites. The Ba.sup.2+ ion being larger than the Ca.sup.2+ ion, the lattice parameters of the Ba.sup.2+ substituted material increase with higher Ba.sup.2+ concentrations as shown in Table 2. The bond distances for different Ba.sup.2+ concentrations were calculated.

(68) TABLE-US-00002 TABLE 2 Lattice parameters of various Ba.sup.2+ substituted materials in the series NaCa.sub.2-xBa.sub.xGeO.sub.4F Ba_mol % a () b () c () V (.sup.3) 0.010 5.3666(2) 7.3287(4) 12.6852(7) 498.92(5) 0.015 5.3667(2) 7.3289(4) 12.6854(8) 498.94(3) 0.020 5.3678(3) 7.3320(3) 12.6864(6) 499.29(4) 0.025 5.3689(2) 7.3312(4) 12.6880(5) 499.34(6) 0.035 5.3704(3) 7.3321(2) 12.6892(6) 499.48(5) 0.040 5.3712(2) 7.3326(3) 12.6883(5) 499.73(4) 0.045 5.3731(2) 7.3330(3) 12.6887(6) 499.75(3)

(69) The plot of the lattice parameters and unit cell volumes versus Ba.sup.2+ concentrations indicate an almost linear behavior (FIG. 4). Our refinements indicate that Ba.sup.2+ is gradually substituting Ca.sup.2+ in the M1 and M2 sites. The changing bond lengths and bond angles for the NaCa.sub.2xBa.sub.xGeO.sub.4F series are shown in Table 3. The BVS values for the atoms in the NaCa.sub.2xBa.sub.xGeO.sub.4F structures are listed in Table 4. The very small change in the BVS value for the M1 and M2 site with increasing Ba.sup.2+ mol %, indicate that the substitution of Ca.sup.2+ by a very low concentration of Ba.sup.2+ does not significantly affect the BVS values.

(70) TABLE-US-00003 TABLE 3 Bond distances and selected bond angles of NaCa.sub.2xBa.sub.xGeO.sub.4F NaCa.sub.2xBa.sub.xGeO.sub.4F x = 0.01 0.015 0.02 0.025 0.035 0.04 0.045 Gel- O1 1.795(2) 1.803(4) 1.800(2) 1.834(7) 1.821(2) 1.837(7) 1.862(4) O2 2 1.794(3) 1.799(5) 1.808(4) 1.803(2) 1.813(4) 1.824(5) 1.825(3) O3 1.780(3) 1.807(4) 1.815(8) 1.817(6) 1.827(7) 1.850(7) 1.859(4) O1--Gel--O2 107.5(4) 106.5(3) 104.6(7) 106.2(4) 107.2(5) 106.1(2) 106.0(1) O1--Gel--O3 112.3(3) 111.5(4) 113.2(3) 110.6(4) 112.0(3) 111.3(4) 111.1(3) M1- O1 2.199(4) 2.246(5) 2.277(3) 2.265(3) 2.280(6) 2.284(6) 2.329(7) O2 2.386(3) 2.403(3) 2.393(3) 2.414(5) 2.434(4) 2.422(5) 2.483(3) O2 2.265(4) 2.298(8) 2.330(5) 2.335(6) 2.361(4) 2.362(4) 2.425(6) O3 2.190(5) 2.289(3) 2.337(5) 2.316(4) 2.190(5) 2.424(3) 2.362(7) F 2.421(3) 2.424(2) 2.429(3) 2.437(3) 2.438(5) 2.452(2) 2.470(4) F 2.427(5) 2.439(6) 2.447(3) 2.500(4) 2.475(2) 2.468(4) 2.482(6) M2- O1 2.207(7) 2.278(6) 2.324(4) 2.341(9) 2.347(6) 2.378(7) 2.380(6) O2 2 2.194(8) 2.265(9) 2.305(5) 2.299(4) 2.308(3) 2.320(6) 2.345(8) O3 2.259(3) 2.302(5) 2.319(2) 2.327(4) 2.357(3) 2.382(3) 2.392(5) F 2.324(6) 2.325(3) 2.331(4) 2.326(8) 2.341(7) 2.354(3) 2.350(6) F 2.514(4) 2.538(7) 2.549(4) 2.556(4) 2.561(4) 2.566(8) 2.569(4)

(71) TABLE-US-00004 TABLE 4 Bond Valence Sum (BVS)s for all the atoms in various NaCa.sub.2xBa.sub.xGeO.sub.4F compounds Ba mol % Atoms 0.00 0.01 0.015 0.02 0.025 0.035 0.04 0.045 Ge 3.67 3.63 3.71 3.68 3.66 3.72 3.67 3.61 M1 1.87 1.84 1.83 1.83 1.82 1.81 1.82 1.81 M2 1.91 1.90 1.90 1.89 1.88 1.86 1.86 1.84 F 1.27 1.26 1.24 1.23 1.20 1.22 1.22 1.20 O1 2.30 2.27 2.35 2.23 2.22 2.21 2.15 2.11 O2 2.13 2.11 2.16 2.12 2.07 1.99 2.01 1.94 O3 2.09 2.11 2.13 2.04 2.15 2.18 2.2 2.05

(72) The changing lattice parameter values with varied Sr.sup.2+ concentration are listed in Table 5. The plots of lattice parameter values against increasing Sr.sup.2+ concentration are shown if FIG. 5.

(73) TABLE-US-00005 TABLE 5 Lattice parameters of various Sr.sup.2+ substituted materials in the series NaCa.sub.2-xSr.sub.xGeO.sub.4F Sr mol % a b c V 0.00 5.3665(3) 7.3270(5) 12.6871(7) 498.72(8) 0.02 5.3728(3) 7.3283(6) 12.6880(6) 499.82(12) 0.03 5.3736(4) 7.3303(6) 12.6896(8) 499.85(10) 0.04 5.3731(4) 7.3321(7) 12.6926(8) 500.37(11) 0.05 5.3754(4) 7.3338(7) 12.6924(9) 500.12(9) 0.06 5.37659(3) 7.3345(6) 12.6931(9) 500.48(9) 0.07 5.3796(3) 7.3347(7) 12.6933(8) 500.81(10) 0.08 5.3808(3) 7.3351(6) 12.6981(9) 500.94(12) 0.09 5.3801(4) 7.3361(7) 12.6963(8) 501.12(9)

(74) Photoluminescence of the Undoped NaCa.sub.2GeO.sub.4F and NaCa.sub.2xBa.sub.xGeO.sub.4F (x=0.01, 0.015, 0.02, 0.025, 0.035, 0.04, 0.045)

(75) FIG. 6 shows the excitation and emission spectra of undoped NaCa.sub.2GeO.sub.4F when excited with light at a wavelength of 240 nm. The undoped oxyfluoride material shows peaks at 422 nm, 468 nm and 540 nm which can be assigned to a oxygen deficient GeO.sub.4 unit.

(76) Compounds in the NaCa.sub.2xBa.sub.xGeO.sub.4F family prepared under reducing condition are self-activating and show faint yellow luminescence under UV light. A comparison of the emission spectra for NaCa.sub.2GeO.sub.4F and NaCa.sub.1.985Ba.sub.0.015GeO.sub.4F at 254 nm excitation is shown in FIG. 7. NaCa.sub.1.985Ba.sub.0.015GeO.sub.4F exhibits a broad emission in 560-600 nm region. The emission spectra of NaCa.sub.1.985Ba.sub.0.015GeO.sub.4F at 365 nm excitation (FIG. 8) shows sharp peak at 464 nm and a broad peak in the 540 to 600 nm range. NaCa.sub.2xBa.sub.xGeO.sub.4F (x=0.01 to 0.045) can be used as yellow emitting phosphor when excited in the near UV region.

(77) Photoluminescent Properties of Ce.sup.3+ Doped Na.sub.1+xCa.sub.22xCe.sub.xGeO.sub.4F (x=0.01 to 0.07)

(78) Photoluminescence measurement for Ce.sup.3+ doped Na.sub.1+xCa.sub.22xCe.sub.xGeO.sub.4F (x=0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07) carried out at room temperature show blue-green luminescence when excited with longer wavelength UV light due to electronic transitions from the 5d to 4f (.sup.2F.sub.5/2 and .sup.2F.sub.7/2) states of Ce.sup.3+. The excitation spectra of Na.sub.1+xCa.sub.22xCe.sub.xGeO.sub.4F (x=0.01) reveals photoluminescent peaks at 415 nm, 430 and 465 nm at an emission wavelength of 555 nm (FIG. 9). This material behaves very similar to Sr.sub.22xCe.sub.xNa.sub.xAlO.sub.4F as was observed by Chen et. al. which shows a blue green emission when excited at 405 nm..sup.11

(79) As NaCa.sub.2GeO.sub.4F is chemically more stable than any of the Sr.sub.3xA.sub.xMO.sub.4F (A=Ca, Ba and M=Al, Ga) materials and furthermore, NaCa.sub.22xCe.sub.xGeO.sub.4F shows an excitation spectrum above 400 nm, this material has potential applications as a phosphor for In.sub.1xGa.sub.xN blue light emitting (390 nm to 470 nm) device. Compared to Ca.sub.2GeO.sub.4:Ce.sup.3+,Li.sup.+, this compound exhibits two emission peaks at 560 and 625 nm under 465 nm excitation (FIG. 10)..sup.29 The two distinct emission peaks are attributed to the fact that Ce.sup.3+ ions occupying two distinct M sites.

(80) The emission spectra of Ce.sup.3+ doped NaCa.sub.22xCe.sub.xGeO.sub.4F (x=0.01, 0.02, 0.03, 0.04, 0.05) at 465 nm and at 430 nm excitation shows peaks near 550 nm and 625 nm with the strongest photoluminescence measured for Na.sub.1.03Ca.sub.1.94Ce.sub.0.03GeO.sub.4F, indicating concentration quenching at Ce.sup.3+ concentrations above 0.03 mol % (FIG. 11).

(81) The CIE coordinate values for different rare earth dopants (Ce.sup.3+, Eu.sup.3+, Eu.sup.2+, Tb.sup.3+) and Ba.sup.2+ substituted NaCa.sub.2GeO.sub.4F samples are listed in Table 6 and the corresponding CIE values are plotted in a CIE diagram (FIG. 12).

(82) TABLE-US-00006 TABLE 6 the corresponding chromaticity Commission International de l'Eclairage (CIE) coordinates of the NaCa.sub.2GeO.sub.4F-based phosphors CIE values Luminescent materials x y Green 1. NaCa.sub.1.96Ce.sub.0.02GeO.sub.4F (Ex 365 nm) 0.3763 0.4231 2. NaCa.sub.1.97Ba.sub.0.01Eu.sub.0.01GeO.sub.4F (Ex 378 nm) 0.3565 0.4183 3. NaCa.sub.1.94Ba.sub.0.02Eu.sub.0.02GeO.sub.4F (Ex 365 nm) 0.3808 0.4269 4. NaCa.sub.1.93Tb.sub.0.07Ge.sub.0.93Al.sub.0.07O.sub.4F (Ex 254 nm) 0.2612 0.3991 Blue-green 5. NaCa.sub.1.95Ba.sub.0.01Ce.sub.0.02GeO.sub.4F (Ex 365 nm) 0.3211 0.3846 6. NaCa.sub.1.94Ba.sub.0.02Ce.sub.0.02GeO.sub.4F (Ex 365 nm) 0.2736 0.3004 7. NaCa.sub.1.92Tb.sub.0.03Ce.sub.0.02GeO.sub.4F (Ex 254 nm) 0.2306 0.2997 8. NaCa.sub.1.97Tb.sub.0.01Ce.sub.0.01GeO.sub.4F (Ex 254 nm) 0.2609 0.3506 Blue 9. NaCa.sub.2GeO.sub.4F (Ex 254 nm) 0.2021 0.2492 10. NaCa.sub.1.985Ba.sub.0.015GeO.sub.4F (Ex 254 nm) 0.2503 0.2741 11. NaCa.sub.1.98Ba.sub.0.02GeO.sub.4F (Ex 254 nm) 0.2088 0.2735 12. NaCa.sub.1.955Ba.sub.0.45GeO.sub.4F (Ex 254 nm) 0.2067 0.2561 White 13. NaCa.sub.2GeO.sub.4F (Ex 365 nm) 0.3075 0.3403 14. NaCa.sub.1.98Ba.sub.0.02GeO.sub.4F (Ex 365 nm) 0.3122 0.3435 15. NaCa.sub.1.97Ba.sub.0.01Eu.sub.0.01GeO.sub.4F (Ex 254 nm) 0.3035 0.2992 Red 16. NaCa.sub.1.94Ba.sub.0.02Eu.sub.0.02GeO.sub.4F (Ex 420 nm) 0.4753 0.5119 17. NaCa.sub.1.9Eu.sub.0.05GeO.sub.4F(Ex 260 nm) 0.5097 0.4657 18. NaCa.sub.1.8Mn.sub.0.1Ce.sub.0.04GeO.sub.4F (Ex 254 nm) 0.4917 0.4775

(83) Photoluminescent Characterization of Na.sub.1.05Ca.sub.1.9Eu.sub.0.05GeO.sub.4F

(84) The excitation and emission spectra of Na.sub.1.05Ca.sub.1.9Eu.sub.0.05GeO.sub.4F at 260 nm excitation is shown in FIG. 13. The bright red luminescence occurs due to the peaks at 540, 588, 610 nm originating from the .sup.5D.sub.0.fwdarw..sup.7F.sub.J (J=0, 1, 2, 3, 4) transitions along with relatively weak peaks at about 535 nm due to the .sup.5D.sub.1.fwdarw..sup.7F.sub.1 transition of Eu.sup.3+.

(85) Photoluminescent characterization of NaCa.sub.22xLi.sub.xTb.sub.xGeO.sub.4F, NaCa.sub.1.93Tb.sub.0.07Ge.sub.0.93Al.sub.0.07O.sub.4F, and Na.sub.1.07Ca.sub.1.86Tb.sub.0.07GeO.sub.4F

(86) We observed that NaLi.sub.0.05Ca.sub.1.9Tb.sub.0.03Ce.sub.0.02GeO.sub.4F exhibits a bright green emission under 254 nm UV light (FIG. 14). The emission spectra shows peaks at 383 nm and 413 nm due to 5d to .sup.2F.sub.5/2 and .sup.2F.sub.7/2 transitions of the Ce.sup.3+ ion and peaks at 435, 455, 484, 545, 584 and 625 nm due to the .sup.5D.sub.3.fwdarw..sup.7F.sub.4, .sup.5D.sub.3.fwdarw..sup.7F.sub.3, .sup.5D.sub.4.fwdarw..sup.7F.sub.6, .sup.5D.sub.4.fwdarw..sup.7F.sub.5, .sup.5D.sub.4.fwdarw..sup.7F.sub.4 and .sup.5D.sub.4.fwdarw..sup.7F.sub.3 transitions of the Tb.sup.3+ ions under 254 nm excitation. As the radius of Tb.sup.3+ ion (92.3 pm) is close to that of the Ca.sup.2+ ion (99 pm), the Tb.sup.3+ ions can easily substitute for the Ca.sup.2+ ion. Ge.sup.4+ was substituted with Al.sup.3+ to compare with Ca.sub.1.93Tb.sub.0.07Al.sub.0.07Ge.sub.0.93O.sub.4..sup.36 This led to an increase in intensity of the green luminescence. When Al.sup.3+ was substituted in the Tb.sup.3+ doped NaCa.sub.2GeO.sub.4F, e.g. NaCa.sub.1.93Tb.sub.0.07Ge.sub.0.93Al.sub.0.07O.sub.4F shows a very strong green luminescence compared to the one observed NaCa.sub.1.9Li.sub.0.05 Tb.sub.0.03Ce.sub.0.02GeO.sub.4F.sub.5 (FIG. 14). This material can be used as a suitable green emitting phosphor.

(87) Na.sub.1.07Ca.sub.1.86Tb.sub.0.07GeO.sub.4F shows green luminescence under UV light. The emission spectrum of Na.sub.1.07Ca.sub.1.86Tb.sub.0.07GeO.sub.4F at 270 nm excitation is plotted in FIG. 16.

(88) Photoluminescence of Mn.sup.2+ Substituted Na.sub.1.04Ca.sub.1.8Mn.sub.0.1Ce.sub.0.04GeO.sub.4F

(89) Mn.sup.2+ substituted Na.sub.1.04Ca.sub.1.8Mn.sub.0.1Ce.sub.0.04GeO.sub.4F gives a bright yellow luminescence under 220 nm and 365 nm UV light. This material can be used as a yellow emitting phosphor for CFLs and near-UV LEDs as combination of yellow and blue light gives cold white light.

(90) Mn.sup.2+ has a 3d.sup.5 electronic configuration and the optical absorption transitions are parity and spin forbidden and hence Mn.sup.2+ dd absorption transitions do not occur readily. Ce.sup.3+ acts as sensitizer and transfers energy to Mn.sup.2+ causing a bright yellow luminescence at 220 nm excitation. Peaks at 423 nm and 487 nm are due to Ce.sup.3+ 5d to .sup.7F.sub.3/2 and .sup.7F.sub.5/2 transitions and the .sup.4T.sub.1.fwdarw..sup.6A.sub.1 transition creates a peak at 534 nm for Na.sub.1.04Ca.sub.1.8Mn.sub.0.1Ce.sub.0.04GeO.sub.4F as shown in FIG. 19a. Excitation spectra at 365 nm and 318 nm are also shown (FIGS. 17b and 17c).

(91) Photoluminescence of Ce.sup.3+ Doped NaCa.sub.2xBa.sub.xGeO.sub.4F

(92) Ce.sup.3+ doped NaCa.sub.2xBa.sub.xGeO.sub.4F show yellowish green luminescence under 254 nm and blue-green luminescence under 365 nm wavelength UV light due to electronic transition from 5d to 4f (.sup.2F.sub.5/2 and .sup.2F.sub.7/2) making it a suitable phosphor for both near and far UV excitation (FIG. 18).

(93) When Ba.sup.2+ substituted materials are doped with Ce.sup.3+ broad emission peak in the yellow-green region is observed.

(94) Photoluminescence of Eu.sup.2+ Doped NaCa.sub.2xBa.sub.xGeO.sub.4F

(95) Emission spectra of Na.sub.1.01Ca.sub.1.97Ba.sub.0.01Eu.sub.0.01GeO.sub.4F synthesized under the flow of 95% Ar/5% H.sub.2 gas at 254 nm excitation is shown in FIG. 19. At 254 nm the excitation peaks appears at 425, 466, 480 nm due to the host lattice and at 535, 612 and 648 nm due to Eu.sup.3+ and at 555 nm due to 5d.sup.14f.sup.6.fwdarw.4f.sup.7 transition of Eu.sup.2+. As the characteristic line emission of Eu.sup.3+ are seen for excitation at 254 nm it is evident that both Eu.sup.2+ and Eu.sup.3+ are present in the system. For the emission wavelength of 610 nm the excitation band in the 360 to 380 nm range with maximum at 378 nm originating from O.sup.2.fwdarw.Eu.sup.3+ charge transfer band caused by electron transfer from 2p orbitals of O.sup.2 ion to 4f orbitals of Eu.sup.3+ ion, was observed (FIG. 20). Excitation spectra of Na.sub.1.02Ca.sub.1.94Ba.sub.0.02Eu.sub.0.02GeO.sub.4F shows a band from 390 nm to 445 nm with maxima at 420 nm due to the 4f.sup.7.fwdarw.4f.sup.65d.sup.1 allowed transition of Eu.sup.2+ ion (FIG. 21). The 4f electron of Eu.sup.2+ can be excited to the 5d energy level as the 5d level overlaps with lower energy 4f level. At 420 nm excitation peaks at 490 nm, 525 nm and 549 nm are seen originating from the transitions .sup.5D.sub.1.fwdarw..sup.7F.sub.2, .sup.5D.sub.0.fwdarw..sup.7F.sub.0, .sup.5D.sub.0.fwdarw..sup.7F.sub.1. A slight shift towards longer wavelength with increasing Eu.sup.2+/Eu.sup.3+ concentration has been observed. This Europium doped material can be used as a suitable phosphor for excitation by near UV or blue emitting In.sub.xGa.sub.1xN LEDs. At 365 nm excitation peaks appear at 464 nm and 480 nm due to the host lattice and broad emission in the range of 530 to 612 nm due to 5d.sup.14f.sup.6.fwdarw.4f.sup.7 transition of Eu.sup.2+.

(96) A comparison of emission spectra of Na.sub.1.01Ca.sub.1.97Ba.sub.0.01Eu.sub.0.01GeO.sub.4F at the excitation wavelengths of 365 nm, 378 nm and 412 nm is shown in FIG. 23. Broad emission bands from 500 to 620 nm range with sharp peaks at 468 and 483 nm are observed at 365 nm and 378 nm excitation and at 412 nm excitation peaks appear at 487 nm, 545 nm and broad peak from 557 nm to 620 nm.

CONCLUSION

(97) Structural and photoluminescent characterization of NaCa.sub.2GeO.sub.4F and a series of rare earth doped materials of the same compound show that NaCa.sub.2GeO.sub.4F is a stable new host lattice for UV phosphors when doped with rare earth. Certain materials can also be new candidates for host materials to be used as phosphor for blue light emitting diodes. Ba.sup.2+ substitution in the calcium site creates self-activating phosphor and the CIE values can be engineered by varying the concentration of the substituent atoms and rare earth elements. The Mn.sup.2+ activated material shows prominent yellow luminescence and this system need to be investigated in more detail.

(98) These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood the aspects of the various embodiments may be interchanged either in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in the appended claims.