Method for Producing a Ceramic Converter Element, Ceramic Converter Element, and Optoelectronic Component

Abstract

A method for producing a ceramic converter element is provided. The method includes providing a phosphor as a starting material, mixing the phosphor and at least one metal oxide powder to form a mixture, and processing the mixture to form a ceramic converter material in which the phosphor is embedded in a ceramic matrix. Further, an optoelectronic component with a ceramic converter element and a ceramic converter element are provided.

Claims

1. A method for producing a ceramic converter element, the method comprising: providing a phosphor as a starting material; mixing the phosphor and at least one metal oxide powder to form a mixture; and processing the mixture to form a ceramic converter material in which the phosphor is embedded in a ceramic matrix material.

2. The method according to claim 1, wherein the phosphor comprises a phosphor selected from the group consisting of doped garnets, oxide based phosphors, nitride based phosphors, oxynitride based phosphors and combinations thereof.

3. The method according to claim 1, wherein the phosphor comprises a doped garnet.

4. The method according to claim 3, wherein the doped garnet comprises YAG and the metal oxide powder comprises YAG and/or Al.sub.2O.sub.3 or wherein the doped garnet comprises LuAG and the metal oxide powder comprises LuAG and/or Al.sub.2O.sub.3.

5. The method according to claim 1, wherein the at least one metal oxide powder comprises a metal oxide powder selected from the group consisting of undoped garnets, oxides of rare earth elements, oxides of transition metals, oxides of alkaline elements, oxides of alkaline earth elements and combinations thereof.

6. The method according to claim 1, wherein the phosphor and the metal oxide powder are free of second phases and/or impurities.

7. The method according to claim 1, wherein the phosphor comprises a dopant that comprises a lanthanide.

8. The method according to claim 7, wherein the phosphor comprises Ce and/or Gd.

9. The method according to claim 1, wherein the phosphor comprises a grain size d50 where 0.5 md5040 m and d9045 m.

10. The method according to claim 1, wherein the phosphor comprises a quantum efficiency QE of at least 90%.

11. The method according to claim 1, wherein the mixing comprises milling.

12. The method according to claim 1, wherein the processing comprises adding at least one additive to the mixture to form a slurry, tape casting the slurry to form a green part, prefiring and/or debinding and sintering the green part to form the ceramic converter material.

13. The method according to claim 12, wherein the sintering is performed in a wet or dry hydrogen atmosphere or in a dry or wet hydrogen-nitrogen atmosphere.

14. The method according to claim 12, wherein the at least one additive is chosen from the group consisting of water, binders, de-foamers, dispersants, plasticizers, and mixtures thereof.

15. A ceramic converter element produced using the method according to claim 1.

16. An optoelectronic component comprising: an active layer sequence emitting electromagnetic radiation of a primary wavelength, and a ceramic converter element produced with the method according to claim 1, the ceramic converter element being applied in a beam path of the active layer sequence and configured to convert the primary wavelength at least partly into a secondary wavelength, wherein the ceramic converter element comprises a quantum efficiency of at least 90%.

17. An optoelectronic component comprising an active layer sequence emitting electromagnetic radiation of a primary wavelength, and a ceramic converter element applied in a beam path of the active layer sequence and converting the primary wavelength at least partly into a secondary wavelength, wherein the ceramic converter element comprises a quantum efficiency of at least 90%.

18. The optoelectronic component according to claim 17, wherein the ceramic converter element comprises a phosphor selected the group consisting from Ce and/or Gd doped YAG, Ce and Gd doped LuAG, and mixtures thereof.

19. The optoelectronic component according to claim 17, wherein the ceramic converter element comprises Ce and/or Gd doped YAG embedded in a matrix chosen from YAG and Al.sub.2O.sub.3 and combinations thereof.

20. The optoelectronic component according to claim 17, wherein the ceramic converter element comprises Ce and/or Gd doped LuAG embedded in a matrix chosen from LuAG and Al.sub.2O.sub.3 and combinations thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Further embodiments and examples are described in the following with respect to the figures and exemplary embodiments.

[0037] FIG. 1 shows a schematic cross-section of an optoelectronic component;

[0038] FIG. 2, which includes FIGS. 2a and 2b, shows SEM images of phosphors used in the method according to an exemplary embodiment;

[0039] FIG. 3, which includes FIGS. 3a, 3b and 3c, shows photographs of casted tapes;

[0040] FIG. 4 shows photographs of sintered platelets;

[0041] FIG. 5, which includes FIGS. 5a and 5b, shows transmission and reflection values;

[0042] FIG. 6, which includes FIGS. 6a-6e, shows SEM images of sintered materials;

[0043] FIG. 7, which includes FIGS. 7a and 7b, shows spectra of sintered materials;

[0044] FIG. 8, which includes FIGS. 8a and 8b, shows conversion lines of sintered materials;

[0045] FIG. 9 shows LPWo-B values;

[0046] FIG. 10 shows spectra of exemplary embodiments of converter elements and reference examples;

[0047] FIG. 11 shows the CQE of exemplary embodiments and reference examples; and

[0048] FIG. 12, which includes FIGS. 12a and 12b, shows absorption and conversion photon measurements of exemplary embodiments and reference examples.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[0049] FIG. 1 shows a schematic cross-section of an optoelectronic component. It comprises substrate 30 on which an active layer sequence 10 is applied. In the beam path of the active layer sequence 10 a ceramic converter element 20 is applied. Active layer sequence 10 and ceramic converter element 20 may be applied in a housing 40, wherein a volume casting 50 may be applied between the housing 40 and the active layer sequence 10. Further elements of the optoelectronic component, like, for example, electrical connections are not shown for the sake of clarity.

[0050] The ceramic converter element 20 may comprise, for example, a YAG:(Gd/Ce) phosphor in a YAG matrix, or a Al.sub.2O.sub.3 matrix.

[0051] The ceramic converter element 20 may be produced as follows.

[0052] As starter material a pre-synthesized YAG:Ce phosphor with a cubic crystal phase with no second phases, a Ce doping level of 0.05 at. % to 6 at. %, preferably 0.1 at. % to 4 at. %, a particle size d50 of 0.5 m to 40 m, preferably 1 m to 20 m, and d90 of 45 m, preferably 25 m respectively, which is highly active and sinterable is used. A further starter material is a YAG powder with a cubic crystal phase with no second phase and a purity of >99.5%, a Ce doping level of 0 at. % to 1 at. %, preferably 0 at. % to 0.02 at. %, a particle size d50 of 0.1 m to 10 m, preferably 0.1 m to 5 m and d9015 m, preferably 8 m respectively, which is highly active and sinterable. Alternatively, or in addition, an Al.sub.2O.sub.3 powder could be used as a matrix having an -Al.sub.2O.sub.3 crystal with no second phases and corresponding characteristics as the YAG powder could be used.

[0053] Table 1 shows an exemplary batch for tape casting comprising the phosphor (Y.sub.0.796Gd.sub.0.2Ce.sub.0.004).sub.3Al.sub.5O.sub.12 in a YAG matrix and the additives:

TABLE-US-00001 TABLE 1 Weight % Density Volume Volume Weight Weight Component** Solids (g/cm3) Percent (cm3) Percent (g) DI Water 0% 1.00 39.92% 14.04 23.32% 14 WB4101 35% 1.03 39.71% 13.96 23.95% 14.38 PL005 100% 1.03 0.68% 0.24 0.41% 0.248 DF002 100% 1.20 0.15% 0.05 0.11% 0.064 Y.sub.0.796 Gd.sub.0.2 100% 4.60 1.41% 0.49 3.79% 2.273 Ce.sub.0.004).sub.3Al.sub.5O.sub.12 YAG 100% 4.56 18.13% 6.38 48.42% 29.07

[0054] WB4101 is an acrylic binder, DF002 is a non-silicone de-foamer, PL005 is a high pH plasticizer.

[0055] When the additives are mixed to the mixture the batch is then cast, dried and cut or punched into the desired size and shape. A desired shape for a sintered ceramic converter element may comprise, for example, a size of 1 mm1 mm with a thickness of 70 m to 300 m. One corner of the converter element may or may not be cut out to provide room for a wire bond to the top surface of an LED chip depending on the chip design. The size can also be as small as 0.5 mm.sup.2 for smaller LED chips.

[0056] The green sheets or parts may be placed on an alumina plate which is then placed in an air atmosphere furnace and heated using a time-temperature cycle of for example: 25 C. to 400 C. for four hours, 400 C. to 1150 C. for four hours, holding at 1150 C. for a period of 0.5 to 2 hours, and cooling to 25 C. within 3 hours.

[0057] During such a thermal process the organic carbon-containing species may be removed, including the organic binders being used to hold the powders as well as the pore-forming additive materials, if any, together. The holding temperature of 1150 C. is high enough to allow the powder particles to neck together, giving the parts sufficient strength to be handled. The pore-forming additives may be burnt out, leaving voids that replicate their sizes and shapes, proportionally depending on sintering temperatures.

[0058] For example, pre-fired ceramic platelets are transferred onto a molybdenum plate and are sintered, for example in a wet hydrogen atmosphere at 1500 to 1825 C. for a period of 1 minute to 2 hours at the peak temperature. Alternatively a hydrogen-nitrogen atmosphere could be chosen either in dry or wet conditions.

[0059] During the hydrogen sintering, the platelets shrink as the ceramic powders sinter and the porosity is removed. If the initial powder particle sizes and the mixing and milling conditions are performed properly and no pore-forming additives are added to the batch, the matrix porosity will be reduced at elevated sintering temperatures to a level that the final converter elements exhibit a high degree of transparency and translucency.

[0060] According to example 1 a batch of the YAG:(Gd/Ce) phosphor (P) with a Gd/Ce ratio of 0/100, and a content of Ce of about 2.2 at. % replacing Yin the YAG crystal is introduced into undoped YAG matrix (M1) with a content of about 11.5 vol %. After milling, adding the pore-forming additives if necessary, casting, drying and punching in the desired part size, the parts are heated and after the thermal process sintered at different temperatures from 1680 C. to 1760 C. QE of the thus obtained samples (PM1) was measured using a laser system.

[0061] According to example 2, a batch of YAG:(Gd/Ce) phosphor (P) with a Gd/Ce ratio of 0/100, a Ce content of about 2.2 at. % replacing Y in YAG was introduced into undoped Al.sub.2O.sub.3 matrix (M2) with a content of about 11.5 vol %. After the process as described above with respect to example 1 and sintered at different temperatures from 1620 C. to 1760 C., the QE values of the thus obtained samples (PM2) were measured.

[0062] Whereas PM1 shows a QE of 98% and PM2 shows a QE of 92%, a reference example R2, a single phase YAG:Ce standard converter shows a QE of 91% and reference example R1, a second phase converter YAG:Ce in Al.sub.2O.sub.3 matrix produced by a mixed oxide process, shows a QE of 90%.

[0063] According to example 3 a YAG:(Gd/Ce) phosphor (P2) with a Gd/Ce ratio of 0/100 and a Ce content of about 3 at. % replacing Y in YAG is introduced into an undoped YAG matrix (M1) with a content of about 70.2 vol %. Following the process as described above but pre-milling the phosphor and sintering at different temperatures from 1620 C. to 1760 C. in wet forming gas N2-H2 (about 3.6 vol %) CQE of the thus obtained samples P2M1-N2-H2 were measured in Oslon Black Flat (OBF) package in integrating sphere. The typical CQE data are listed in Table 2. For comparison a standard product using phosphor powder made by co-precipitated processes is also included in Table 2 as Reference Example at similar Cx values. The Reference Example is a single phase YAG:Ce standard converter with 15 at. % Gd and 0.2 at. % Ce doped YAG.

[0064] According to example 4 a batch of YAG:(Gd/Ce) phosphor (P2) with a Gd/Ce ratio of 0/100, and a content of Ce of about 3 at. % replacing Yin YAG was introduced into undoped YAG matrix (M1) with a content of 7.2 vol %. Following the process as described above but pre-milling the phosphor and sintering at different temperatures from 1620 C. to 1760 C. in wet H2, CQE values of the thus obtained samples P2M1-H2 were measured using an OBF package in sphere. The typical CQE data are listed in Table 2. Further listed in Table 2 are the values of Lm/Wo-b being calculated using the lumens (Lm) from the emission spectra divided by the blue chip optical power (Wo-b) and LER which is calculated using lumens (Lm) integrated from the emission spectra divided by its emission spectra power integrated (Wvis).

TABLE-US-00002 TABLE 2 Sample CQE (%) LER (Lm/Wvis) Lm/Wo-b P2M1-N2-H2 63.1% 301.5 185.3 P2M1-N2-H2 63.6% 303.8 186.9 P2M1-N2-H2 63.1% 305 187.3 P2M1-N2-H2 64.8% 295.5 185.8 P2M1-N2-H2 64.3% 293.5 184.6 P2M1-N2-H2 62.8% 304.5 186.2 P2M1-N2-H2 63.6% 303.8 187.7 P2M1-N2-H2 63.3% 305.8 187.8 P2M1-H2 62.7% 271.7 173.8 P2M1-H2 62.4% 280.3 176.1 P2M1-H2 62.9% 275.1 175.4 P2M1-H2 63.0% 276 175.8 P2M1-H2 63.2% 281.4 178.2 P2M1-H2 62.9% 282.5 178.4 P2M1-H2 63.2% 283.7 179.3 P2M1-H2 63.7% 279.5 178.3 Reference Example 2 62.4% 263.7 165.6 Reference Example 2 61.9% 267.7 166.7 Reference Example 2 62.6% 268.3 167.9 Reference Example 2 62.8% 267.1 168.0 Reference Example 2 62.6% 266.5 167.3 Reference Example 2 63.0% 264.8 167.2 Reference Example 2 62.2% 269.1 167.7 Reference Example 2 62.1% 266.2 167.0

[0065] In the following P designates a YAG:Ce powder with a content of Ce of about 3 at. % and a grain size d50 of about 17 m. This phosphor has large grains, is well-crystallized and pre-synthesized for having a high QE. P1 designates the phosphor being cast and sintered. PM1 designates the phosphor in a YAG matrix, the phosphor having a content of 11.5 vol %. PM2 designates the phosphor in an Al.sub.2O.sub.3 matrix with a phosphor having a content of 11.5 vol %. M1 designates the matrix YAG being cast and sintered. M2 designates the matrix Al.sub.2O.sub.3 being cast and sintered. Further, P2M1-H2 designates a YAG:Ce phosphor with a content of Ce of about 3 at. % and a d50 of about 7 m in a YAG matrix, the phosphor having a content of 7.2 vol % and being sintered in a wet hydrogen atmosphere. Accordingly, P2M1-N2-H2 designates a YAG:Ce phosphor with a content of Ce of about 3 at. % and a d50 of about 7 m in a YAG matrix, the phosphor having a content of 7.2 vol % and being sintered in a wet hydrogen nitrogen atmosphere.

[0066] FIG. 2 shows SEM images of the phosphor P being not surface treated and having a QE of about 99% and a d50 of about 17 m. The color point of this phosphor is suitable, for example, for headlamp color boxes. The particle diameter d50 is not ideal for ceramic processing in the present matrix method. FIG. 2b is an amplification of FIG. 2a.

[0067] The slurry rheology of the phosphor P is difficult to control but still able to be tape cast even if the standard binder level is too high for the large grains, and the colloidal dispersion is difficult. The sample PM2 worked better for tape-casting. The pure phosphor samples P1, especially in a size of 25 mm25 mm and thickness of 120 m often warped, which is attributed to particle settling during the casting process, but the samples PM1 and PM2 show a lower warpage. The tape-cast samples P1 and PM2 are shown in FIG. 3a (P1), 3b (P1) and 3c (PM2) by photographs.

[0068] FIG. 4 shows a photograph of sintered parts of the samples PM1, PM2, P1, M1 and M2. It can be seen that the YAG samples PM1 and M1 exhibit a higher transparency than the Al.sub.2O.sub.3 samples PM2 and M2 respectively.

[0069] FIG. 5a shows the transmission values T (%) in dependence of the wavelength (nm) of sintered samples PM1, PM2, P1, M1 and M2, FIG. 5b shows the reflection values Ref (%) in dependence of the wavelength (nm) of the same samples in wavelength ranges of 300 to 800 nm.

[0070] Table 3 summarizes the values for absorption ABS and transmission T of samples P, P1, PM1, PM2, M1 and M2, all of them being sintered at 1720 C., and reference samples R1 (a second phase sample produced by conventional second phase approach i.e. mixed oxide process with extra Al.sub.2O.sub.3 for matrix) and R2 (single phase sample as explained in context with Table 2), QE and absorption measured by laser-sphere.

TABLE-US-00003 TABLE 3 % T Description ABS (%) QE(%) (700 nm) P 53 99 P1 81 88 29% PM1 70 98 54% PM2 71 92 48% M1 5 38 84% M2 5 2 60% Reference 1 (second phase sample) 59 90 75% Reference 2 (single phase sample) 50 91 84%

[0071] FIGS. 6a to 6e show SEM images of the microstructures of the samples PM1 (FIG. 6a), PM2 (FIG. 6b), P1 (FIG. 6c), M1 (FIG. 6d), and M2 (FIG. 6e), all of them being sintered at 1720 C. In FIG. 6a a beginning of exaggerated grain growth (EGG) with some BaAl.sub.2O.sub.4 phases can be observed. Also in the sample PM2 large grains of alumina with pores in grains and BaAl.sub.2O.sub.4 can be observed at the surface (FIG. 6b, left) and in the fracture (FIG. 6b, right). The sample P1 is poorly sintered and has a large grain size with BaAl.sub.2O.sub.4 and CeO.sub.2 phases on its surface (FIG. 6c, right) and throughout the bulk (fracture in FIG. 6c, left). The matrix M1 has a smaller grain size, as can be seen in FIG. 6d, and the matrix M2 shown in FIG. 6e has an exaggerated grain growth and pores inside the grains.

[0072] FIGS. 7a and 7b show spectra (FIG. 7a shows the intensity I (mw/nm) in dependence of the wavelength (nm) and FIG. 7b shows the normalized intensity I.sub.norm in dependence of the wavelength (nm)) of the matrix M1, M2, the samples PM1, PM2 and the phosphor P1 and P in comparison to a blue LED. The measurements were performed with a 1 mm1 mm0.1 mm ceramic phosphor element on an LED in sphere. It can be seen that the intensity of PM1 is higher than the intensity of PM2 which higher than the intensity of P1. P1 shows a very low blue transmission and some Ce contamination can be observed in the pure matrix M1. Further a fairly high blue transmission can be seen in sample M1, a slightly less blue transmission in sample M2. No spectral shift can be recognized in comparison to the blue LED. Further the red shift being a Ce re-absorption is greatest in sample P1 having a high scattering due to a poor sintering as can be seen in FIG. 7b.

[0073] It could be shown that the sample P, thus the YAG:Ce powder, has a very high QE of 99% being measured in laser sphere (Lab 30). But the ceramic made with P alone did not maintain its high QE value but showed a reduced value of 88%, possibly due to the poor sintering behavior and/or the appearance of BaAl.sub.2O.sub.4 and CeO.sub.2 phases. The sample PM1 shows high QE of 98% and high lumens on an LED. Sample PM2 had a QE of 92% and decreased lumens, but still a higher QE than conventional YAG:Ce in Al.sub.2O.sub.3 through oxide approach, i.e., YAG:Ce phosphor formed from mixture of Y.sub.2O.sub.3, Al.sub.2O.sub.3, CeO.sub.2 etc. and standard products single phase ceramic converter (90% and 91%). The transmission of M1 is higher than in M2 and thus the sample PM1 shows a higher transmission than the sample PM2. The undoped YAG ceramic M1 exhibited weak emission being attributed to a Ce contamination from the slurry processing or from the sintering furnace.

[0074] In the following the effect of atmosphere on the sintering of the materials is examined. The phosphor here is a YAG phosphor doped with Ce (3%) with a high QE and a d50 of about 7 m with agglomerates and designated P2. The matrix is a YAG matrix and the phosphor has a content in the matrix of 7.2 vol %. The sintering takes place in two atmospheres. The standard being 5 lpm (liter per minute) wet H.sub.2 (0 C. dew point). The thus sintered samples are designated as P2M1-H2. The other atmosphere is an 8 lpm N.sub.2, with <0.3 lpm wet H.sub.2 (0 C. dew point) with an amount of about 1.5 to 3% H.sub.2. These samples are designated as P2M1-N2-H2.

[0075] FIG. 8 show conversion lines (the coordinate Cy in dependence of coordinate Cx) of reference samples R1, R2 and the samples P2M1-N2-H2 and P2M1-H2. FIG. 8a shows the results of the measurement on OT, an in-house designed pin-hole sphere-measurement system, FIG. 8b shows the results of the measurement on dry LEDan in-house designed system but with ceramic converter placed on LED chip in a sphere system. The sintered platelets have conversion lines close to the Reference examples with slight green shifts.

[0076] FIG. 9 shows that the samples P2M1-H2 and P2M1-N2-H2 have a higher LPWo-b, which is defined and calculated using lumens of emission spectra divided by the blue chip optical power (Wo-b), than reference sample R1 at similar color points Cx.

[0077] FIG. 10 shows spectra recorded on LEDs (without glue) in sphere. The samples P2M1-H2 and P2M1-N2-H2 are measured and their intensity I in dependence of the wavelength (nm) is compared to a photopic curve (PC), being the CIE standard curve used in the CIE 1931 color space. The luminous flux (or power) a light source is defined by the photopic luminosity function. It can be shown that there is only a minor shift of spectra for the samples sintered in N2-H2 vs H2. The photopic curve provides a reference only.

[0078] The data analysis of samples P2M1-H2 and P2M1-N2-H2 shows that the CQE of the P2M1-N2-H2 is 1% higher than Reference example R2 and 0.7% higher than in the sample P2M1-H2.

[0079] This is also shown in FIG. 11 where the CQE in dependence of Cx is the highest for sample P2M1-N2-H2 being 1% higher than Reference example R2 and the CQE is higher for forming gas than for a standard wet hydrogen sintering.

[0080] Generally it can be shown that CQE is statistically higher for forming gas than in wet hydrogen alone and also for materials having a YAG matrix than Reference example R2.

[0081] FIG. 12 shows measurements of the blue absorption (blue abs) and the conversion photons (cony) in dependence of Cx of different samples sintered in H2 and in N2-H2 as well as of reference sample R2 (FIG. 12a). It can be shown that the luminous efficacy of radiation (LER) increases linearly with Cx due to higher emission to blue transmission ratio (FIG. 12b). The matrix materials sintered in N2-H2 show more blue absorption and more conversion photons leading to a lower percentage of pump-through and higher percentage of conversion. The higher CQE being observed is not caused by a color shift.

[0082] The scope of protection of the invention is not limited to the examples given hereinabove. The invention is embodied in each novel characteristic and each combination of characteristics, which particularly includes every combination of any features which are stated in the claims, even if this feature or this combination of features is not explicitly stated in the claims or in the examples.