Patent Publication Number: US-2007114520-A1

Title: Radiation emitting device and method of manufacturing the same

Description:
RELATED APPLICATIONS  
      This patent application claims the priority of European patent application no. 05019106.3 filed Sep. 2, 2005 and 05024592.7 filed Nov. 10, 2005, the disclosure content of which is hereby incorporated by reference  
     FIELD OF THE INVENTION  
      The present invention is directed to a radiation emitting device and, in particular, to increasing the out-coupling efficiency of the radiation produced by the device. The invention is also related to a method for manufacturing such a device.  
     BACKGROUND OF THE INVENTION  
      The publication “Organic light emitting device with an ordered monolayer of silica microspheres as a scattering medium” published in Applied Physics Letters Vol. 76, No. 10 of Mar. 6, 2000 discloses an organic light emitting device “OLED” based on organic thin films having a glass substrate and a monolayer of hexagonally closed packed arrays of silica spheres with a submicrometer size attached to the glass substrate through which the emitted light comes out. The arrays of silica microspheres scatter light which is wave guided within the glass substrate and contribute to an increase in the amount of light emitted towards the viewer.  
     SUMMARY OF THE INVENTION  
      One object of the invention is to provide a radiation emitting electronic device having an increased out-coupling efficiency of the radiation produced by the device.  
      This and other objects are attained in accordance with one aspect of the invention directed to a radiation emitting electronic device comprising a substrate, a radiation emitting functional area on the substrate and a radiation out-coupling material comprising polysilsesquioxane and inorganic nanoparticles arranged in the optical path of the radiation emitting functional area.  
      Due to the radiation out-coupling material such a device has a higher external radiation efficiency compared to a similar device which lacks such a radiation out-coupling material. The inorganic nanoparticles can form inter alia scattering centers in the radiation out-coupling material thereby leading to an increased fraction of out-coupled radiation in this device. The polysilsesquioxane (POSS) material can build up a matrix in which the inorganic nanoparticles are distributed, thereby forming a so-called guest-host-system e.g.(guest=POSS; host=inorganic nanoparticles).  
      The term polysilsesquioxane denotes polymeric silica-oxygen compounds of the following general formula Si 2     n   R 2     n   O 3     n    wherein the index n is a non-negative integer and all the substituents R can independently of each other be any substituent for example an inorganic substituent such as hydrogen or organic substituents such as alkyl groups, which potentially can contain further functional groups. The substituents can even contain inorganic atoms such as e.g. Si atoms. The index n can be any number, preferably n=10-12 for cage-like POSS materials.  
      In a further embodiment of the invention the radiation out-coupling material is substantially transparent for the emitted radiation of the radiation out-coupling material. The term “substantially transparent” means that the radiation out-coupling material has a transparency of at least 50%, or 70% for the emitted radiation, preferably greater than 90% most preferred greater than 95%. The transparency of the radiation out-coupling material can for example be determined using densitometers or transmission-spectrometers. It is also possible to determine the transparency by measuring the absorption of the sample.  
      The nanoparticles can have a size of around 100 nm to 1 μm, preferably 200 nm to 500 nm or can even have a size of less than 100 nm in one dimension. Due to their small size the nanoparticles can effectively scatter the radiation generated by the functional area without absorbing too much of the emitted radiation (see for example  FIG. 4 ).  
      In contrast to other polymeric materials for example polymethyl-methacrylate (PMMA) or polycarbonate, polysilsesquioxane has the advantage that it has a higher glass transition temperature T g  and also shows an enhanced durability due to a reduced temperature dependency of the aging of this material.  
      The polysilsesquioxane matrix with the inorganic nanoparticles can also provide a higher out-coupling of the radiation produced by the electronic device via radiation refraction (see for example  FIG. 4 ).  
      The polysilsesquioxane of the radiation out-coupling material can be obtainable by reacting molecules of the following general formula:  
                 
 
 wherein the substituent R is selected from: 
          organic epoxides, hydrogen, alkyl-groups, alcohols, alkoxy-groups and ester-groups and     the substituent R′ can be independently of each other a —O—Si(Alkyl) 2 -Glycidoxy-alkyl-group with alkyl ═C 1  to C 12  alkyl groups, so that a molecule of the following general formula might result:  
                 
       

      Alternatively the three R′ groups can together form a bridging group so that a molecule of the following generals formula results:  
                 
 
      Molecules with the above mentioned general formulae can easily be adopted for different combinations of polysilsesquioxane and inorganic nanoparticles by e.g. varying the substituents R or R′ in order to be suitable for different applications. For example organic epoxides as substituent R or R′ can be introduced into the above-mentioned molecules in order to generate side chains which are important for the polymerization of these molecules to yield the final polysilsesquioxane. Silsesquioxane monomers with the above-mentioned general formula preferably contain one or two substituents R having functional groups used for polymerization, for example epoxide groups. These groups can be used to incorporate the monomers into a polymeric network. Depending whether the monomers form the endpoints of a polymeric chain or are located within the larger chain, one, two, three or even more of the substituents R can comprise polymerizable groups. Monomers with more than two polymerizable groups can be used to form for example a highly crosslinked network of polysilsesquioxane, thereby also changing the chemical nature of this polymer when compared to a polysilsesquioxane which is not so highly crosslinked.  
      The substituents R can also comprise unreactive organic groups in order to ensure a good dispersion and compatibilization with the inorganic nanoparticles. The substituents R also enable an adjusting of the viscosity. For example R can be selected from a group consisting of straight or branched alkyl groups, organic epoxides, hydrogen, alcohols, alkoxy-groups and ester-groups. Moreover one or more substituents R can also comprise one or more reactive groups for polymerization, for example co- or homo-polymerization. Molecules with such a general formula can easily be incorporated into a thermally and chemically robust hybrid organic/inorganic polysil-sesquioxane framework. Polysilsesquioxane material obtainable via reaction of molecules with the above-mentioned general formulae can easily be used as a matrix for the inorganic nanoparticles of the radiation out-coupling material. The silsesquioxane monomers with the above-mentioned formulae and the inorganic nanoparticies are preferably mixed and then polymerised using heat or UV radiation to form the radiation out-coupling material.  
      In another embodiment of the invention the radiation emitting electronic device can comprise an OLED. An OLED device comprises a functional stack located on a substrate. The functional stack comprises at least one or more organic functional layers sandwiched between two conductive first and second layers. The conductive layers function as electrodes (cathode and anode). When a voltage is applied to the electrodes, charge carriers are injected through these electrodes into the functional layers and upon recombination of the charge carriers visible radiation can be emitted (electroluminescence). The organic functional stack on the substrate can be encapsulated by a cap, which can comprise, for example, glass or ceramic. The radiation emitted by such an OLED device can for example be light in the visible range from about 400 nm to about 800 nm, or can also be light emitted in the infrared or UV range. The first conductive layer can e.g. comprise transparent materials such as indium-tin-oxide ITO, zinc oxide and the second conductive layer can comprise metals such as Ca, Mg, Ba, Ag, Al or a mixture thereof or can also comprise the above mentioned transparent materials of the first conductive layer. The second conductive layer can also comprise thin layers of e.g. LiF or CsF.  
      In another embodiment of the invention the radiation emitting electronic device can also comprise for example an inorganic light emitting LED, including for example ZnS as a functional material.  
      In a further embodiment of the invention the radiation out-coupling material can comprise 30 to 70 weight % polysilsesquioxane and 70 to 30 weight % of the inorganic nanoparticles. Within such a weight %-range of polysilsesquioxane and transparent inorganic nanoparticles most of the radiation generated by the radiation emitting electronic device can be coupled out of the device via refraction and scattering and is not back scattered or reflected back into the interior of the device. Preferably the radiation out-coupling material comprises around 30 weight % polysilsesquioxane and around 70 weight % of the inorganic nanoparticles or 50 weight % POSS and 50 weight % inorganic nanoparticles.  
      The inorganic nanoparticles of the radiation out-coupling material can comprise metal oxide particles, for example they can be selected from titanium dioxide, zinc oxide and indium zinc oxide. These materials are especially well suited to be used as inorganic nanoparticles for scattering radiation emitted from an electronic device. Another advantage of the radiation emitting electronic device of this embodiment of the invention is, that the inorganic nanoparticles used are already in the oxidized form and uniform in size. The composition of the polysilsesquioxane and the inorganic nano-particles can therefore be well defined and homogeneous. The attractive van der Waals interactions of the polysilsesquioxane matrix can also be adapted to the polarity of the inorganic nanoparticles resulting in similar polarity, so that no phase separation is expected and the conditions for long-term stability are largely given.  
      In a further embodiment of the invention the radiation out-coupling material comprises a polysilsesquioxane matrix with inorganic nanoparticles dispersed therein, wherein the nanoparticles has a higher refractive index then the polysilsesquioxane matrix. Such a material is especial well suited to allow the scattering of the radiation emitted by the device so that the radiation is out-coupled of the device. In this case the polysilsesquioxane matrix might have a refractive index of about 1.6 and the nanoparticles may have a refractive index of about 1.7 to 2.2, or between 1.6 to 1.7. Preferably the refractive index of the radiation out-coupling material is as high as possible.  
      The radiation out-coupling material further can be arranged in a layer-wise manner on the radiation emitting functional area. Thus an arrangement can result in a very effective out-coupling effect of the radiation reduced by the functional area.  
      Furthermore in another embodiment of the invention the substrate of the radiation emitting electronic device is substantially transparent for the emitted radiation and the radiation out-coupling material is arranged preferably in a layer wise manner on one of the main surface areas of the substrate. In this case the radiation emitted by the functional area can effectively be out-coupled out of the device via the transparent substrate.  
      The substrate can furthermore be selected from glass, metal, polymer silicon and ceramic.  
      These materials can for example be designed in such a way that they are substantially transparent for the emitted radiation and furthermore can be designed in such a way so that the substrate is not just substantially transparent but also flexible. This can be done for example by using transparent polymers such as in order to form flexible substantially transparent substrates. As mentioned above the term “substantially transparent” means that the substrate is at least 70 to 80%, preferably more than 90% transparent for the emitted radiation.  
      In another embodiment of the present invention the radiation emitting electronic device can further comprise a cap encapsulating the radiation emitting functional area. This cap can also be substantially transparent for the emitted radiation and in this case the radiation out-coupling material is preferably arranged between the radiation emitting functional area and the cap in order to enhance the out-coupling efficiency of the radiation emitted through the cap. Such a radiation emitting electronic device with a cap can comprise just a transparent substrate or just a transparent cap or also both a transparent substrate and a transparent cap in order to emit radiation through the substrate and the transparent cap at the same time.  
      The transparent inorganic nanoparticles can be titanium dioxide nanoparticles. The titanium dioxide is preferably in the rutile modification.  
      In another embodiment of the invention the radiation out-coupling material comprises a layer with at least a first and a second sub-layer, said sub-layers having different ratios of polysilsesquioxane and inorganic nanoparticles (concentration gradient).  
      Preferably the ratios of polysilsesquioxane and inorganic nanoparticles in the at least two sub-layers are varied in such a way so that the second sub-layer which is nearer to the outside of the device has a lower refractive index than the first sub-layer which is located nearer to the interior of the device. Such a variation of the refraction indices can advantageously decrease the difference between the refraction indices of the second sub-layer and the refraction index of air (about 1.0) so that the so-called “index jump” can be reduced and the fraction of out-coupled radiation can be increased. It is also possible for the radiation out-coupling material to comprise more than two sub-layers, for example three or four sub-layers having a gradually decreasing refractive index when going from the interior of the device to the exterior. The refractive index of the sub-layers can be varied by changing the ratio of polysilsesquioxane to the inorganic nanoparticles (the more nanoparticles the higher the refractive index).  
      The radiation out-coupling material in one embodiment of the invention can comprise at least one lens. The lens can enhance the intensity of the emitted radiation along the main direction of the emission by focussing the radiation and emitting it along one direction. As shown in  FIGS. 2A and 2B  the radiation out-coupling material can for example comprise one lens ( FIG. 2A ) or can also comprise an array of small microlenses as shown in  FIG. 2B .  
      In yet another embodiment of the invention phosphors are included in the radiation emitting electronic device. These phosphors are able to convert the radiation emitted by the radiation emitting functional area into radiation with a different wavelength, thereby for example changing the colour of visible light emitted by the radiation emitting electronic device. The phosphors can for example be cerium doped garnets, nitride phosphors, ionic phosphors like SrGa 2 S 4 :Eu 2+ , SrS:Eu 2+ , fluorescent dyes, quantum dots or conjugated polymers or mixtures thereof. Phosphors can also be used e.g. to downconvert radiation of a short wavelength (for example corresponding to the blue range) to white light of a longer wavelength The output spectrum of the radiation emitting device can then be a combination of unconverted radiation and converted white light.  
      These phosphors might be arranged in the optical path of the device as a separate layer or might be included in the radiation-outcoupling material. For example the phosphors could be included in the polysilsesquioxane matrix of a separate layer comprising the radiation-outcoupling material, so that this material could function as a radiation-outcoupling layer and also as a radiation conversion layer.  
      Another aspect of the invention is directed to a method of manufacturing a radiation emitting electronic device. A substrate is provided, and a radiation emitting functional area is produced on the substrate. A radiation out-coupling material is provided comprising polysilsesquioxane and inorganic nanoparticles in the optical path of the functional area.  
      In a further embodiment of this method of the invention the radiation out-coupling material is formed by polymerizing a blend of silsesquioxane monomers and the inorganic nanoparticles in step C). Preferably a suspension of the monomers and the nanoparticles in a solvent, for example aliphatic or cycloaliphatic solvents such as cyclohexane is polymerized using UV radiation or heat. The temperatures for the polymerization step can be between 100 and 180° C. The suspension of the silsesquioxane monomers and the transparent inorganic nanoparticles is preferably formed on the substrate of the radiation emitting device, by e.g. using wet deposition techniques, for example spin casting or doctor blade techniques. The substrate may be transparent for a bottom-emitting device or may be opaque in the case of a top-emitting device.  
      In a further embodiment of the method of the invention the radiation out-coupling material can also be formed in the shape of at least one lens. This structuring can be performed by using for example hot embossing, UV embossing methods, spin casting, laser structuring or injection moulding. A substrate, for example a silicon wafer can be structured using photolithographic techniques thereby generating a “negative” form of the lenses to be formed. Subsequently the material for the radiation out-coupling material is applied onto the structured wafer and hardened by e.g. polymerisation, thereby forming the at least one lens. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
      In the following some embodiments of the invention will be explained in more detail by Figures and embodiments. All Figures are just simplified schematic representations presented for illustration purposes only.  
       FIGS. 1A  to  1 C show different embodiments of a radiation emitting electronic device formed as an OLED.  
       FIGS. 2A  to  2 D show different embodiments of an OLED with a radiation out-coupling material comprising one lens or an array of microlenses.  
       FIGS. 3A and 3B  depict other embodiments of the invention wherein the radiation out-coupling material comprises two sub-layers.  
       FIG. 4  is a schematic representation showing one possible mode of action of the out-coupling material.  
       FIG. 5  is a graph showing the differences in the out-coupled light between an OLED according to one embodiment of the invention and a conventional OLED. 
    
    
     DETAILED DESCRIPTION OF THE DRAWINGS  
       FIG. 1A  shows a cross-sectional view of a radiation emitting electronic device  1  according to one embodiment of the invention. The radiation emitting device  1  is formed e.g. as an organic light emitting diode (OLED). A functional stack of a first electrode  10 A, at least one organic functional layer  15  on the first electrode  10 A and a second electrode  10 B is arranged on a transparent substrate  5 , which is formed of a transparent material for example glass or transparent polymer. In-between the first electrode  10 A and the substrate  5  a radiation out-coupling material layer  20  is formed, which enhances the fraction of out-coupled light produced in the organic functional layer  15 . The main direction of emission of light is indicated by an arrow marked with the reference number  100 . The radiation out-coupling material layer  20  is arranged in the main direction of the emitted light i.e. in the optical path of the light emitting organic functional area  15 . In the case that such an OLED also emits light through its side faces  1 A,  1 B or through its second electrode  10 B, additional radiation out-coupling material layers  20  can also be formed on the side faces or the second electrode.  
       FIG. 1B  depicts a cross-sectional view of another organic electronic device  1  according to another embodiment of the invention. In contrast to the electronic device of  FIG. 1A  the radiation out-coupling material is arranged in the form of a layer  20  on the main surface area of the substrate  5  opposite to the functional stack  10 A,  15 ,  10 B. In this case the amount of out-coupled light from the OLED  1  can also be enhanced.  
       FIG. 1C  shows another embodiment of the invention. In this case an additional transparent encapsulation  30  is formed over the functional stack  10 A,  15 ,  10 B. This encapsulation is formed by using a transparent material, for example glass or polymer, so that the light generated by the functional stack can be emitted through this encapsulation  30 , which also may be a thin film encapsulation. A radiation out-coupling layer  20  is arranged between the encapsulation  30  and the second electrode  10 B in the optical path  100  indicating the main direction of the emission of the generated light. It is also possible that the OLED device of  FIG. 1C  is not just a top-emitting but also a bottom-emitting device, as indicated by the dashed arrow  110 . In this case an additional radiation out-coupling material layer  20  may be present, as shown in  FIG. 1A  or  1 B.  
       FIG. 2A  shows an OLED device  1  having a lens  20 E comprising the radiation out-coupling material  20 . In contrast to the layers  20  shown in the  FIGS. 1A  to  1 C this lens is also able to focus the intensity of the emitted radiation in the emission direction in the optical path  100  of the OLED device  1 .  
       FIG. 2B  depicts another cross-sectional view of an OLED device  1  according to another embodiment of the invention. In contrast to  FIG. 2A , not one big lens  20 E but a microarray  20 F of a lot of microlenses is formed from the radiation out-coupling material. A layer  20 F formed in such a manner can also focus the out-coupled light and increases the fraction of out-coupled light. Devices with such a microarray of lenses are easier for encapsulation, can be used for flexible LEDs and are still thin compared to an LED with one big microlense. This array of microlenses can also form a so called surface-relief diffractive optical element (DOE).  
       FIGS. 2C and 2D  show the devices of  FIGS. 2A and 2B  respectively, where the big lens  20 E and the microarray of lenses  20 F are both arranged on the substrate  5  instead of the second electrode  10 B of the functional stack. The devices of the  FIGS. 2C and 2D  are both bottom-emitting devices, whereas the devices of the  FIGS. 2A and 2B  are top-emitting devices. Radiation-emitting devices of another embodiment of the invention can also be both, top- and bottom-emitting devices.  
       FIG. 3A  shows in cross-sectional view an organic radiation emitting device  1  according to another embodiment of the invention. In this case the radiation out-coupling layer  20  comprises two sub-layers  20 A and  20 B. As mentioned, above both sub-layers  20 A and  20 B can have a different refractive index, the refractive index decreasing from layer  20 A to  20 B thereby increasing the fraction of out-coupled light. Such a layer  20  including the sub-layers can easily be formed by depositing thin sub-layers having different ratios of polysilsesquioxane and for example titanium dioxide particles as transparent inorganic nanoparticles.  
       FIG. 3B  depicts a bottom-emitting device wherein the radiation out-coupling layer  20  comprising two sub-layers  20 A and  20 B is arranged on the substrate  5 .  
       FIG. 4  shows in cross-sectional view one possible mode of action of the radiation out-coupling layer  20 . This layer  20  comprises a polysilsesquioxane matrix  20 D with uniformly dispersed inorganic transparent nanoparticles  20 C such as e.g. titanium dioxide particles. These titanium dioxide particles have a higher refractive index than the polysilsesquioxane matrix  20 D. The nanoparticles  20 C can act as scattering centers, scattering light denoted by the arrow  210  emitted from the emitter  25  which otherwise would be trapped in the device due to reflection. Apart from that the radiation out-coupling layer  20  also out-couples light via refraction as shown by the arrow denoted with the reference number  200 .  
      In all embodiments shown in FIGS.  1  to  4  the transparent inorganic nanoparticles are titanium dioxide particles.  
     Embodiment  
      A dispersion containing 70 weight % titanium dioxide particles (particles size 300 nm) and 30 weight % tris-glycidylisopropyl-silsesquioxane monomers of the following formula:  
                 
 
      With R=iso-butyl in cyclohexane (10 weight % of the full mass in solution) was applied via spin coating on the transparent substrate of an OLED device. Subsequently the film was dried at room temperature for half an hour using vacuum for five minutes and furthermore polymerized under argon atmosphere at 240°.  
      The luminance of this OLED device was compared to the luminance of a conventional OLED device having no radiation out-coupling material. The result of this comparison is shown in the graph in  FIG. 5 . The x-axis denotes the viewing angle in degree [°] and the y-axis denotes the luminance in [Cd/m 2 ]. The curve marked with the reference number  300  shows the luminance of an OLED device with a radiation out-coupling area according to the invention, and the curve with the reference numeral  310  shows the same luminance of a conventional OLED device having no radiation out-coupling layer. It can clearly be seen that the radiation out-coupling layer enhances the luminance of the OLED device (10% enhancement at 0° C.).  
      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 feature 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. Variations of the invention are for example possible regarding the composition and the size of the inorganic nanoparticles, the shape of the radiation out-coupling material and the substrate and the layer setup.