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COMPOSITION AND ITS USE
CROSS-REFERENCE TO RELATED
This is a continuation of copending international application PCT/DE97/02139, filed Sep. 22, 1997, which designated the United States.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a wavelength-converting casting composition based on a transparent epoxy casting resin which is mixed with a luminous substance, for an electroluminescent component having a body that emits ultraviolet, blue or green light.
2. Description of the Related Art
A component of that type has become known, for instance, from German published, non-prosecuted patent application DE 38 04 293. The reference describes an arrangement with an electroluminescent diode or laser diode, in which the emissions spectrum emitted by the diode is shifted toward longer wavelengths, by means of a plastic element mixed with a fluorescing, light-converting, organic colorant. The light emitted by the arrangement as a result has a different color from what the light emitting diode emitted. Depending on the type of colorant added to the plastic, it is possible to produce LED arrays that light up in different colors with one and the same type of light-emitting diode (LED).
In many potential applications for LEDs, such as in display elements in motor vehicle dashboards, illumination in aircraft and automobiles, and in LED displays capable of showing full color, there is an increasing demand for LED arrays with which mixed color light and in particular white light can be generated.
However, the prior art casting compositions of the type referred to at the outset with organic luminous substances exhibit a shift in the color location, that is, the color of the light emitted by the electroluminescent component, under temperature and temperature/humidity stresses.
Japanese patent disclosure JP-07 176 794-A describes a white-light-emitting planar light source, in which two diodes that emit blue light are disposed on one face end of a transparent plate and emit light into the transparent plate. The transparent plate is coated on one of the two opposed main sides with a fluorescing substance that emits light when it is excited with the blue light of the diodes. The light emitted by the fluorescing substance has a different wavelength from the blue light emitted by the diodes. In this known component, it is especially difficult to apply the fluorescing substance in such a way that the light source emits homogeneous white light. Moreover, replicability and mass production presents major problems, because even slight fluctuations in the layer thickness of the fluorescing layer, for instance from irregularities of the surface of the transparent plate, cause a change in the white of the light emitted.
SUMMARY OF THE INVENTION
It is accordingly an object of the invention to provide a wavelength-converting casting mass, which overcomes the above-mentioned disadvantages of the prior art devices and methods of this general type and with which electroluminescent components can be produced that emit homoge
neous mixed-colored light, and which enables mass production at reasonable engineering effort and expense and with maximally replicable component characteristics. The emitted light should be color-stable even under temperature and 5 temperature/humidity stresses. It is a further object to specify a use for the casting mass and a method for producing the composition.
With the foregoing and other objects in view there is provided, in accordance with the invention, a wavelength1° converting casting composition, for converting a wavelength of ultraviolet, blue or green light emitted by an electroluminescent component, comprising: a transparent epoxy casting resin; s an inorganic luminous substance pigment powder dispersed in the transparent epoxy resin, the pigment powder comprising luminous substance pigments from a phosphorus group having the general formula A3B5X12:M;
20 the luminous substance pigments having grain sizes = 20 fim and a mean grain diameter d50 = 5 fim. In accordance with an added feature of the invention, the mean grain diameter d50 of the luminous substance pigments is between one and two micrometers. 25 Inorganic/mineral luminous substances are extremely stable with regard to temperature and temperature/humidity stresses.
In accordance with an additional feature of the invention, the composition includes the following parts: 30 a) epoxy casting resin = 60% by weight;
b) luminous substance pigments>0 and =25% by weight;
c) thixotropic agent>0 and = 10% by weight;
d) mineral diffusor>0 and = 10% by weight; 35 e) processing adjuvant>0 and =3% by weight;
f) hydrophobic agent>0 and =3% by weight; and
g) adhesion promoters>0 and =2% by weight.
Suitable epoxy casting resins are described for instance in
German published, non-prosecuted patent application 26 42
40 465 (pp. 4-9, in particular examples 1-4), and in European patent disclosure EP 0 039 017 (pp. 2-5, in particular examples 1-8). The disclosures of those documents are hereby expressly incorporated by reference.
Pyrogenic silicic acid is for instance used as the thixo
45 tropic agent. The thixotropic agent is used to thicken the epoxy casting resin, so as to reduce the sedimentation of the luminous substance pigment powder. The flow and wetting properties are also adjusted for processing the casting resin. CaF2 is preferably used as a mineral diffusor for optimiz
50 ing the luminous pattern of the component.
Glycol ether is for instance suitable as a processing adjuvant. It improves the compatibility between the epoxy casting resin and the luminous substance pigment powder and is thus used to stabilize the dispersion of luminous
55 substance pigment powder and epoxy casting resin. To that end, surface modifiers based on silicone can also be employed.
The hydrophobic agent, such as liquid silicone wax, is also used to modify the pigment surface; in particular, the
60 compatibility and wettability of the inorganic pigment surface is improved with the organic resin.
The adhesion promoter, such as functional alkoxysiloxane, improves the adhesion between the pigments and the epoxy resin in the cured state of the casting
65 composition. As a result it is attained that the boundary face between the epoxy resin and the pigments will not rupture, for instance in response to temperature fluctuations. Gaps
between the epoxy resin and the pigments would cause light losses in the component.
The epoxy casting resin, preferably with a reactive triple oxiran ring, preferably includes a monofunctional and/or multifunctional epoxy casting resin system (=80% by 5 weight, such as bisphenol-A-diglycidyl ether), a reactive diluent (=10% by weight, such as aromatic monoglycidyl ether), a multifunctional alcohol (=5% by weight), a degassing agent based on silicone ( = 1% by weight), and a decolorizing component to adjust the color number (=1% by weight).
In accordance with another feature of the invention, the luminous substance pigments are substantially spherical particles or flakelike particles. The tendency to clumping of such pigments is advantageously very slight. The H20 content is below 2%. 15
In the production and processing of epoxy casting resin components with inorganic luminous substance pigment powders, in general not only wetting but also sedimentation problems occur. Especially luminous substance pigment powders with d50 = 5 fim have a strong tendency to clump- 20 ing. In the last-named composition of the casting composition, the luminous substance pigments, with the above-indicated particle size, can advantageously be substantially free of clumps and can be dispersed homogeneously in the epoxy casting resin. This dispersion is stable 2s even under long-term storage of the casting composition. Essentially no problems of wetting and/or sedimentation occur.
In accordance with a further feature of the invention, the luminous substance pigments are particles of Ce-doped 30 garnets, such as, particularly, YAG:Ce particles. An advantageous dopant concentration is 1%, for example, and an advantageous luminous substance concentration is 12%, for example. The preferred high-purity luminous substance pigment powder also advantageously has an iron content of = 5 35 ppm. A high iron content leads to high light losses in the component. The luminous substance pigment powder is highly abrasive. The iron content in the casting composition can therefore rise considerably during production. Iron contents in the casting composition<20 ppm are advantageous. 40
The inorganic luminous substance YAG:Ce has the particular advantage, among others, that this involves insoluble color pigments with an index of refraction of approximately 1.84. As a result, along with the wavelength conversion, dispersion and scattering effects occur that lead to good 45 mixing of blue diode emissions with yellow converter radiation.
It is also especially advantageous that the luminous substance concentration in the epoxy resin when inorganic luminous substance pigments are used is not limited by the 50 solubility, as is the case for organic colorants.
For further reduction of clumping, the luminous substance pigments may advantageously be provided with a silicone coating.
With the above and other objects in view there is also 55 provided, in accordance with the invention, a method of producing a wavelength-converting casting composition, for converting a wavelength of ultraviolet, blue or green light emitted by an electroluminescent component, the method which comprises: 60 providing a base of transparent epoxy casting resin; providing a luminous substance pigment powder of luminous substance pigments from a phosphorus group having the general formula A3B5X12:M; tempering the luminous substance pigment powder at a 65 temperature of =200° C. and subsequently mixing the tempered pigment powder with the epoxy casting resin.
Tempering is preferably effected for approximately ten hours. As a result, again the tendency to clumping can be reduced.
As an alternative or in addition for this purpose, the luminous substance pigment powder, before being mixed with the epoxy casting resin, can be slurried in a higherboiling alcohol and subsequently dried. A further possibility for reducing clumping is to add a hydrophobic silicone wax to the luminous substance pigment powder before the powder is mixed with the epoxy casting resin. Surface stabilization of the phosphors by heating the pigments in the presence of glycol ethers, for instance for 16 hours at T>60° C, is especially advantageous.
To avoid problematic contamination upon dispersal of the luminous substance pigments, caused by abrasion, reaction vessels, agitators and dispersing devices as well as rolling mechanisms of glass, corundum, carbide and nitride materials as well as especially hardened types of steel are used. Clump-free luminous substance dispersions are also obtained by ultrasonic methods or by the use of screens and glass ceramic frits.
An especially preferred inorganic luminous substance for producing optoelectronic components that light up white is the phosphorous YAG:Ce (Y3Al5012:Ce3+). This phosphorous can be especially simply mixed with transparent epoxy casting resins conventionally used in LED technology. Also conceivable as luminous substances are other garnets, doped with rare earths, such as Y3Ga5012:Ce3+, Y(Al,Ga) 5012:Ce3+, and Y(Al,Ga)5012:Tb3+.
To generate mixed-colored light, the thiogallates doped with rare earths are moreover especially suitable, examples being CaGa2S4:Ce3+ and SrGa2S5:Ce3+. Once again, the use of aluminates doped with rare earths, such as YA103:Ce3+, YGa03:Ce3+, Y(Al,Ga)03:Ce3+, and orthosilicates doped with rare earths, M2Si05:Ce3+ (M:Sc,Y,Sc), such as Y2Si05:Ce3+ is conceivable. In all the yttrium compounds, the yttrium can in principle also be replaced with scandium or lanthanum.
Therefore, in the phosphorous group A3B5X12:M, the variables may stand for the following exemplary elements: A=Y, Ca, Sr; B =A1, Ga, Si; X=0, S; and M=Ce3+, Tb3+.
Preferably, the casting composition according to the invention is used in a radiation-emitting semiconductor body, in particular with an active semiconductor layer or semiconductor layer sequence of GaJn^JST or Ga-^^JST, which in operation emits an electromagnetic radiation of the ultraviolet, blue and/or green spectral range. The luminous substance particles in the casting composition convert some of the radiation originating in this spectral range into radiation with a longer wavelength, in such a way that the semiconductor component emits mixed radiation, and in particular mixed-colored light comprising this radiation as well as radiation from the ultraviolet, blue and/or green spectral range. This means for instance that the luminous substance particles spectrally selectively absorb some of the radiation emitted by the semiconductor body and emit in the longer-wave range. Preferably, the radiation emitted by the semiconductor body has a relative maximum intensity at a wavelength lambda X=520 nm, and the wavelength range spectrally selectively absorbed by the luminous substance particles is outside this maximum intensity.
It is also advantageously possible for a plurality of different kinds of luminous substance particles, which emit at different wavelengths, to be dispersed in the casting composition. This is preferably achieved by means of different doping in different host lattices. This advantageously makes it possible to generate manifold color mixtures and
color temperatures of the light emitted by the component. This is especially of interest for LEDs capable of emitting full color.
In a preferred use of the casting composition of the invention, a radiation-emitting semiconductor body (such as 5 an LED chip) is at least partly enclosed by the casting composition. The casting composition is preferably simultaneously used as a component envelope (housing). The advantage of a semiconductor component in accordance with this embodiment is essentially that conventional production lines used to make conventional LEDs (such as radial LEDs) can be used to produce it. For the component envelope, instead of the transparent plastic used for this purpose in conventional LEDs, the casting composition can simply be employed.
With the casting composition of the invention, it is 15 possible in a simple way, with a single colored light source, particularly an LED with a single semiconductor body that emits blue light, to create mixed-colored and in particular white light. For instance to generate white light with a semiconductor body that emits blue light, some of the 20 radiation emitted by the semiconductor body is converted out of the blue spectral range into the yellow spectral range, which is complementary in color to blue, by means of inorganic luminous substance particles.
The color temperature or color location of the white light 2s can be varied by a suitable choice of the luminous substance, its particle size, and its concentration. In addition, luminous substance mixtures can also be employed, and as a result advantageously the desired tonality of the color of the emitted light can be adjusted very precisely. 30
Especially preferably, the casting composition is used in a radiation-emitting semiconductor body in which the emitted radiation spectrum has a maximum intensity at a wavelength between 420 nm and 460 nm, and in particular at 430 nm (examples being semiconductor bodies based on Gslxa11_ 35 xN) or 450 nm (such as semiconductor bodies based on GaJn^JST). With such a semiconductor component, nearly all the colors and mixed colors in the CIE chromaticity diagram can advantageously be generated.
Instead of the radiation-emitting semiconductor body of 40 electroluminescing semiconductor material, however, some other electroluminescing material may be used, such as polymer material.
With the objects of the invention is view there is further provided, in accordance with the invention, a light-emitting 45 semiconductor component, comprising:
a semiconductor body formed of a semiconductor layer sequence and being capable, during an operation of the semiconductor component, of emitting electromagnetic radiation in at least one of an ultraviolet, blue, and 50 green spectral range; a wavelength-converting casting composition disposed in a vicinity of the semiconductor body, the casting composition being formed of a transparent epoxy casting resin and an inorganic luminous substance pigment 55 powder dispersed in the transparent epoxy resin, the pigment powder comprising luminous substance pigments from a phosphorus group having the general formula A3B5X12:M and having grain sizes = 20 fim and a mean grain diameter d50 = 5 fim; 60 the luminous substance pigments converting a portion of the radiation originating from the ultraviolet, blue and green spectral range into radiation of a higher wavelength, such that the semiconductor component emits mixed radiation including the higher-wavelength 65 radiation and radiation from at least one of the ultraviolet, blue and green spectral range.
In other words, the casting composition is especially suitable for a light-emitting semiconductor component (for instance an LED), in which the electroluminescing semiconductor body is disposed in a recess of a prefabricated housing, optionally already provided with a leadframe, and the recess is provided with the casting composition. This kind of semiconductor component can be produced in great numbers on conventional production lines. All that is needed, after mounting of the semiconductor body in the housing, is to fill the recess with the casting composition.
A semiconductor component that emits white light can be produced with the casting composition according to the invention advantageously by choosing the luminous substance in such a way that a blue radiation emitted by the semiconductor body is converted into complementary wavelength ranges, in particular blue and yellow, or additive color triads, such as blue, green and red. The yellow or green and red light is generated via the luminous substances. The color tonality (color location in the CIE chromaticity diagram) of the white light thus produced can then be varied by means of a suitable choice of the luminous substance or luminous substances in terms of their mixture and concentration.
To improve the mixing of the radiation emitted by an electroluminescing semiconductor body with the radiation converted by the luminous substance and thus to improve the homogeneity of color of the light emitted by the component, in an advantageous feature of the casting composition according to the invention a blue-luminescing colorant, which attenuates a so-called directional characteristic of the radiation emitted by the semiconductor body. The term "directional characteristic" is understood to mean that the radiation emitted by the semiconductor body has a preferential emission direction.
A semiconductor component according to the invention that emits white light, with an electroluminescing semiconductor body emitting blue light, can be especially preferably achieved by admixing the inorganic luminous substance YAG:Ce (Y3Al5012:Ce3+) with the epoxy resin used for the casting composition. Some of the blue radiation emitted by the semiconductor body is shifted by the inorganic luminous substance (Y3Al5012:Ce3+) into the yellow spectral range and thus into a wavelength range that is complementary in color to the color blue. The color tonality (color location in the CIE chromaticity diagram) of the white light can then be varied by means of a suitable choice of the colorant concentration.
In addition, light-scattering particles, so-called diffusers, can be added to the casting composition. As a result, the color impression and the emission characteristics of the semiconductor component can advantageously be still further optimized.
With the casting composition of the invention, advantageously an ultraviolet radiation emitted by an electroluminescing semiconductor body along with the visible radiation can advantageously be converted into visible light. This markedly increases the brightness of the light emitted by the semiconductor body.
A particular advantage of semiconductor components according to the invention that emit white light, and in which YAG:Ce is used in particular as the luminescenceconverting colorant, is that this luminous substance on excitation with blue light causes a spectral shift of approximately 100 nm between absorption and emission. This leads to a substantial reduction and reabsorption of the light emitted by the luminous substance and thus to a higher light yield. Moreover, YAG:Ce advantageously has high thermal and photochemical (such as UV) stability (substantially
higher than organic luminous substances) so that even white-emitting diodes for outdoor use and/or high temperature ranges can be produced.
YAG:Ce has by now proved itself to be the best-suitable luminous substance in terms of reabsorption, light yield, 5 thermal and photochemical stability, and processability. However, the use of other Ce-doped phosphors, in particular Ce-doped types of garnet, is also conceivable.
The wavelength conversion of the primary radiation is determined by the crystal field cleavage of the active tran- 10 sition metal centers in the host lattice. By substituting Gd and/or Lu for Y, or Ga for Al in the Y3A15012 garnet lattice, the emission wavelengths can be shifted in various ways, and this can also be done by the type of doping. By substituting Eu3+ and/or Cr3+ for Ce3+ centers, correspond- 15 ing shifts can be brought about. Corresponding dopings with Nd3+ and Er3+ even make it possible, because of the greater ion radii and thus reduced crystal field cleavage, to make components that emit infrared (IR) light. Other features which are considered as characteristic for the invention are 20 set forth in the appended claims.
Although the invention is illustrated and described herein as embodied in a wavelength-converting casting composition, its use, and method for its production, it is nevertheless not intended to be limited to the details shown, 25 since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the 30 invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic sectional view of a first semiconductor component with a casting composition according to the invention;
FIG. 2 is a schematic sectional view of a second semi conductor component with a casting composition according to the invention;
FIG. 3 is a schematic sectional view of a third semiconductor component with a casting composition according to 45 the invention;
FIG. 4 is a schematic sectional view of a fourth semiconductor component with a casting composition according to the invention;
FIG. 5 is a schematic sectional view of a fifth semicon- 50 ductor component with a casting composition according to the invention;
FIG. 6 is a graph of an emission spectrum of a semiconductor body that emits blue light, with a layer sequence on the basis of GaN;
FIG. 7 is a graph of the emissions spectra of two semiconductor components with a casting composition according to the invention, which emit white light; and
FIG. 8 is a graph of the emissions spectra of further 60 semiconductor components that emit white light.
DESCRIPTION OF THE PREFERRED
Reference is now had to the figures of the drawing in 65 which elements that are identical or that function identically are identified by the same reference numerals throughout. In
the light-emitting semiconductor component of FIG. 1, the semiconductor body 1 is secured by its back-side contact 11 to a first electrical terminal 2 by means of an electrically conductive joining means such as a metal solder or an adhesive. The front-side contact 12 is joined to a second electrical terminal 3 by means of a bond wire 14.
The free surfaces of the semiconductor body 1 and portions of the electrical terminals 2 and 3 are enclosed directly by a hardened, wavelength-converting casting or potting composition 5. The casting composition preferably has the following: epoxy casting resin 80 to 90% by weight, luminous substance pigments (YAG:Ce) = 15% by weight, diethylene glycol monomethyl ether = 2% by weight, Tegopren 6875-45^2% by weight, Aerosil 200^5% by weight.
The exemplary embodiment of a semiconductor component according to the invention shown in FIG. 2 differs from that of FIG. 1 in that the semiconductor body 1 in portions of the electrical terminals 2 and 3 are enclosed not by a wavelength-converting potting mass but by a transparent envelope 15. The transparent envelope 15 does not cause any change in the wavelength of the radiation emitted by the semiconductor body 1 and for instance comprises an epoxy, silicone or acrylate resin conventionally used in LED technology, or some other suitable radiation-permeable material, such as inorganic glass.
A layer 4 is applied to the transparent envelope 15. The layer 4 comprises a wavelength-converting casting composition and, as shown in FIG. 2, covers the entire surface of the envelope 15. It is equally conceivable for the layer 4 to cover only a portion of the surface. The layer 4 for instance comprises a transparent epoxy resin which is mixed with luminous substance particles 6. Once again, for a semiconductor component that emits white light, YAG:Ce is preferred as the luminous substance.
FIG. 3 illustrates a particularly advantageous and preferred embodiment of the invention. The first and second electrical terminals 2, 3 are embedded in an opaque, and optionally prefabricated, basic housing 8 that has a recess 9. The term "prefabricated" is understood to mean that the basic housing 8 is already finished at the terminals 2, 3, for instance by means of injection molding, before the semiconductor body is mounted on the terminal 2. The basic housing 8, by way of example, is formed of opaque plastic, and in terms of its form the recess 9 is embodied as a reflector 17 for the radiation emitted by the semiconductor body in operation (the reflection optionally being achieved by means of suitable coating of the inside walls of the recess 9). Such basic housings 8 are used in particular for LEDs that are surface-mounted on printed circuit boards. They are applied, before mounting of the semiconductor body, to a conductor strip (lead frame) that has the electrical terminals 2, 3, the application for instance being done by injection molding.
The recess 9 is filled with a casting composition 5, whose composition is equivalent to that given above in conjunction with the description of FIG. 1.
FIG. 4 shows a so-called radial diode. Here, the electroluminescing semiconductor body 1 is secured, for instance by soldering or adhesive bonding, in a part 16, embodied as a reflector, of the first electrical terminal 2. Such housing constructions are known in LED technology and therefore require no further description here. The free surfaces of the semiconductor body 1 are covered directly by a casting composition 5 containing luminous substance particles 6, and the casting composition in turn is surrounded by a further transparent housing envelope 10.