Patent Application
20120057337
The invention relates to a conversion material, particularly for a white or colored light source comprising a semiconductor light source, as well as a light source comprising said conversion material.
The invention is intended to provide, in particular, a conversion material for at least partial conversion of the radiation of a primary light source, in which the primary radiation can comprise blue light, for example, into light of other wavelengths, which are referred to hereinafter also as secondary radiation and can comprise yellow light, for example, with the overlap of the primary and, as the case may be, broadband secondary radiation being capable of producing colored or white light.
Through the appropriate selection of the conversion material and the tuning of the overall system, it is possible in this way to adjust light colors or color coordinates of this light source.
Employed for the conversion of the radiation of the primary light source into light of other wavelengths are luminophores, which are also conventionally referred to as “phosphors.” These luminophores are generally embedded in a matrix, through which the primary light radiates. The extent of the conversion can be adjusted by means of the thickness of the conversion material and the type and concentration of doping or dopings with luminophores.
The color coordinates of the emitted light can be adjusted within certain limits in this case through the extent of conversion, so that, when white light is produced, both warm and cold white points of the resulting overall radiation are made possible.
The production of white light, for example, by superimposing blue light, which is emitted by a primary light source, and yellow light, which is produced by conversion of the blue light of the primary light source, has been known for some time.
The technical solution established at the present time is based on phosphors that are present and bound in a polymer matrix, which generally is composed of epoxy resins or silicones.
A drawback in the case of these embodiments is, in particular, the sensitivity of the polymers toward environmental conditions, such as moisture and radiation, in particular short wavelengths (UV), and toward elevated temperatures of greater than 120° C., for example. Occurring separately or in combination, these lead to the deterioration or aging of the optical polymer properties, which are already in part non-optimal in any case. On account of the swelling, hazing, discoloration (yellowing, browning), or even decomposition of the polymers that then ensues, the performance and service life of these used optical systems are strongly impaired.
With increasing performance capacity, in particular light output, of the semiconductor light sources based on LED and laser diodes (LD), the thermal stability takes on increasing importance, because the increase in the performance of these light sources is achieved, among other things, by way of semiconductor systems with high allowable power densities and high currents, whereby the overall system is exposed not only to higher radiation power but also higher thermal load.
The temperature level that is already usual at the present time lies at about and markedly above 150° C. and, in some cases, even above 180° C. and follows a clear trend toward temperatures of greater than 200° C. Hence, in long-term use of several tens of thousands of hours and longer, the polymers already find themselves in the limit of their applicability at the present time and are to be classified as limiting parameters for the service life of such light sources.
In EP 0 936 682 B9 (Nichia, “Light emitting device and display device”) a GaN-based blue-light-emitting diode (LED) is described as primary light source along with a yellow fluorescing luminophore for conversion, which is based on (Y1-rGdr)3Al5O12:Ce with r between 0 and 1. Transparent materials, such as epoxy resin, urea resin, silicone resin, or glass, are used as the matrix for embedding the luminophore.
In this case, however, all of the above-mentioned drawbacks of the polymers are manifested. No consideration is paid in this document to the intrinsic drawbacks of certain types of glass, such as occur, for example, in the case of Zn phosphates of certain compositions, such as reactivity with luminophores—for example, also redox reactions in this environment and intrinsic coloration, which have a negative influence on the conversion and performance properties of the overall light source.
US 2006/0113906 A1 (Nichia, “Light emitting device and method of manufacturing thereof”) describes a diode having a glass plate for covering and for protecting the light-emitting chip, with the glass necessarily composed of B2O3 (20-30 wt %) and ZnO (50-60 wt %) and optionally composed of SiO2 (0-10 wt %) and/or TiO2 (0-10 wt %) and/or other components, having a glass temperature Tg between 200° C. and 700° C., preferably 430° C. to 600° C., and possibly containing fluorescent substances for light conversion. A glass plate is described as a cover of a semiconductor chip, the glass plate being arranged at a distance from the chip. It is further described that the glass can contain a luminophore, although no consideration is paid to how this glass can be manufactured with this luminophore, even though experience has shown that, for example, Ce:YAG and also other luminophores cannot be processed in the glass melt, as would be required in order to obtain the glass plate described here as cover. During the usual thermal treatment, there generally exists a tendency toward mutual chemical reaction between glass and luminophore, as long as the two components have not explicitly been matched to each other in this respect. Furthermore, in the specific design of the glass with its luminophore in each case, intrinsic coloration as well as demixing can ensue.
Described in EP 1 471 777 A2 is a luminophore that is activated with Ce and has a garnet structure, in which terbium and Y, Lu, Sc, La, Gd, or Sm is a main component of the host lattice.
The sealing compound used comprises polymers having all of the drawbacks already described.
DE 10 137 641A1 describes a dome-shaped matrix for embedding luminophores, which is formed from a glassy body. Between the chip, which emits the primary light, and the dome with the embedded luminophores is found a recess, which is filled with an optically transparent medium having a high refractive index. This dome can be made of a glass, which can contain a luminophore, a fluorescing glass, or a fluorescing glass ceramic. It is described how luminophores can be fundamentally embedded in glass, but no consideration is paid to the fact that, in the case of unsuitable glasses, the luminophore is attacked during the embedding process and thereby loses its conversion properties at least partially or even entirely and the transmission properties of the glass are adversely affected by this process, and hence the efficiency of the LED can be strongly reduced, because, in this case, there is a pronounced tendency toward intrinsic coloration.
DE 102005023134 describes the use of a luminophore that is embedded in a glass matrix. Described as glass matrix are two glass families, a boron crown glass (containing, for example, 16-25% K2O) and a lanthanum crown glass (containing, for example, 5-25% ThO2). In this publication also, the producibility of the glass converter system is not considered and the negative influences to be expected on the overall system, comprising primary light source and converter, are still present. Moreover, because of the boron crown glass, a negative interaction between chip and converter is to be expected on account of the high alkali content and the alkali migration, particularly at higher temperatures, into the semiconductor, which is strongly detrimental to the service life. The lanthanum crown glass mentioned there is characterized in a negative manner by the content of ThO2 and is additionally expensive because of the raw materials used. Its environmental compatibility during manufacture, use, and recycling poses an additional serious problem.
U.S. Pat. No. 6,642,618 B2 describes the use of a layer made of a sol-gel glass, which has been doped with fluorescing substances, as conversion material. Coming into use as fluorescing substances are sulfides of the type (Sr,Ba,Ca)Ga2S4:Eu2+. The glass, produced by a sol-gel route, contains at least one component from the group PbO, Ga2O3, Bi2O3, CdO, ZnO, BaG, and Al2O3. The sol-gel route entails, in turn, drawbacks in regard to the variability of a converter in and of itself, because only very thin layers with a thickness of less than 10 μm can be prepared in compact form.
The preparation of compact solids by the sol-gel route is possible in principle, but it is complicated because of long drying times of greater than 24 h, which result in its classification as being expensive and impractical for many important applications.
Furthermore, the known glass also contains components prohibited according to RoHS.
The abbreviation RoHS (Engl. Restriction of the use of certain hazardous substances in electrical and electronic equipment) refers to, in summary, EC Directive 2002/95/EC, prohibiting certain substances in the manufacture and processing of electrical and electronic equipment and components, as well as its respective implementation in national legislation, which maximally allows 0.01 weight percent of cadmium, maximally 0.1 weight percent of lead, mercury, hexavalent chromium, PBB, and PBDE, respectively.
This thickness of the sol-gel layers limits, in turn, the ability to be doped with luminophores and, as a result, only a greatly restricted number of reasonable color coordinates, above all those with a blue-biased color impression, can be adjusted and, accordingly, the efficiency of the system has an upper limit. On account of reduced eye sensitivity, blue fractions contribute only slightly to the overall luminosity. The composition of conventional sol-gel precursors, which, depending on their type, also contain chemically very aggressive substances (notable concentrations of mineral acids), entails at least the possibility that the chip will be damaged during its manufacture.
EP 1 605 526 A describes the use of glass plates containing embedded conversion materials as well as the division of these plates and the processing thereof to domes. The matrix glass contains at least one component from the group GeO2, TeO2, PbO, CaO, and B2O3. Drawbacks, however, including the aforementioned problems, include the Pb content subjected to an RoHS prohibition as well as the use of expensive GeO2 and toxic TeO2 raw materials.
The Patent Abstracts of Japan, Publication number: 2007-123410 describe a light-emitting diode that is covered with a highly refractive glass in which phosphors are embedded. The doped glass is obtained by joint (simultaneous) melting of pulverized glass shards and the respective phosphors. The glass used necessarily contains TeO2 (40-53 mol %), B2O3 (5-30 mol %), and ZnO (3-20 mol %) as well as, optionally, Ga2O3, Bi2O3, GeO2, Y2O3La2O3, Gd2O3 (0-7 mol %), and Ta2O5. The risk of intrinsic coloration of this glass on account of the Bi2O3 and TeO2 content, on the one hand, and, on the other hand, the drawbacks already mentioned above, as well as the use of expensive and in part toxic raw materials (TeO2, Ga2O3, Bi2O3, GeO2), which are present, in part, in high proportions, are extremely detrimental for the commercial use thereof. Furthermore, the commercial applicability thereof in special instances is placed in question on account of an elevated demixing/crystallization tendency.
The Patent Abstracts of Japan, Publication number: 2007-016171 describes a wavelength conversion material made of oxynitride glass with a softening point of 700° C. or higher and nitride-based fluorescent materials distributed therein, with the luminophores already being added in the melt or else it being possible to produce practicably the glass itself from luminophore.
The drawbacks, such as reactivity and intrinsic color, are present here as well. Elevated mutual reactivity is to be expected, in particular, in an elevated temperature regimen at temperatures of greater than 600° C. In addition, the production of oxynitride glasses is complicated and expensive in comparison to the production of silicate glasses, for example.
Disclosed in WO 2007/145047 A1 is a wavelength conversion material made of a low-melting glass containing the main components SnO, B2O3, and P2O5 and nitride-based fluorescent materials distributed therein. The glass or glass family described here tends toward coloration on account of the P2O5 content and hence is unsuitable, at least in certain compositions, for the preparation of an effective wavelength converter.
EP 1 880 983 describes a composite material, which is obtained by mixing and baking a glass powder, blended with a luminophore. The converter produced in this way achieves an energy conversion efficiency of at least 10%. The described glass contains—as do many of those already mentioned—high proportions of, for example, ZnO, B2O3, and alkalis, with the entailed drawbacks. For the described composition ranges and the described production methods, these lead, in particular, to the potential of intrinsic coloration. Hence, the efficiency of the overall system is reduced and can, if at all, lie only slightly above the claimed limit of 10%.
In summary, the prior art describes light sources based on LED or laser diode light sources having wavelength converters comprising luminophores and matrix materials, for which the matrix materials, in particular, have intrinsic weaknesses and drawbacks. In the case of polymers, these are especially their instability toward thermal load and environmental influences as well as their relatively low refractive index.
In the case of the inorganic matrix materials mentioned, these drawbacks include:
Separately or taken together, these lead to inefficient converters with low light outputs or even to functionless examples, which the inventor was able to demonstrate by the inventor's own experiments for several of the aforementioned glasses and glass families.
The invention is intended to provide an inorganic wavelength conversion material having a matrix glass with at least one embedded luminophore for the production of white or colored light by additive color mixing of light of differing wavelengths or spectra of differing character in terms of their spectral curve.
This problem is solved by a conversion material having the features of claim 1, which, preferably, is produced according to a method having the features of method 22*. Advantageous embodiments are subjects of the respective dependent claims. sic; “method of claim 24”?—Translator's note.
This conversion material comprises a glass, which is referred to hereinafter also as the matrix or matrix glass. The starting material for the matrix glass exists in the form of a bulk/volume material or as loose powder obtained from it.
The bulk material or volume material describes the matrix glass after its production, that is, after its melting, and before the formation of a frit and/or before the grinding of the glass to a powder. Accordingly, the bulk material is a “compact” or fused glass body. It is a solid material or a body with uniform density. The bulk material can be present, for example, as a glass plate or a glass block.
Specifically present in the framework of the present invention is a conversion material, which comprises a matrix glass
The converter is suitable, in particular, for a white or colored light source comprising a semiconductor light source as the primary light source.
The sintered compact is also referred to as a sintered glass body. It is formed by the matrix glass, which has been ground to a powder and is “bonded” by means of sintering. The matrix glass is ground. The powder is placed in a mold. The sintered compact is formed by a sintering of the powder.
The grain size distribution in accordance with the invention, d10>=0.7 μm, d50>=3 μm, and d90<=150 μm, is determined on the powder.
Preferably, the sintered compact is sintered and/or the distribution of the grain sizes is chosen in such a manner that, for the sintered compact without an embedded luminophore, the sum of transmission and reflection in the spectral region from 350 nm to 800 nm and in the spectral region in which the primary light source emits light is at least greater than 80%, preferably greater than 85%, most preferably greater than 90%.
In particular, the sintered compact is sintered and/or the distribution of the grain sizes is chosen in such a manner that, in a spectral region from 350 to 800 nm, a quotient of Thalf:Tforward lies at 1<Thalf:Tforward<=70. The ratio makes possible a characterization of the produced sintered compact in terms of its transmission and/or scattering behavior. For further details and for the definition of the parameters Thalf and Tforward, reference is made to the discussions below in relation to
Also lying in the scope of the invention is a conversion material for a white or colored light source comprising a semiconductor light source as the primary light source, comprising
The inventors have recognized that the properties of the matrix glass as such and, in particular, of the glass powder formed from it, which, after sintering, forms the matrix for the embedded luminophore, exerts a decisive influence on the optical properties of the converter.
The inventors have recognized, on the one hand, that the size and distribution of the grain size of the matrix glass exerts a substantial influence on the optical properties of the sintered matrix glass (undoped) and the converter element (doped with phosphor). On the other hand, the inventors have also recognized that the chosen size of the grains, tending toward larger diameters, exerts an advantageous influence on the optical properties of the sintered matrix glass (undoped) and the converter element (doped with phosphor). This contrasts with the prior art, according to which an attempt was rather made to supply a powder with a small grain size—for example, one with a mean diameter d50 of less than about 2.5 μm.
The prevailing opinion in this case proceeds from the assumption that grains that are too coarse lead to increased porosity in a sintered compact, so that this would produce an effect of massive, uncontrollable scattering centers, and hence it would be expected that the result would be an optical regimen of the converter element that could not be adjusted in a controlled manner. The efficiency of a body or converter element produced in this way would drop to an unsatisfactory level.
The inventors have found, by contrast, that, by means of the grain size distribution in accordance with the invention, the optically relevant regimen, made up of transmission, reflection, absorption, and/or scattering, can be adjusted or modified in a targeted manner. Additionally, they have found that the large or coarse grains lead, as a result, to nearly transparent sintered compacts and, moreover, are more readily sinterable.
Coming into use as a transparent matrix in the present invention, in a first group of preferred embodiments, is a glass whose thermal expansion coefficient lies between 3 and 11·10−6 K−1 and whose refractive index nd assumes values above 1.6 or equal to 1.6.
The matrix glass is further characterized in that the phosphor used (for example, Ce:YAG) is not at all attacked or dissolved out or not to a notable extent during the melting/annealing/sintering, which would result in at least a restriction or total loss of its functionality.
The body obtained after melting/annealing/sintering is to be referred to below also as a sintered compact or else as converter or conversion material.
The composition of the matrix glass is free of toxic and/or environmentally questionable components.
In the use state of the conversion material, the conversion material comprises at least one luminophore with a grain size having a mean diameter d50 between 1 μm and 50 μm, especially preferably between 1 μm and 20 μm, most preferably between 1 μm and 15 μm.
In an alternative or supplemental embodiment of the invention, the conversion material comprises at least one luminophore with a grain size having a mean diameter d50 of less than 300 nm, especially preferably less than 100 nm, and most preferably less than 40 nm.
The primary radiation is absorbed through the addition of the luminophore. The secondary radiation produced, as well as the primary radiation, is additionally scattered. In order to ensure an adequate absorption and hence conversion of the primary radiation, the scattering of the primary radiation should not be too large. This is achieved either by relatively large luminophore particles (d50 between 1 μm and 50 μm, especially preferably between 1 μm and 20 μm, and most preferably between 1 μm and 15 μm) or else by nanoscale particles (d50 less than 300 nm, especially preferably less than 100 nm, and most preferably less than 40 nm). If the luminophore particles are too large, they are difficult to process in the sintering process. In addition, the practicable particle size has an upper limit dictated by the thickness of the conversion element (typically <250 μm).
Also lying in the scope of the invention is a method for producing the conversion material. The production takes place preferably by way of melting the glass raw materials, formation of a frit (or thin shards) by pouring the melt into, for example, water (or between cooled rollers), grinding of the frit to a glass powder, treatment of the matrix glass powder with fluorescence substances (phosphors), and thermal treatment, such as, for example, sintering, to form a new glass body/glass matrix composite material, the converter. The grinding of the matrix glass to a powder takes place in such a manner that the powder has a grain size distribution of grain sizes d10>=0.7 μm, d50>=3 μm, and d90<=150 μm.
The method is particularly suitable for the production of a conversion material in accordance with the invention.
In one embodiment, the sintering takes place in a specific atmosphere. The specific atmosphere is preferably supplied by nitrogen, forming gas, and/or argon or as a reduced pressure, such as, for example, as a vacuum of down to 10−6 mbar. This type of process design protects the luminophore against external influences, such as, for example, against oxidation or reduction. In addition, the embedding in certain glasses is thereby made possible at all. Furthermore, it is also possible in this way to adjust certain redox states in the matrix glass and/or the luminophore. By sintering at reduced pressure, it is possible to minimize or adjust the number and/or the size of possible pores. In an alternative or supplement, this can also be achieved by pressure sintering (uniaxially or isostatically), whereby the adjustment of specific atmospheres is to be observed in accordance with advantageous parameters for the material combinations to be processed. This takes place at a pressure in a range from 100 to 3000 bar, preferably from 500 to 2500 bar, most preferably from 500 to 1500 bar. This thermal treatment takes place, in turn, in a temperature range of up to approximately 150 K above the softening temperature (EW) of the glass or in such a way that the viscosity of the employed glass lies in a range between h=1014 dPas and
h=106 dPas, preferably between h=1013.5 dPas and h=107 dPas, especially preferably between h=1010 dPas and h=107 dPas. The annealing in this case can be carried out with a dwell time in a range of 0 to 300 min, preferably 15 to 300 min, especially preferably 100 to 180 min.
The luminophores—for example, Ce:YAG—are used with a grain size having a mean grain diameter d50 between 1 μm and 50 μm, especially preferably between 1 μm and 20 μm, most preferably between 1 μm and 15 μm. In an alternative or supplement, the luminophore is used with a grain size having a mean grain size diameter d50 of less than 300 nm, especially preferably less than 100 nm, and most preferably less than 40 nm.
In another embodiment of the method, the luminophores are subjected to a pretreatment, preferably thermal pretreatment. The temperatures are to be chosen depending on the type of luminophore. Preferably, the pretreatment takes place in a specific atmosphere. This is supplied, in particular, by nitrogen, forming gas, and/or argon or as a reduced pressure—for example, as a vacuum of down to 10−6 mbar.
In another embodiment of the invention, a protective layer, for example, for protection against chemical attack of the phosphor by the glass and vice versa during the sintering or one provided as a barrier layer against, for example, moisture in the LED system, is formed on the surface or outer side with the luminophore. This takes place prior to the blending with the matrix glass. This protective layer “shields” the luminophore from environmental influences and/or thermal influences. The luminophore is encapsulated. As a result, a degradation of the luminophore can be prevented or at least reduced. The protective layer optionally can be inorganic. It is formed or deposited, for example, by means of wet-chemical methods, sol-gel methods, PVD and/or CVD.
As an alternative or supplement, an end-processed and post-processed conversion element may also be furnished with a protective layer in accordance with one of the aforementioned methods, for example. A barrier layer against moisture, for example, represents one possible embodiment for a protective layer.
In an enhancement of the method, an additional temperature-assisted and, optionally, pressure-assisted (uniaxial or isostatic) treatment of the sintered compact takes place after sintering. As a result, the optical regimen of the conversion material or the undoped sintered matrix glass, already described above, is further optimally adjusted, and a solid composite is achieved and/or possible tensions are eliminated.
In one embodiment, the mentioned additional annealing is a second sintering. The further anealing is carried out preferably at a pressure in a range from 250 to 2500 bar, preferably from 500 to 1500 bar. Furthermore, the additional annealing is carried out at a temperature such that the viscosity of the employed glass lies in a range between
h=1014 dPas and h=106 dPas, preferably between h=1013.5 dPas and h=107 dPas, especially preferably between h=1010 dPas and h=107 dPas. The additional annealing is carried out in this case with a dwell time in a range from 30 to 600 min, preferably from 60 to 300 min, especially preferably from 100 to 180 min.
The glass matrix is further characterized in that, even as a pure, compact, fused glass body or a glass plate (also referred to above as bulk material), it has no intrinsic color from the above process and hence both primary light and secondary light are unchanged in an ideal way; this means that they are supplied for the color mixture without attenuation or spectrally changed by absorptions.
Accordingly, in general, this thereby takes into consideration the conversion of light of a wavelength w1 or of a spectral wavelength region w1 to light of a wavelength w2 of a spectral wavelength region w2 or, when n luminophores are used, to light of the wavelength wn or of a spectral wavelength region wn, in order to obtain, in the sum, light with the fundamental spectral distribution Z1*w1+z2*w2+ . . . +zn*wn, the factor z giving the proportions and color strengths of the associated wavelengths or wavelength regions that are involved in the color mixture.
On the basis of a primary light source, such as, for example, an LED (light-emitting diode) or LD (laser diode), the spectrum of which emits, at least partially, light corresponding to the excitation spectra of the luminophores, this leads to the emission of light of other wavelengths. The light source employed can, but need not, contribute to the mixture with its own light, which, at least in part, has not been converted to other wavelengths.
Accordingly, it is advantageous also to provide an inorganic matrix material/matrix glass, which
Accordingly made possible, without limiting the generality in regard to the generation of further light colors, is the conversion of blue to yellow light, so as to obtain, in the sum, white light or the physiological color impression of white light. White light refers in the following not only to the complete spectrum of visible light, but rather, in particular, also to any kind of light that produces, at least in humans, the impression of white light.
In particular, the invention comprises preferably:
In the conversion of UV light in the described cases, one additional luminophore, which emits in the blue spectral region, is required in each case.
A first group of preferred matrix glasses in accordance with the invention has the following properties:
The following glasses and glass families fulfill the requirements in accordance with the invention quite well in a surprising manner:
Lanthanum borosilicate glasses with a zinc fraction, aluminum borosilicates with an yttrium fraction, and alkaline-earth silicates
Sample glasses are:
Furthermore, it is advantageously possible with the present invention to provide, among other things, a glass matrix for conversion materials, with which, in particular also on account of ecological considerations, without the use of Tl2O, TeO2, and As2O3 and preferably also without the component Bi2O3, desired and advantageous optical properties (nd/vd) are made possible at simultaneously lower processing temperatures.
These glasses should not have any haze, crystallization, and intrinsic coloration as the matrix glass and should, furthermore, be sinterable without intrinsic color and be as little chemically reactive as possible toward the later contained luminophores.
For a first group of matrix glasses in accordance with the invention, these have a refractive index nd of nd>=1.6 and preferably a lower processing temperature. They should also be easy to melt and to process as well as have an adequate devitrifying stability, which makes possible a production of glasses in continuously running assemblies.
Provided, in particular, is an arsenic-free and preferably Bi2O3-free glass with a refractive index nd of nd≧1.6, which comprises the following components (in wt % based on oxide).
The following table comprises Examples 2 to 4 of the first group.
The following table comprises Example 5 of the first group:
The following table comprises Example 6 of the first group:
Preferably
The glass in accordance with the invention is preferably also free of coloring and/or optically active, as well as laser-active, components.
In particular, the glass in accordance with the invention is preferably free of components that are sensitive to oxidation, such as, for example, Ag2O or Bi2O3, and/or free of toxic components or components hazardous to health, such as, for example, the oxides of Tl, Te, Be, and As.
In accordance with another embodiment of the present invention, the glass mentioned in this description and in the claims is also preferably free of other components not mentioned in the claims; that is, in accordance with such an additional embodiment, the glass essentially comprises the mentioned components. The expression “essentially comprises” means in this case that other components are present at most as impurities, but are not added intentionally to the glass composition as individual components.
The glass in accordance with the invention can contain conventional refining agents in small amounts. Preferably, the sum of the added refining agents is at most 2.0 wt %, more preferably at most 1.0 wt %. As refining agent, the glass in accordance with the invention can contain at least one of the following components (in wt %, additively to the remaining glass composition):
Fluorine and fluorine-containing compounds also tend to vaporize during the melting and fusing operation and during the sintering process and, as a result, make more difficult a precise adjustment of the glass composition or, after sintering, the glass matrix. The glass in accordance with the invention is therefore preferably also free of fluorine.
The tables contain exemplary embodiments in the preferred composition ranges. The glasses described in the examples were produced using different process parameters, which are associated with the physical properties of the glasses.
The raw materials for the oxides are weighed, one or more refining agents, such as, for example, As2O3, are added, and subsequently well mixed. The glass quantity is fused at approximately 1330° C. in a discontinuous melting assembly and afterwards refined (1380° C.) and homogenized. At a pouring temperature of about 1380° C., the glass can be poured and processed to the desired dimensions as, for example, ribbons. In large-volume, continuous assemblies, the temperatures can be lowered, according to experience, by at least approximately 100 K.
Ribbons are obtained by pouring the glass over two rollers. They can be better ground to powder, a precursor for sintering, than shards.
The properties of the glass thus obtained are presented in the following table as Example 6.
The examples described below both of the first group and of the second group of embodiments in accordance with the invention are subject to essentially the same method of production in each case.
Powders of the starting glasses, ground to a grain size having a distribution of d10>=0.7 μm, d50>=3 μm, and d90<=150 μm, are weighed with a luminophore—for example, Ce:YAG having a grain size with a mean diameter d50 between 1 μm and 50 μm, especially preferably between 1 μm and 20 μm, most preferably between 1 μm and 15 μm, based on weight percent—and blended in a mixing assembly—for example, a Turbula tumbling mixer (model T2C/Willi A. Bachofen company/Basel) or Speedmix (model DAC 150 FVZ/Hauschildt Engineering)—for 1 to 120 min, preferably 1 to 5 min (Speedmix) or 15 to 120 min (Turbula), most preferably 1 to 3 min (Speedmix) or 60 to 120 min (Turbula).
Here, the d502 or else median value is the value that gives a grain size at which 50% of the particles are finer and 50% are coarser that this given value. 2[Translator's Note] “D50” in the original
There also exist nanoscale phosphors, that is, luminophores with outer dimensions in the range of several nanometers, in particular of less than 100 to 200 nm, that can also be used.
The powder mixture or else the pure glass powder is subsequently taken in portions in such a way that a powder body having a diameter of approximately 10 mm, preferably 5 mm, most preferably less than 5 mm, but at least 1 mm, and a height of approximately 3 mm or 1 mm or 0.5 to 0.1 mm can be prepared.
The bulk is deposited on a thermally stable substrate in, for example, a tube- or ring-shaped element that delimits the bulk and is compacted manually and/or fed uniaxially (for example, press of the Paul Weber company; Model PW40) and/or cold-isostatically (press of the Paul Weber company; Model KIP500E) to a pressing process, which can be optimally designed by addition of convention processing auxiliaries. The pressure range for the uniaxial pressing lies at 100 to 5000 bar, preferably 500 to 2500 bar. This takes place in such a manner that, subsequently, the outer delimitation can be removed.
Afterwards, the annealing of the samples takes place at temperature and time regimens (heating rates and dwell times) that are appropriate for the matrix glasses in terms of their softening temperature. Depending on the slope of the viscosity curve of the glass and without general restriction, the target temperatures T of the annealing lie in the range between the EW (softening temperature) and Va (processing temperature), usually in a regimen of EW+150 K, or such that the viscosity of the employed glass lies in the range between h=1014 dPas and h=106 dPas, preferably between h=1013.5 dPas and h=107 dPas, especially preferably between h=1010 dPas and h=107 dPas.
The heating takes place such that it is possible to assume an equilibrated temperature level in the oven and for the bulk or, as the case may be, several bulks.
In particular, the time regimen to be chosen in this case depends typically on the type, size, and design (also the control) of the annealing assembly. In the present oven (Nabertherm model N70/H; Naber C16 control and Eurotherm model 2604), heating rates of from 1 K/min to 30 K/min, preferably 1 K/min to 20 K/min, most preferably 1 K/min to 10 K/min, to the target temperature and dwell times before cooling with oven characteristic curve of 0 to 60 min, preferably 0 to 30, most preferably 10 to 30 min, have proven useful.
After the annealing or annealings, the composite bodies thus created, comprising glass matrix and at least one luminophore, are post-processed, with grinding and/or polishing agents of grain size<1 μm (single sided) being used, so that, as a result, surfaces that are raw on both sides or on one side or are polished are present.
The measurement of the optical data for reflection and transmission took place in a conventional spectrometer (for example, Perkin Elmer Lambda 9 or 900), with sample in front of (transmission) or in back of (reflection) an integration sphere, in the wavelength region from 250 to 2500 nm, at least, however, in the region from 300 to 800 nm, in order to determine the aforementioned parameters. The determination of the parameters Thalf and Tforward also takes place by means of the integration sphere. For further details, reference is made to the discussions in regard to
The internal conversion quantum yield of the luminophores embedded in the glass matrix was reduced in relation to the internal conversion quantum yield of the non-embedded luminophores by not more than 20%, preferably by not more than 10%, and most preferably by not more than 5%. The internal conversion quantum yield was measured in each case by means of the decay time of excited optical transitions in the luminophores.
The following described glasses and glass families of a second preferred group of exemplary embodiments fulfill the requirements in accordance with the invention as well, but have a refractive index that is less than 1.6.
The refractive index of these glasses lies preferably at 1.43 to 1.6 and most preferably at 1.45 to 1.49. As a result, these glasses are matched relatively well to the refractive index of the light sources/units of surrounding polymers (epoxides or silicones, including polymer with nd between 1.3 and 1.6).
Furthermore, the difference from the refractive index of air, which is, ultimately, the medium surrounding the entire light source system, is markedly reduced.
This matching is important in indirect contact of converter material to semiconductor element and further surrounding (components) elements in order to out-couple efficiently exciting light from the converter (for example, the light of a blue LED), which passes through the converter, as well as light generated in the converter. Here, indirect contact is understood to mean an arrangement without direct mechanical contact; this means, in particular, that the evanescent fields of the disseminating light, which surround the respective materials, do not measurably overlap at all or essentially not at all.
Preferable glasses of this group comprise, for example, zinc phosphates, borosilicates, aluminum borosilicates, and alkaline-earth silicates.
Sample glasses are:
Advantageously provided with the present invention is, among other things, a glass matrix for conversion materials, with which, particularly on account of ecological considerations, without the use of Tl2O, TeO2, and As2O3 and preferably also without the component Bi2O2, desired and advantageous optical properties (nd/vd) are made possible at simultaneously low processing temperatures.
These glasses have no haze, crystallization, and intrinsic coloration as matrix glass and, furthermore, are sinterable without intrinsic coloration. In this case, these glasses are only slightly chemically reactive toward the luminophores used.
Furthermore, these glasses are easy to melt and to process and have an adequate demixing and crystallization stability, which makes possible a manufacture of glasses in continuously operating assemblies.
In particular, an arsenic-free and preferably Bi2O3-free glass with a refractive index glass nd of nd<1.6 provided, which comprises the following components (in wt % based on oxide).
The following table comprises Example 1 of the second group:
Preferably
The following table comprises Example 2 of the second group:
Preferably
The following table comprises Example 3 of the second group:
Preferably
The following table comprises Example 5 of the second group:
The following table comprises Example 6 of the second group:
The glass in accordance with the invention is preferably also free of coloring and/or optically active, as well a laser-active, components.
In particular, the glass in accordance with the invention is preferably also free of components that are sensitive to oxidation, such as, for example, Ag2O or Bi2O3, and/or free of toxic components or components hazardous to health, such as, for example, the oxides of Tl, Te, Be, and As. In any case, the glass is preferably free of arsenic.
In accordance with an embodiment of the present invention, the glass is also preferably free of other components not mentioned in the claims; that is, in accordance with such an additional embodiment, the glass essentially comprises the mentioned components.
The expression “essentially comprises” means in this case that other components are present at most as impurities, but are not added intentionally to the glass composition as individual components.
The glass in accordance with the invention can contain conventional refining agents in small amounts. Preferably, the sum of the added refining agents is at most 2.0 wt %, more preferably at most 1.0 wt %. As refining agent, the glass in accordance with the invention can contain at least one of the following components (in wt %, additively to the remaining glass composition):
Fluorine and fluorine-containing compounds also tend to vaporize during the melting and fusing operation and during the sintering process and, as a result, make more difficult a precise adjustment of the glass composition or, after sintering, the glass matrix. The glass in accordance with the invention is therefore preferably also free of fluorine.
The glasses described in the examples were produced using different process parameters, which are associated with the physical properties of the glasses.
The raw materials for the oxides are weighed, one or more refining agents, such as, for example, Sb2O3, are added, and subsequently well mixed. The glass quantity is fused at approximately 1320° C. in a discontinuous melting assembly and afterwards refined (1370° C.) and homogenized. At a pouring temperature of about 1320° C., the glass can be poured and processed to the desired dimensions as, for example ribbons. In large-volume, continuous assemblies, the temperatures can be lowered, according to experience, by at least approximately 100 K.
Ribbons are obtained by pouring the glass over two rollers. They can be better ground to powder, a precursor for sintering, than shards.
The properties of the glass thus obtained are presented in the following Table 5 as Example 8.
The examples described below in regard to the glasses of the second group are subject to essentially the same method of production in each case (see for this the glasses of the first group). For further or lacking details, reference is made to the preceding description.
Powders of the starting glasses, ground to a grain size having the distribution of d10>=0.7 μm, d50>=3 μm, and d90<=150 μm, are weighed with a luminophore—for example, Ce:YAG having a grain size with a mean diameter d50 between 1 μm and 50 μm, especially preferably between 1 μm and 20 μm, most preferably between 1 μm and 15 μm, based on weight percent—and blended in a mixing assembly—for example, a Turbula tumbling mixer (model T2C/Willi A. Bachofen company/Basel) or Speedmix (model DAC 150 FVZ/Hauschildt Engineering)—for 1 to 120 min, preferably 1 to 5 min (Speedmix) or 15 to 120 min (Turbula), most preferably 1 to 3 min (Speedmix) or 60 to 120 min (Turbula).
The powder mixture or else the pure glass powder is subsequently taken in portions in such a way that a powder body having a diameter of approximately 12 mm/8 mm/<5 mm and a height of approximately 3 mm/2/1 can be prepared.
The bulk is deposited on a thermally stable substrate in, for example, a tube- or ring-shaped element that delimits the bulk and is compacted manually and/or fed uniaxially and/or cold-isostatically to a pressing process, which can be optimally designed by addition of convention processing auxiliaries. This takes place in such a manner that, subsequently, the outer delimitation can be removed.
Afterwards, the annealing of the samples takes place at temperature and time regimens (heating rates and dwell times) that are appropriate for the matrix glasses in terms of their softening temperature. Depending on the slope of the viscosity curve of the glass and without general restriction, the target temperatures T of the annealing lie in the range between the EW, the softening temperature, and Va, the processing temperature, of the matrix glass usually in a regimen of EW+150 K.
The heating takes place such that it is possible to assume an equilibrated temperature level in the oven and for the bulk or, as the case may be, several bulks.
In particular, the time regimen to be chosen in this case depends typically on the type, size, and design (also the control) of the annealing assembly. In the present oven (Nabertherm model N70/H; Naber C16 control and Eurotherm model 2604), heating rates of from 1 K/min to 30 K/min, preferably 1 K/min to 20 K/min, most preferably 1 K/min to 10 K/min, to the target temperature and dwell times before cooling with oven characteristic curve of 0 to 60 min, preferably 0 to 30, most preferably 10 to 30 min, have proven useful.
After the annealing or annealings, the composite bodies thus created, comprising glass matrix and at least one luminophore, are post-processed, with grinding and/or polishing agents of grain size<400 μm (two-sided) as well as, depending on the case, for example, diamond polishing agents of grain size up to <1 μm (single sided) being used, so that, as a result, surfaces that are raw on both sides or on one side or are polished are present. The measurement of the optical data for reflection and transmission takes place in a conventional spectrometer, with sample in front or at the input (transmission) or in back or behind at the output (reflection) of an integration sphere, in the wavelength region from 250 to 2500 nm, at least, however, in the region from 300 to 800 nm, in order to determine the aforementioned values.
The present invention will be explained below on the basis of
First of all,
The integration sphere 3 has a diameter of 60 mm and a sphere aperture with a diameter of about 12 to 15 mm. A rectangular diaphragm (cross section: 6×12 mm2) is positioned before the sphere 3 as an additional component. A light source 1, which emits essentially only parallel light in relation to the beam axis as measuring beam, is positioned at a spacing of approximately 50 cm from the integration sphere 3. The measuring beam has a cross section of 4×10 mm2. A sample 2 to be investigated is arranged at various distances between the integration sphere 3 and the light source 1. The sample 2 has an outer diameter greater than about 12 mm or greater than about 12 mm times greater than 12 mm (for a rectangular sample 2). The thickness of the sample lies at about 1 mm (±0.05 mm). A spectrometer 4 with a photodetector for detecting the light registered by the integration sphere 3 is arranged in the beam direction directly behind the integration sphere 3.
During the measurement of Thalf, the sample 2 is positioned at a distance of less than or equal to about 3 mm from the integration sphere 3 in order to register both the directly transmitted portion of the light and the portions scattered in the sample 2 emitted from the parallel light source 1.
By contrast, during the measurement of Tforward, the sample 2 is positioned at a distance from the integration sphere 3. The distance is about 43 cm. As a result, essentially only the directly transmitted portion or the portion transmitted in the forward direction is registered.
This kind of measurement makes possible a classification of the undoped samples 2 investigated here and/or, as the case may be, the doped samples 2 in regard to their transmission and/or scattering behavior. The classification of the samples 2 or the characterization of the samples 2 can be expressed by the quotient Thalf:Tforward.
For an ideally optically transparent, non-scattering sample 2, such that the light beams would run exclusively in the beam direction, a value of 1 or nearly 1 would be obtained for the ratio Thalf:Tforward. By contrast, a sample with a high scattering behavior would lead to very large values of Thalf:Tforward.
During the measurement of the transmission, the sample 2 is thus positioned before and, in particular, at the input of the integration sphere 3. In contrast to this, during the measurement of reflection, the sample 2 is positioned behind and, in particular, at the output of the integration sphere 3. The detector of the spectrometer 4 is located at any point on the circumference of the integration sphere 3.
Illustrated in
These optical characteristic sizes can be measured, for example, by means of a commercially available spectrometer (for example, Perkin Elmer Lambda 9 or 900).
Illustrated to this end in
The illustration is explained on the basis of Example 11 KGV3 (line V): 10% of the grains or particles have a diameter of less than about 23.6 μm, 50% of the particles have a diameter of less than about 55.8 μm, and 90% of the particles have a diameter of less than 94.9 μm. It can be seen that the particles for 11 KGV3 have the largest diameters.
The process parameters used for the Glass Examples 2 KGV1 (II), 2 KGV2 (I), 11 KGV1 (IV), 11 KGV3 (V) are summarized in Table 8. In this case, two different methods are given for the Glass Example 2 KGV1: (II) with double annealing, that is, sintering and subsequent thermal treatment, as well as, for example, a second sintering, and (III) with single annealing or sintering. The parameter (t@T/′) describes the dwell time at T in minutes.
Illustrated to this end, finally, in
The matrix glass described above can be used for creating a light source, in particular a white or colored light source, with the matrix glass containing the luminophore or luminophores corresponding to a conversion material that preferably comprises the features of the conversion material defined in one of claims 1 to 21 and preferably is produced by means of a method having the features of one of claims 22 to 28.
In a preferred embodiment, the light source comprises a primary light source, in particular a semiconductor light source, which emits light with wavelengths in the region from 225 nm to 520 nm, preferably from 350 nm to 480 nm, most preferably with wavelengths in the region from 400 nm to 480 nm.
In an alternative embodiment, the primary light source comprises an LED, which emits light with a wavelength in the region from 400 nm to 480 nm, preferably 420 nm to 480 nm.
In another preferred embodiment, the primary light source comprises a UV LED, which emits light with a wavelength in the region 235 nm to 400 nm, preferably 350 nm to 400 nm.
In yet another embodiment, the primary light source comprises the primary light source of a semiconductor laser diode, which emits light with a wavelength in the region from 400 nm to 480 nm.
The light source can have one or more, in particular also several different, primary light sources.
Further descriptions of these light sources as well as their spatial arrangement and properties may be found in the application titled “Optik-Konverter-System für (W) LEDs” [Optical Converter System for (W) LEDs] with the internal file reference 08SGL0020DEP or P 3156 and in the application titled “Gehäuse für LEDs mit holier Leistung” [Housing for LEDs with High Power”] with the internal file reference 08SGL0060DEP or P 3063 of the same applicant, which were filed on the same day as this application and which are also in full scope a part of the content of this application by way of reference.
With several primary light sources and several luminophores, it is possible to create a light source with which it is possible to emit light at the following color coordinates in (X, Y) color space, in particular by selecting the luminophore or luminophores as well as by adjusting the concentration of the luminophores and/or the thickness of the converter material:
In this way, a color space within the traverse ABCDE is defined or enclosed, within which light of all color coordinates can essentially be emitted from the light source.
The adjustment of the color coordinates within the aforementioned traverse as well as the traverse discussed below can be undertaken at one time and in a definitively defined manner by establishing the ratio and concentration of the respective luminophores as well as, in the case of several light sources, the intensity of emission of the respective light sources.
Furthermore, in the case of several primary light sources, it is additionally possible, within a certain scope, to change the color coordinate by changing the intensity of the emission of one or more primary light sources.
In another embodiment of the light source, it is possible to emit light at the following color coordinates in (X, Y) color space, in particular by selecting the primary light source, by selecting the luminophore or luminophores as well as by adjusting the concentration of the luminophores and/or the thickness of the converter material:
In yet another embodiment of the light source, it is possible to emit light at the following color coordinates in (X, Y) color space, in particular by selecting the primary light source, by selecting the luminophore or luminophores as well as by adjusting the concentration of the luminophores and/or the thickness of the converter material:
In yet another embodiment of the light source, it is possible to emit light at the following color coordinates in (X, Y) color space, in particular by selecting the primary light source, by selecting the luminophore or luminophores as well as by adjusting the concentration of the luminophores and/or the thickness of the converter material:
In this way, it is possible to create, in particular, saturated colors green-yellow-orange (amber) NOPQ and, moreover, it is possible, to create all saturated colors in the spectral region from 535 nm to 610 nm by selection of the primary light source or light sources, which, otherwise, would have only low efficiencies with pure LEDs.
For understanding the following patent claims, it is noted that, for a first embodiment of the invention, the term “in the spectral region in which the primary light source emits light” allows comprises only the spectral region of a single primary light source. This single primary light source is, in this case, one of the primary light sources mentioned in the preceding description or in the following claims.
In further embodiments in accordance with the invention, the term “in the spectral region in which the primary light source emits light” comprises the spectral region of more than only a single primary light source. In this case, two or more than two primary light sources with various emission spectra may be used, in particular in order to span a larger color spaces as well. However, these two or more primary light sources also each comprise only the primary light sources mentioned only in the preceding description or in the following claims.
It is obvious to the skilled practitioner that the described embodiments are to be understood as examples. The invention is not limited to these, but rather can be varied in diverse ways without departing from the spirit of the invention. The features of the individual embodiments and the features mentioned in the general part of the description can each be combined both among each other and with each other.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2008 021 438.8 | Apr 2008 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2009/003111 | 4/29/2009 | WO | 00 | 6/16/2011 |
