Title of Invention	"LIGHT EMITTING COMPONENT COMPRISING ORGANIC LAYERS"
Abstract	The invention relates to a light-emitting component having organic layers, in particular to an organic light-emitting diode. The component has at least one doped charge carrier transport layer (2), a light-emitting layer (4) and contact layers (1, 5) and also has a blocking layer (3; 3') wherein an organic material is provided between the charge carrier transport layer (2,2') and the light-emitting layer (4). The energy levels of the charge carried transport layer are chosen in such a way that efficient doping is possible and the blocking layer nevertheless ensures that non-radiating recombination processes on the interface with the emitting layer are prevented.

Title of Invention

"LIGHT EMITTING COMPONENT COMPRISING ORGANIC LAYERS"

Abstract

The invention relates to a light-emitting component having organic layers, in particular to an organic light-emitting diode. The component has at least one doped charge carrier transport layer (2), a light-emitting layer (4) and contact layers (1, 5) and also has a blocking layer (3; 3') wherein an organic material is provided between the charge carrier transport layer (2,2') and the light-emitting layer (4). The energy levels of the charge carried transport layer are chosen in such a way that efficient doping is possible and the blocking layer nevertheless ensures that non-radiating recombination processes on the interface with the emitting layer are prevented.

Full Text	Light-Emitting Component Comprising Organic Layers Description The invention relates to a light-emitting component comprising organic layers, in particular an organic light-emitting diode according to the generic clause of Claim 1. Since the demonstration of low operating voltages by Tang et al., 1987 [C.W. Tang et al. Appl. Phys. Lett. 51 (12) 913 (1987)], organic light-emitting diodes have been promising candidates for the realization of large-area displays. They consist of a sequence of thin (typically 1 nm to 1 urn) layers of organic materials, which preferably are produced by vacuum deposition or by spin-on deposition in their polymer form. After electrical contacting by metallic layers they form a great variety of electronic or optoelectronic components, such as for example diodes, light-emitting diodes, photodiodes and transistors, which, in terms of properties, compete with established components based on inorganic layers. In the case of organic light-emitting diodes (OLEDs), light is produced and emitted by the light-emitting diode by the injection of charge carriers (electrons from one side, holes from the other) from the contacts into adjacent organic layers as a result of an externally applied voltage, subsequent formation of excitons (electron-hole pairs) in an active zone and radiant recombination of these excitons. The advantage of such organic components as compared with conventional inorganic components (semiconductors such as silicon, gallium arsenide) is that it is possible to produce large-area elements, i.e., large display elements (visual displays, screens). Organic starting materials, as compared with inorganic materials, are relatively inexpensive (less expenditure of material and energy). Moreover, these materials, because of their low processing temperature as compared with inorganic materials, can be deposited on flexible substrates, which opens up a whole series of new applications in display and illuminating engineering. The basic construction of such a component represents an arrangement of one or more of the following layers: 1. Carrier, substrate 2. Base electrode, hole-injecting (positive pole), usually transparent 3. Hole-injecting layer 4. Hole-transporting layer (HTL) 5. Light-emitting layer (EL) 6. Electron-transporting layer (ETL) 7. Electron-injecting layer 8. Cover electrode, usually a metal with low work function, electron-injecting (negative pole) 9. Encapsulation, to shut out ambient influences. This is the most general case; often several layers are omitted (except 2nd, 5th and 8th), or else one layer combines several properties. US 5,093,698 discloses that the hole-conducting and/or the electron-conducting layer may be doped with other organic molecules, in order to increase their conductivity. Further research, however, has failed to pursue this approach. Additional well-known approaches for the improvement of electrical properties of OLEDs (i.e., especially operating voltage and light-emission efficiency) are: 1) Improving the light-emitting layer (novel materials) [Hsieh et al., US 5,674,635]; 2) Constructing the light-emitting layer of a matrix material and a dopant, where transfer of energy takes place from the matrix to the dopant and radiant recombination of excitons takes place only on the dopant [Tang et al., US 4,769,292, US 5,409,783, H. Vestweber, W. Riess: "Highly efficient and stable organic light-emitting diodes," in Synthetic Metal 91 (1997), pp. 181-185]; 3) Producing polymers (capable of spin-on deposition) or substances of low molecular weight (capable of vacuum deposition) which combine a number of favorable properties (conductivity, layer formation), or producing them of a mixture of a variety of materials (especially in the case of polymer layers) [Mori et al., US 5,281,489]; 4) Improving the injection of charge carriers into organic layers by using a number of teyers with stepwise coordination of their energy levels, or using appropriate mixtures of a number of substances [Fujii et al., US 5,674,597, US 5,601,903, Sato et al., US 5,247,226, Tominaga et al., Appl. Phys. Lett. 70 (6), 762 (1997), Egusa et al., US 5,674, 597]; 5) Improving the transport properties of transport layers by admixing a more suitable material with the transport layer. There, transport takes place in for example the hole layer on the dopant/the admixture (in contrast to the doping mentioned above, in which transport of the charge carriers takes place on the molecules of the matrix material) [Y. Hamada et al., EP 961,330 A2]. Unlike light-emitting diodes based on inorganic materials, which have long found wide use in practice, organic components have hitherto had to be operated at considerably higher voltages . The reason for this lies in the poor injection of charge carriers from the contacts into organic layers and in the comparatively poor conductivity and mobility of charge-carrier transport layers. A potential barrier is formed at the contact material/charge-carrier transport layer interface, which makes for a considerable increase in operating voltage. The use of contact materials with a fairly high energy level (= low work function) for the injection of electrons into the adjacent organic layer, as is shown schematically in US 5,093,698, or contact materials with still lower energy levels (higher work functions) for the injection of holes into an adjacent organic layer, might provide a remedy. In the first case, the extreme instability and reactivity of the corresponding metals and, in the second case, the low transparency of these contact materials speaks against this. In practice, therefore, at this time indium tin oxide (ITO) is used almost exclusively as the injection contact for holes (a transparent degenerate semiconductor), whose work function, however, is still too small. Used for the injection of electrons are materials such as aluminum (Al), Al in combination with a thin layer of lithium fluoride (LiF), magnesium (Mg), calcium (Ca) or a mixed layer of Mg and silver (Ag). The use of doped charge-carrier transport layers (p-doping of the HTL by admixture of acceptor-like molecules, n-doping of the ETL by admixture of donorlike molecules) is described in US 5,093,698. By doping in this sense is meant that the admixture of doping substances into the layer increases the equilibrium charge-carrier concentration in this layer, compared with the pure layers of one of the two substances concerned, which results in improved conductivity and better charge-carrier injection from the adjacent contact layers into this mixed layer. The transport of charge carriers then still takes place on the matrix molecules. According to US 5,093,698, the doped layers are used as injection layers at the interface to the contact materials, the light-emitting layer being found in between (or, when only one doped layer is used, next to the other contact). Equilibrium charge-carrier thickness, increased by doping, and associated band bending, facilitate charge-carrier injection. The energy levels of the organic layers (HOMO = highest occupied molecular orbital or highest energetic valence band energy; LUMO = lowest unoccupied molecular orbital or lowest energetic conduction band energy), according to US 5,093,698, should be obtained so that electrons in the ETL as well as holes in the HTL can be injected into the EL without further barriers, which requires very high ionization energy of the HTL material and very low electron affinity of the ETL material. However, such materials are hard to dope, since extremely strong acceptors and donors would be required, so that these conditions cannot be fully met on both sides with materials that are actually available. Now, if HTL and ETL materials that do not meet these conditions are used, when voltage is applied an accumulation of charge carriers develops in the transport layers at the interfaces to the emitting layer (EL). Such an accumulation in principle promotes non-radiant recombination of excitons at the interface by, for example, the formation of exciplexes (these consist of a charge carrier in the HTL and ETL and of the opposite charge carrier in the EL). Such exciplexes recombine mainly non-radiantly, so that exciplex formation represents a non-radiant recombination mechanism. In addition, the problem of exciplex formation becomes more acute when doped HTLs and ETLs are used, since in doped materials the Debye shielding length is very small and hence high charge-carrier thicknesses occur directly at the interface. In addition, dopants in the immediate vicinity of the EL may result in quenching of fluorescence by, for example, Fbrster transfer. Blocking layers in OLEDs for improving the charge carrier balance in the respective light-emitting layer are disclosed in the literature. Their function consists of preventing charge carriers from leaving the light-emitting layer. In the case of electrons in the emitter layer, therefore, the condition is that the LUMO of the electron blocking layer (which is located between the emitter and the hole-transport layers) must lie distinctly over the LUMO of the emitter layer and the blocking layer must be designed thick enough so that no tunneling of electrons into the following hole-transport layer can take place. For the holes in the emitter layer, the same arguments apply to the energies of the HOMOs. Examples of this may be found in: M.-J. Yang and AT. Tsutsui: "Use of poly(9-vinylcarbazole) as host material of iridium complexes in high-efficiency organic light-emitting devices" in Jpn. J. Appl. Phys. 39 (2000), Part 2, No. 8A, pp. L828-L829; R.S. Deshpande et al.: "White-light-emitting organic electroluminescent devices based on interlayer sequential energy transfer" in Appl. Phys. Lett. 75 (1999) 7, pp. 888-890; M. Hamaguchi and K. Yoshino: "Color-variable emission in multilayer polymer electroluminescent devices containing electron-blocking layer" in Jpn. J. Appl. Phys. 35 (1996), Part 1, No. 9A, pp. 4813-4818. The selection of suitable blocking layers and hence the restriction of possible emission zones is of special importance for the production of special blue OLEDs. Reference to exciplex formation between organic emitter materials and undoped transport materials with low ionization energy are found in: K. Itano et al.: "Exciplex formation at the organic solid-state interface: yellow emission in organic light-emitting diodes using green-fluorescent tris(8-quinolinolato) aluminum and hole-transporting molecular materials with low ionization potentials" in Appl. Phys. Lett. 72 (1998) 6, pp. 636-638; T. Noda et al. "A blue-emitting organic electroluminescent device using a novel emitting amorphous molecular material, 5,5'-bis(dimesitylboryl)-2,2'-bithiophene" in Adv. Mater. 11 (1999) 4, pp. 283-285. In the latter, the use of a blocking layer for reducing this effect is proposed, although not in connection with doped transport layers. The basic dilemma, that materials with deep-lying HOMO are hard to p-dope, but materials with high-lying HOMO promote exciplex formation at the interface to the emitting layer, has not yet been recognized in the professional literature. Accordingly, there are also no patents that propose solutions to this problem. The object of the invention is to indicate a light-emitting component on the basis of doped charge-carrier transport layers, which can be operated at a reduced operating voltage and has high light-emission efficiency. According to the invention, the object is accomplished, in conjunction with ' the features mentioned in the generic clause of Claim 1, in that between the doped charge-carrier transport layer and the light-emitting layer, there is provided a blocking layer of an organic material, the blocking layer being obtained so that the occurrence of non-radiant recombination channels, in particular due to exciplex formation at the interface to the emitter layer, is prevented. The component preferably is realized in that the energy levels of the blocking layers, charge-carrier transport layers and emitter layers are adapted to one another as j follows (see list of reference characters and numerals and Figure 3): a) Condition for p-doped hole-transport layer (2) and hole-side blocking layer (3): EvP > Evbiockp (highest occupied molecular energy level (in the valence band, HOMO) of the injection and transport layer for holes > HOMO energy of the hole-side blocking layer), b) Condition for n-doped electron-transport layer (2') and electron-side blocking layer (3'): Ecn c) Condition for hole-side blocking layer (3) and emitting layer (4): Evbiockp- Evei d) Condition for electron-side blocking layer (3') and emitting layer (4): Ecbiockn - Ecei > - 0.3 eV (LUMO energy of electron-side blocking layer - LUMO energy of light-emitting layer > - 0.3 eV). There, deviations from the stated values should always correspond to several kT at the operating temperature of the component (by several kT is meant up to 5 kT, i.e., approx. 5*25 meV at room temperature). The charge-carrier transport layer is doped by an admixture of an organic or inorganic substance (dopant). There, the energy level of the majority charge-carrier transport state is selected so that, with the given dopant, efficient doping is possible (as complete as possible charge transfer from matrix to dopant). According to the invention, the blocking layer is located between the charge-carrier transport layer and a light-emitting layer of the component, in which conversion of the electric energy of the charge carrier injected by flow of current through the component takes place in light. According to the invention, the substances of the blocking layer are selected so that when voltage is applied (in the direction of the operating voltage), because of its energy level no accumulation of majority charge carriers (HTL-side: holes, ETL-side: electrons) in the blocking layer occurs at the interface to the emitting layer. In order to realize this condition simultaneously with the demand for more efficient dopability, an energy barrier for the injection of charge carriers from the transport layer into the blocking layer is accepted. In this respect, this approach clearly differs from that presented in the patent of Ogura et al., EP 1,017,118 A2: None of the examples listed in the latter patent meets the above conditions. Accordingly, the light-emitting diodes mentioned there are also clearly poorer with respect to operating voltage as well as to efficiency than the examples given by us. The blocking layer proposed in patent EP 1,017,118 A2 acts only to prevent the injection of minority charge carriers. This function can also be satisfied by the blocking layer proposed by us, i.e., it should in addition meet the condition that minority charge carriers are efficiently arrested at the light-emitting layer/blocking layer interface. In a preferred embodiment of the component, the energy levels of the blocking layers and of the emitter layer therefore satisfy the following conditions: a) Condition for hole-side blocking layer (3) and emitting layer (4): Ecbiockp > ECei (LUMO energy of hole-side blocking layer > LUMO energy of light-emitting layer), b) Condition for electron-side blocking layer (3') and emitting layer (4): Evbiockp energy of light-emitting layer). Additionally advantageous for a component of this patent is the fact that the energy gap of the doped transport layers is selected great enough so that injection of minority charge carriers from the emitting layer into the doped transport layer is not even possible when the blocking layer is so thin that it can be tunneled through. According to the invention, this is accomplished in that the following conditions are met: a) Condition for p-doped hole-transport layer (2) and emitting layer (4): EcP > ECei (LUMO of injection and transport layer for holes > LUMO energy of light-emitting layer), b) Condition for electron-side blocking layer (2') and emitting layer (4): Evn HOMO energy of light-emitting layer). An advantageous embodiment of a structure of an OLED according to the invention contains the following layers: 1. Carrier, substrate, 2. Base electrode, hole-injecting (anode = positive pole), preferably transparent, 3. p-doped hole-injecting and transporting layer, 4. Hole-side blocking layer (typically thinner than p-doped layer in item 3) of a material whose band levels match the band levels of the enclosing layers, 5. Light-emitting layer, 6. Thinner electron-side blocking layer of a material whose band positions match the band positions of the layers enclosing them, 7. Highly n-doped electron-injecting and transporting layer, 8. Cover electrode, usually a metal with low work function, electron-injecting (cathode = negative pole), 9. Metal protection, to shut out ambient influences. According to the invention, the substances of the blocking layers are selected so that when voltage is applied (in the direction of the operating voltage), their energy levels allow them to inject charge carriers efficiently into the light-emitting layer (EL) and non-radiant recombination processes such as exciplex formation at the interface to the EL are unlikely, but charge carriers in the EL cannot be injected into the said second layer. This means that the substances of the blocking layers, according to the invention, are selected so that when voltage is applied (in the direction of the operating voltage), because of their energy levels they arrest majority charge carriers (hole-side: holes, electron-side: electrons) mainly at the doped charge-carrier transport layer/ blocking layer interface, but arrest minority charge carriers efficiently at the light-emitting layer/blocking layer interface. It is likewise within the scope of the invention when only one blocking layer is used, because the band levels of the injecting and transporting layer and of the light-emitting layer already match one another on one side. Alternatively, only one side (hole- or electron-conducting) may be doped. In addition, the functions of charge-carrier injection and of charge-carrier transport into layers 3 and 7 may be divided among a number of layers, of which at least one is doped. Molar doping concentrations typically lie in the range of 1:10 to 1:10000. If the dopants are substantially smaller than the matrix molecules, in exceptional cases there may alternatively be more dopants than matrix molecules in the layer (up to 5:1). The dopants may be organic or inorganic. Typical layer thicknesses for the blocking layers lie in the range of 1 nm to 20 nm, but they may alternatively be thicker. Typically, the blocking layers are thinner than their corresponding adjacent doped layers. The layer thicknesses of the blocking layers must be great enough to prevent exciplex formation between charged molecules of the substances in the corresponding adjacent mixed layers and charged molecules of the electroluminescent layer and quenching of luminescence by dopants themselves. In summary, the accomplishment according to the invention may be described as follows: In order to be able to p-dope an organic transport material efficiently (explained here only for the hole side, the electron side follows analogously with exchange of the terms HOMO and LUMO), its ionization potential must be relatively small, owing to which a greater HOMO distance between the transport layer and the emitter layer is obtained. A consequence of efficient doping is that all dopants are present in the layer completely ionized (in the case of p-doping the dopants, the acceptors, are all negatively charged). Therefore, electron injection from the emitter layer to the dopants of the transport layer is no longer possible. This disadvantage, which no longer exists with efficient doping, is gone into in the patent of Ogura et al., EP 1,017,118 A2. There, it is taken care of by blocking layers for preventing the injection of electrons from the emitter layer into the hole-transport layer. In contrast to this, in the accomplishment proposed here the blocking layer may be selected extremely thin, since it is designed mainly to prevent exciplex formation but need not represent a tunnel barrier for charge carries (in contrast to the patent of Ogura et al, EP 1,017,118 A2) Light-emitting component comprising organic layers, in particular organic light-emitting diode, consisting of at least one doped charge-carrier transport layer, a light-emitting layer and contact layers, characterized in that between the charge-carrier transport layer and the light emitting layer there is provided a blocking layer of an organic material wherein the transport layer, Light Emitting layer and blocking layer must fulfill all the following conditions for their energy level:- (a) Condition for p-doped hole-transport layer(2) and hole-side blocking layer(3): EVp>Evbiockp [highest occupied molecular energy level(in the valance band, HOMO) of the injection and transport layer for holes>HOMO energy of the hole-side blocking layer], (b) Condition for n-doped electron-transport layer(2') and electron-side blocking layer(3'): Ecn (c) Condition for hole-side blocking layer(3) and emitting layer(4): Evbiockp-Evei (d) Condition for electron-side blocking layer(3') and emitting layer(4): Ecbiockn-Ecei> -0.3eV(LUMO energy of electron-side blocking layer-LUMO energy of light-emitting layer>-0.3eV) (e) Condition for hole-side blocking layer(3) and emitting layer(4): Ecbiockp> ECei(LUMO energy of hole-side blocking layer > LUMO energy of light-emitting layer) (f) Condition for electron-side blocking layer(3') and emitting layer(4): EvbiockP (g) Condition for p-doped hole transport layer (2) and emitting layer (4): EcP> Ecei (LUMO of injection and transport layer for electron > LUMO energy of light-emitting layer) (h) Condition for electron-side blocking layer(2') and emitting layer(4): EVn The invention is described below in greater detail by means of examples. In the drawings, Figure 1 shows a theoretically ideal doped OLED structure Figure 2 a doped OLED without blocking layer, existing in practice, Figure 3 a doped OLED with blocking layers Figure 4 an OLED doped only on the hole side, with blocking layer there A theoretically ideal structure is represented in Figure 1, consisting of an anode (EA), a highly p-doped hole injection and transport iayer (Evp, EcP, EFP), an electroluminescent layer (Evei, Ecei, EFei), a highly n-doped electron-injecting and transport layer (Evn, ECn, EFn) and a cathode. When voltage is applied (anode polarized positively), holes from the anode and electrons from the cathode are injected in the direction of the light-emitting layer. Since no barrier occurs (Evp > Evei) for holes at the interface of the p-doped layer to the light-emitting layer, nor for electrons at the interface of the n-doped layer to the light emitting layer (Ecn > ECei), and a higher barrier exists (Ecei EVp) at the interface of the light emitting layer to the p-doped and n-doped layer for electrons and holes respectively, the charge carriers (electrons and holes) collect in the light-emitting layer, where they can efficiently form excitons and recombine radiantly. In reality, layer combinations with the parameters mentioned above are not yet to be found and perhaps will never be found, since these layers must bring together a great number of some opposing properties. A realizable layer structure looks like the one shown in Figure 2 (schematic band levels). The organic acceptor thus far best known for p-doping of organic materials (tetra-fluoro-tetracyano-quinodimethane F4 - TCNQ) is capable, because of its band level ECpdot. of doping materials efficiently at a valence band level of about EvP = - 5.0...-5.3 eV. The material most used for producing electroluminescence, aluminum-tris-quinolinate (Alq3) has a valence band level of Evei = - 5.65 eV. Thus, the holes conducted into the p-doped layer are blocked at the interface to the electroluminescent layer (EvP > Evei)- The same applies to the interface between n-doped and light-emitting layer (Ecn EVn), as described earlier for the theoretically ideal case. However, the result of this is that when voltage is applied, charge carriers accumulate at the interfaces of the doped layers to the light-emitting layer. Upon accumulation of an opposite charge on two sides of an interface, increased non-radiant recombination processes occur due, for example, to formation of exciplexes, which again reduces the efficiency of conversion of electrical into optical energy. Thus, with an LED having this layer structure, the operating voltage can be reduced by doping, but only at the cost of efficiency. According to the invention, the disadvantage of the previous structures is avoided by OLEDs with doped injection and transport layers in combination with blocking layers. Figure 3 shows a suitable arrangement. Between the hole-injecting and conducting layer and the light-emitting layer, there is here located an additional layer, the hole-side blocking layer. The most important conditions for the selection of this layer are: Evbiockp - Evel Ecei. so that electrons cannot leave the light-emitting layer. Similarly, and with the same arguments, the following must apply on the electron side: Ecwockn- Ecei > - 0.3 eV and Evbiockn Evei and Ecn longer present in the immediate vicinity of excitons in the light-emitting layer, so that quenching of luminescence by dopants is ruled out. This arrangement is characterized by the following advantages: A high charge-carrier thickness of both kinds in the light-emitting layer even at low voltages Outstanding injection of charge carriers from anode and cathode into the p- and n-doping charge-carrier transport layers Outstanding conductivities in the doped layers Because of their small thickness only small voltage losses in the blocking layers No formation of exciplexes, because of spatial separation of charge carriers of unlike polarity No quenching by dopants Together, this results in high conversion efficiencies at low operating voltage for OLEDs having this layer structure. In this connection, mixed layers known in the literature, which increase the recombination efficiency of excitons, or likewise well-known phosphorescent material systems with their high quantum efficiency, may alternatively be used for the light-emitting layer. According to the invention, layers doped on only one side (hole or electron side) may alternatively be used in combination with a blocking layer (only one) described above (Figure 4). The layer sequence according to the invention necessarily results in a stepwise increase of the transport levels EA vice versa, a stepwise decrease of the transport levels EK As a preferred example, an accomplishment is to be indicated here, in which the combination of p-doped injection and transport layer and blocking layer is used only on the hole side. The OLED has the following layer structure: 1. Anode: indium tin oxide (ITO) 2. p-doped layer: 100 nm Starburst ATDATA 50:1 doped with F4-TCNQ 3. Hole-side blocking layer: 10 nm triphenyldiamine (TPD) 4. Electroluminescent and (in this case) conventional electron-conducting layer: 65 nm Alq3 5. Cathode: 1 nm LiF in combination with aluminum (LiF improves injection at the contact). The mixed layer (2nd) was produced in a vacuum deposition process in mixed deposition. In principle, such layers may alternatively be produced by other methods, such as, for example, deposition on one another of the substances with subsequent possibly temperature-controlled diffusion of the substances into one another; or by other deposition (e.g., spin-on deposition) of the already mixed substances in or outside a vacuum. The blocking layer was likewise deposited under vacuum, but may alternatively be produced differently, e.g., by spin-on deposition in or outside a vacuum. The energy levels of the HOMO and LUMO energies are: 1. ITO work function EA ~ - 4.6 eV (highly preparation-dependent) 2. TDATA: EVp = - 5.1 eV, ECp « -2.6 eV 3. TPD: Evbiockp = - 5.4 eV, ECbiockP = - 2.3 eV 4. Alq3: EVei = - 5.65 eV, ECei = - 2.9 eV 5. Al: EK = - 4.3 eV In this arrangement, the requirements EvbiockP-Evei Ecei (0.6 eV), as well as EVp > Evwockp (0.3 eV) are met. In this preferred embodiment, the LUMO of the hole=transport layer (TDATA ECp) is distinctly higher (0.3 eV) than the LUMO of the emitter layer (Alq3 ECei). This is not absolutely necessary but is advantageous, in order not to permit tunneling of electrons from the emitter layer into the hole-transport layer through the thin blocking layer. At 3.4 V, this OLED has a luminescence of 100 cd/m2, with an efficiency of 5 cd/A. With an undoped TDATA layer, 100 cd/m2 are obtained only at about 7.5 V. In an OLED as described above, but without a TPD blocking layer, the characteristic data are: 8 V for 100 cd/m2 and an efficiency poorer by a factor of 10! This example shows how effective the combination of doped transport layer and blocking layer is with regard to optimization of operating voltage and light-emission efficiency. An additional embodiment of the component according to the invention consists in that additional small quantities (0.1 - 50%) of an emissive colorant are mixed into the emitter layer (in the literature, this admixture is also called doping - but not doping in the sense of this patent - and admixtures therefore are called emitter dopants). These may, for example, be quinacridone in Alq3 in the example mentioned above or a triplet-emitter such as Ir(ppy) (tris(2-phenylpyridine)iridium) in matrix materials such as TCTA (tris(carbazolyl)-triphenylamine), BCP (bathocuproine), CBP (dicarbazole-biphenyi) and the like. For a triplet emitter, the concentration of the emitter dopant is usually greater than 1 %. For these combinations of material, the blocking layer must prevent exciplex formation between the blocking layer materials and the emitter dopants. Exciplex formation in electron-hole pairs on molecules of blocking layer material and matrix material may thus be possible, as long as majority charge carriers are able to pass over directly (i.e., even without exciplex formation from electron-hole pairs on blocking layer molecules and emitter dopant molecules) into states of the emitter dopant, and therefore exciplex formation on blocking layer molecules/ matrix molecules is then prevented. Therefore, the positions of HOMO and LUMO levels of the emitter dopant are important energy conditions for the connection of blocking layers to light-emitting layers: a) Condition for hole-side blocking layer (3) and emitting layer with emitter dopant (4): Evbiockp - Eveidotand b) Condition for electron-side blocking layer (3rd) and emitting layer with emitter dopant (4): Ecbiockn - ECei > - 0.3 eV (LUMO energy of electron-side blocking layer -LUMO energy of emitter dopant in the light-emitting layer > - 0.3 eV). List of reference characters and numerals EA work function of anode EvP highest occupied molecular energy level (in the valence band, HOMO) of the injection and transport layer for holes ECp lowest unoccupied molecular energy level (conduction band or LUMO) of the injection and transport layer for holes Ecpdot LUMO energy of p-doping material (acceptor) EFP Fermi level of p-doped layer Evbiockp HOMO energy of hole-side blocking layer Ecbiockp LUMO energy of hole-side blocking layer t^Fblockp Fermi level of hole-side blocking layer Evei HOMO energy of light-emitting layer Ecei LUMO energy of light-emitting layer EFei Fermi level of light-emitting layer Evbiockn HOMO energy of electron-side blocking layer tCblockn LUMO energy of electron-side blocking layer CFblockn Fermi level of electron-side blocking layer Evn HOMO energy of injection and transport layer for electrons Ecn LUMO energy of injection and transport layer for electrons Evndot HOMO energy of n-doping material (donor) EFH Fermi level of injection and transport layer for electrons EK work function of cathode 1 - anode 2 - hole-transport layer 2' - electron-transport layer 3 - hole-side blocking layer 3" - electron-side blocking layer 4 - light-emitting layer 5 - cathode 6 - electron-transporting and light-emitting layer WE CLAIM: 1. Light-emitting component comprising organic layers, in particular organic light-emitting diode, consisting of at least one doped charge-carrier transport layer (2), a light-emitting layer (4) and contact layers (1,5), characterized in that between the charge-carrier transport layer (2) and the light emitting layer (4) there is provided a blocking layer (3) of an organic material wherein the transport layer(2), Light Emitting layer(4) and blocking layer(3) must fulfill all the following conditions for their energy level:- (a) Condition for p-doped hole-transport layer(2) and hole-side blocking layer(3): EVp>Evblockp [highest occupied molecular energy level(in the valance band, HOMO) of the injection and transport layer for holes>HOMO energy of the hole-side blocking layer], (b) Condition for n-doped electron-transport layer(2') and electron-side blocking layer(3'): Ecn (c) Condition for hole-side blocking layer(3) and emitting layer(4): Evblockp-Evel (d) Condition for electron-side blocking layer(3") and emitting layer(4): Ecbiockn-Ecei> -0.3eV(LUMO energy of electron-side blocking layer-LUMO energy of light-emitting layer>-0.3eV) (e) Condition for hole-side blocking layer(3) and emitting layer(4): EcbiockP> ECel(LUMO energy of hole-side blocking layer > LUMO energy of light-emitting layer) (f) Condition for electron-side blocking layer(3') and emitting layer(4): Evbiockp (g) Condition for p-doped hole transport layer (2) and emitting layer (4): Ecp> Ecel (LUMO of injection and transport layer for electron > LUMO energy of light-emitting layer) (h) Condition for electron-side blocking Iayer(2') and emitting layer(4): Evn 2. Light-emitting component comprising organic layers as claimed in claim 1, wherein the component consists of a hole-injecting anode (1), a hole-transport layer (2) for hole conduction from a principal organic substance and acceptorlike doping substance, a first organic hole-side blocking layer (3), a light-emitting layer (4), a second organic electron side blocking layer (3'), an electron-transport layer (2') for the conduction of electrons from a principal organic substance and donor-like doping substance, and a cathode (5) for the injection of electrons. 3. Light-emitting component comprising organic layers as claimed in claim 1 or 2, wherein anode (1) and cathode (5) are metallic. 4. Light-emitting component comprising organic layers as claimed in claims 1 to 3, wherein the layer sequence of hole-transport layer (2), blocking layer (3) and light-emitting layer (4) is repeatedly provided. 5. Light-emitting component comprising organic layers as claimed in claims 1 to 4, wherein the light-emitting layer consists of a plurality of layers. 6. Light-emitting component comprising organic layers as claimed in claims 1 to 5, wherein a contact-improving layer is in each instance provided between the anode (1) and the hole-transport layer (2) and/or between the electron- transport layer (2') and the cathode (5). 7. Light-emitting component comprising organic layers as claimed in claims 1 to 6, wherein the molar concentration of the admixture in the hole-transport layer (2) and/or in the electron transport layer (2') lies in the range of 1:100,000 to 5:1, referred to the ratio of doping molecules to principal substance molecules. 8. Light-emitting component comprising organic layers as claimed in claims 1 to 7, wherein the layer thickness of the hole-transport layer (2) and/or of the electron-transport layer (2') and pf the blocking layers (3,3') lie in the region of 0.1 nm to 50µm. 9. Light-emitting component comprising organic layers as claimed in claim 8, wherein the blocking layer (3,3') is thinner than its corresponding adjacent doped layers. 10. Light-emitting component comprising organic layers as claimed in claims 1 to 9, wherein the blocking layer (3,3') is sized with respect to adjacent energy layers so that majority charge carriers are arrested predominantly at the charge-carrier transport layer/blocking layer interface and minority carriers at the light-emitting layer/blocking layer interface. 11. Light-emitting component comprising organic layers as claimed in 1 to 10. wherein the layer thickness of the blocking layer (3,3') is sized so that exciplex formation between charged molecules of the substances in the corresponding adjacent transport layer (2,2') and charged molecules of the electroluminescent layer and quenching of luminescence by dopants is prevented. 12. Light-emitting component comprising organic layers as claimed in claim 1. wherein the energy levels refer to a combined state of layers. 13. Light-emitting component comprising organic layers as claimed in any of the above claims substantially as described in the specification and illustrated in the accompanying drawings.

Full Text

Light-Emitting Component Comprising Organic Layers Description
The invention relates to a light-emitting component comprising organic layers, in particular an organic light-emitting diode according to the generic clause of Claim 1.
Since the demonstration of low operating voltages by Tang et al., 1987 [C.W. Tang et al. Appl. Phys. Lett. 51 (12) 913 (1987)], organic light-emitting diodes have been promising candidates for the realization of large-area displays. They consist of a sequence of thin (typically 1 nm to 1 urn) layers of organic materials, which preferably are produced by vacuum deposition or by spin-on deposition in their polymer form. After electrical contacting by metallic layers they form a great variety of electronic or optoelectronic components, such as for example diodes, light-emitting diodes, photodiodes and transistors, which, in terms of properties, compete with established components based on inorganic layers.
In the case of organic light-emitting diodes (OLEDs), light is produced and emitted by the light-emitting diode by the injection of charge carriers (electrons from one side, holes from the other) from the contacts into adjacent organic layers as a result of an externally applied voltage, subsequent formation of
excitons (electron-hole pairs) in an active zone and radiant recombination of these excitons.
The advantage of such organic components as compared with conventional inorganic components (semiconductors such as silicon, gallium arsenide) is that it is possible to produce large-area elements, i.e., large display elements (visual displays, screens). Organic starting materials, as compared with inorganic materials, are relatively inexpensive (less expenditure of material and energy). Moreover, these materials, because of their low processing temperature as compared with inorganic materials, can be deposited on flexible substrates, which opens up a whole series of new applications in display and illuminating engineering.
The basic construction of such a component represents an arrangement of one or more of the following layers:
1. Carrier, substrate
2. Base electrode, hole-injecting (positive pole), usually transparent
3. Hole-injecting layer
4. Hole-transporting layer (HTL)
5. Light-emitting layer (EL)
6. Electron-transporting layer (ETL)
7. Electron-injecting layer
8. Cover electrode, usually a metal with low work function, electron-injecting (negative pole)
9. Encapsulation, to shut out ambient influences.
This is the most general case; often several layers are omitted (except 2nd, 5th and 8th), or else one layer combines several properties.
US 5,093,698 discloses that the hole-conducting and/or the electron-conducting layer may be doped with other organic molecules, in order to increase their conductivity. Further research, however, has failed to pursue this approach.
Additional well-known approaches for the improvement of electrical properties of OLEDs (i.e., especially operating voltage and light-emission efficiency) are:
1) Improving the light-emitting layer (novel materials) [Hsieh et al., US 5,674,635];
2) Constructing the light-emitting layer of a matrix material and a dopant, where transfer of energy takes place from the matrix to the dopant and radiant recombination of excitons takes place only on the dopant [Tang et al., US 4,769,292, US 5,409,783, H. Vestweber, W. Riess: "Highly efficient and stable organic light-emitting diodes," in Synthetic Metal 91 (1997), pp. 181-185];
3) Producing polymers (capable of spin-on deposition) or substances of low molecular weight (capable of vacuum deposition) which combine a number of favorable properties (conductivity, layer formation), or producing them of a mixture of a variety of materials (especially in the case of polymer layers) [Mori et al., US 5,281,489];
4) Improving the injection of charge carriers into organic layers by using a
number of teyers with stepwise coordination of their energy levels, or
using appropriate mixtures of a number of substances [Fujii et al.,
US 5,674,597, US 5,601,903, Sato et al., US 5,247,226, Tominaga et al., Appl. Phys. Lett. 70 (6), 762 (1997), Egusa et al., US 5,674, 597];
5) Improving the transport properties of transport layers by admixing a
more suitable material with the transport layer. There, transport takes
place in for example the hole layer on the dopant/the admixture (in
contrast to the doping mentioned above, in which transport of the
charge carriers takes place on the molecules of the matrix material)
[Y. Hamada et al., EP 961,330 A2].
Unlike light-emitting diodes based on inorganic materials, which have long found wide use in practice, organic components have hitherto had to be operated at considerably higher voltages . The reason for this lies in the poor injection of charge carriers from the contacts into organic layers and in the comparatively poor conductivity and mobility of charge-carrier transport layers. A potential barrier is formed at the contact material/charge-carrier transport layer interface, which makes for a considerable increase in operating voltage. The use of contact materials with a fairly high energy level (= low work function) for the injection of electrons into the adjacent organic layer, as is shown schematically in US 5,093,698, or contact materials with still lower energy levels (higher work functions) for the injection of holes into an adjacent organic layer, might provide a
remedy. In the first case, the extreme instability and reactivity of the corresponding metals and, in the second case, the low transparency of these contact materials speaks against this. In practice, therefore, at this time indium tin oxide (ITO) is used almost exclusively as the injection contact for holes (a transparent degenerate semiconductor), whose work function, however, is still too small. Used for the injection of electrons are materials such as aluminum (Al), Al in combination with a thin layer of lithium fluoride (LiF), magnesium (Mg), calcium (Ca) or a mixed layer of Mg and silver (Ag).
The use of doped charge-carrier transport layers (p-doping of the HTL by admixture of acceptor-like molecules, n-doping of the ETL by admixture of donorlike molecules) is described in US 5,093,698. By doping in this sense is meant that the admixture of doping substances into the layer increases the equilibrium charge-carrier concentration in this layer, compared with the pure layers of one of the two substances concerned, which results in improved conductivity and better charge-carrier injection from the adjacent contact layers into this mixed layer. The transport of charge carriers then still takes place on the matrix molecules. According to US 5,093,698, the doped layers are used as injection layers at the interface to the contact materials, the light-emitting layer being found in between (or, when only one doped layer is used, next to the other contact). Equilibrium charge-carrier thickness, increased by doping, and associated band bending, facilitate charge-carrier injection. The energy levels of the organic layers (HOMO = highest occupied molecular orbital or highest energetic valence band energy; LUMO = lowest unoccupied molecular orbital or lowest energetic conduction
band energy), according to US 5,093,698, should be obtained so that electrons in the ETL as well as holes in the HTL can be injected into the EL without further barriers, which requires very high ionization energy of the HTL material and very low electron affinity of the ETL material. However, such materials are hard to dope, since extremely strong acceptors and donors would be required, so that these conditions cannot be fully met on both sides with materials that are actually available. Now, if HTL and ETL materials that do not meet these conditions are used, when voltage is applied an accumulation of charge carriers develops in the transport layers at the interfaces to the emitting layer (EL). Such an accumulation in principle promotes non-radiant recombination of excitons at the interface by, for example, the formation of exciplexes (these consist of a charge carrier in the HTL and ETL and of the opposite charge carrier in the EL). Such exciplexes recombine mainly non-radiantly, so that exciplex formation represents a non-radiant recombination mechanism. In addition, the problem of exciplex formation becomes more acute when doped HTLs and ETLs are used, since in doped materials the Debye shielding length is very small and hence high charge-carrier thicknesses occur directly at the interface. In addition, dopants in the immediate vicinity of the EL may result in quenching of fluorescence by, for example, Fbrster transfer.
Blocking layers in OLEDs for improving the charge carrier balance in the respective light-emitting layer are disclosed in the literature. Their function consists of preventing charge carriers from leaving the light-emitting layer. In the case of electrons in the emitter layer, therefore, the condition is that the LUMO of
the electron blocking layer (which is located between the emitter and the hole-transport layers) must lie distinctly over the LUMO of the emitter layer and the blocking layer must be designed thick enough so that no tunneling of electrons into the following hole-transport layer can take place. For the holes in the emitter layer, the same arguments apply to the energies of the HOMOs. Examples of this may be found in: M.-J. Yang and AT. Tsutsui: "Use of poly(9-vinylcarbazole) as host material of iridium complexes in high-efficiency organic light-emitting devices" in Jpn. J. Appl. Phys. 39 (2000), Part 2, No. 8A, pp. L828-L829; R.S. Deshpande et al.: "White-light-emitting organic electroluminescent devices based on interlayer sequential energy transfer" in Appl. Phys. Lett. 75 (1999) 7, pp. 888-890; M. Hamaguchi and K. Yoshino: "Color-variable emission in multilayer polymer electroluminescent devices containing electron-blocking layer" in Jpn. J. Appl. Phys. 35 (1996), Part 1, No. 9A, pp. 4813-4818. The selection of suitable blocking layers and hence the restriction of possible emission zones is of special importance for the production of special blue OLEDs.
Reference to exciplex formation between organic emitter materials and undoped transport materials with low ionization energy are found in: K. Itano et al.: "Exciplex formation at the organic solid-state interface: yellow emission in organic light-emitting diodes using green-fluorescent tris(8-quinolinolato) aluminum and hole-transporting molecular materials with low ionization potentials" in Appl. Phys. Lett. 72 (1998) 6, pp. 636-638; T. Noda et al. "A blue-emitting organic electroluminescent device using a novel emitting amorphous molecular material, 5,5'-bis(dimesitylboryl)-2,2'-bithiophene" in Adv. Mater. 11
(1999) 4, pp. 283-285. In the latter, the use of a blocking layer for reducing this effect is proposed, although not in connection with doped transport layers. The basic dilemma, that materials with deep-lying HOMO are hard to p-dope, but materials with high-lying HOMO promote exciplex formation at the interface to the emitting layer, has not yet been recognized in the professional literature. Accordingly, there are also no patents that propose solutions to this problem.
The object of the invention is to indicate a light-emitting component on the basis of doped charge-carrier transport layers, which can be operated at a reduced operating voltage and has high light-emission efficiency.
According to the invention, the object is accomplished, in conjunction with ' the features mentioned in the generic clause of Claim 1, in that between the doped charge-carrier transport layer and the light-emitting layer, there is provided a blocking layer of an organic material, the blocking layer being obtained so that the occurrence of non-radiant recombination channels, in particular due to exciplex formation at the interface to the emitter layer, is prevented. The component preferably is realized in that the energy levels of the blocking layers, charge-carrier transport layers and emitter layers are adapted to one another as j follows (see list of reference characters and numerals and Figure 3):
a) Condition for p-doped hole-transport layer (2) and hole-side blocking layer (3):
EvP > Evbiockp (highest occupied molecular energy level (in the valence band, HOMO) of the injection and transport layer for holes > HOMO energy of the hole-side blocking layer),

b) Condition for n-doped electron-transport layer (2') and electron-side
blocking layer (3'):
Ecn c) Condition for hole-side blocking layer (3) and emitting layer (4): Evbiockp- Evei d) Condition for electron-side blocking layer (3') and emitting layer (4): Ecbiockn - Ecei > - 0.3 eV (LUMO energy of electron-side blocking layer - LUMO energy of light-emitting layer > - 0.3 eV).
There, deviations from the stated values should always correspond to several kT at the operating temperature of the component (by several kT is meant up to 5 kT, i.e., approx. 5*25 meV at room temperature).
The charge-carrier transport layer is doped by an admixture of an organic or inorganic substance (dopant). There, the energy level of the majority charge-carrier transport state is selected so that, with the given dopant, efficient doping is possible (as complete as possible charge transfer from matrix to dopant). According to the invention, the blocking layer is located between the charge-carrier transport layer and a light-emitting layer of the component, in which conversion of the electric energy of the charge carrier injected by flow of current through the component takes place in light. According to the invention, the substances of the blocking layer are selected so that when voltage is applied (in
the direction of the operating voltage), because of its energy level no accumulation of majority charge carriers (HTL-side: holes, ETL-side: electrons) in the blocking layer occurs at the interface to the emitting layer. In order to realize this condition simultaneously with the demand for more efficient dopability, an energy barrier for the injection of charge carriers from the transport layer into the blocking layer is accepted.
In this respect, this approach clearly differs from that presented in the patent of Ogura et al., EP 1,017,118 A2: None of the examples listed in the latter patent meets the above conditions. Accordingly, the light-emitting diodes mentioned there are also clearly poorer with respect to operating voltage as well as to efficiency than the examples given by us. The blocking layer proposed in patent EP 1,017,118 A2 acts only to prevent the injection of minority charge carriers. This function can also be satisfied by the blocking layer proposed by us, i.e., it should in addition meet the condition that minority charge carriers are efficiently arrested at the light-emitting layer/blocking layer interface. In a preferred embodiment of the component, the energy levels of the blocking layers and of the emitter layer therefore satisfy the following conditions:
a) Condition for hole-side blocking layer (3) and emitting layer (4):
Ecbiockp > ECei (LUMO energy of hole-side blocking layer > LUMO energy of
light-emitting layer),
b) Condition for electron-side blocking layer (3') and emitting layer (4):
Evbiockp energy of light-emitting layer).
Additionally advantageous for a component of this patent is the fact that the energy gap of the doped transport layers is selected great enough so that injection of minority charge carriers from the emitting layer into the doped transport layer is not even possible when the blocking layer is so thin that it can be tunneled through. According to the invention, this is accomplished in that the following conditions are met:
a) Condition for p-doped hole-transport layer (2) and emitting layer (4):
EcP > ECei (LUMO of injection and transport layer for holes > LUMO energy
of light-emitting layer),
b) Condition for electron-side blocking layer (2') and emitting layer (4):
Evn HOMO energy of light-emitting layer).
An advantageous embodiment of a structure of an OLED according to the invention contains the following layers:
1. Carrier, substrate,
2. Base electrode, hole-injecting (anode = positive pole), preferably transparent,
3. p-doped hole-injecting and transporting layer,
4. Hole-side blocking layer (typically thinner than p-doped layer in item 3) of a material whose band levels match the band levels of the enclosing layers,
5. Light-emitting layer,
6. Thinner electron-side blocking layer of a material whose band positions match the band positions of the layers enclosing them,
7. Highly n-doped electron-injecting and transporting layer,
8. Cover electrode, usually a metal with low work function, electron-injecting (cathode = negative pole),
9. Metal protection, to shut out ambient influences.
According to the invention, the substances of the blocking layers are selected so that when voltage is applied (in the direction of the operating voltage), their energy levels allow them to inject charge carriers efficiently into the light-emitting layer (EL) and non-radiant recombination processes such as exciplex formation at the interface to the EL are unlikely, but charge carriers in the EL cannot be injected into the said second layer. This means that the substances of the blocking layers, according to the invention, are selected so that when voltage is applied (in the direction of the operating voltage), because of their energy levels they arrest majority charge carriers (hole-side: holes, electron-side: electrons) mainly at the doped charge-carrier transport layer/ blocking layer interface, but arrest minority charge carriers efficiently at the light-emitting layer/blocking layer interface.
It is likewise within the scope of the invention when only one blocking layer is used, because the band levels of the injecting and transporting layer and of the light-emitting layer already match one another on one side. Alternatively, only one side (hole- or electron-conducting) may be doped. In addition, the functions of charge-carrier injection and of charge-carrier transport into layers 3 and 7 may
be divided among a number of layers, of which at least one is doped. Molar doping concentrations typically lie in the range of 1:10 to 1:10000. If the dopants are substantially smaller than the matrix molecules, in exceptional cases there may alternatively be more dopants than matrix molecules in the layer (up to 5:1). The dopants may be organic or inorganic. Typical layer thicknesses for the blocking layers lie in the range of 1 nm to 20 nm, but they may alternatively be thicker. Typically, the blocking layers are thinner than their corresponding adjacent doped layers. The layer thicknesses of the blocking layers must be great enough to prevent exciplex formation between charged molecules of the substances in the corresponding adjacent mixed layers and charged molecules of the electroluminescent layer and quenching of luminescence by dopants themselves.
In summary, the accomplishment according to the invention may be described as follows: In order to be able to p-dope an organic transport material efficiently (explained here only for the hole side, the electron side follows analogously with exchange of the terms HOMO and LUMO), its ionization potential must be relatively small, owing to which a greater HOMO distance between the transport layer and the emitter layer is obtained. A consequence of efficient doping is that all dopants are present in the layer completely ionized (in the case of p-doping the dopants, the acceptors, are all negatively charged). Therefore, electron injection from the emitter layer to the dopants of the transport layer is no longer possible. This disadvantage, which no longer exists with efficient doping, is gone into in the patent of Ogura et al., EP 1,017,118 A2.
There, it is taken care of by blocking layers for preventing the injection of electrons from the emitter layer into the hole-transport layer.
In contrast to this, in the accomplishment proposed here the blocking layer may be selected extremely thin, since it is designed mainly to prevent exciplex formation but need not represent a tunnel barrier for charge carries (in contrast to the patent of Ogura et al, EP 1,017,118 A2)
Light-emitting component comprising organic layers, in particular organic light-emitting diode, consisting of at least one doped charge-carrier transport layer, a light-emitting layer and contact layers, characterized in that between the charge-carrier transport layer and the light emitting layer there is provided a blocking layer of an organic material wherein the transport layer, Light Emitting layer and blocking layer must fulfill all the following conditions for their energy level:-
(a) Condition for p-doped hole-transport layer(2) and hole-side blocking layer(3): EVp>Evbiockp [highest occupied molecular energy level(in the valance band, HOMO) of the injection and transport layer for holes>HOMO energy of the hole-side blocking layer],
(b) Condition for n-doped electron-transport layer(2') and electron-side blocking layer(3'):
Ecn (c) Condition for hole-side blocking layer(3) and emitting layer(4):
Evbiockp-Evei (d) Condition for electron-side blocking layer(3') and emitting layer(4):
Ecbiockn-Ecei> -0.3eV(LUMO energy of electron-side blocking layer-LUMO energy of light-emitting layer>-0.3eV)
(e) Condition for hole-side blocking layer(3) and emitting layer(4):
Ecbiockp> ECei(LUMO energy of hole-side blocking layer > LUMO energy of light-emitting layer)
(f) Condition for electron-side blocking layer(3') and emitting layer(4): EvbiockP (g) Condition for p-doped hole transport layer (2) and emitting layer (4):
EcP> Ecei (LUMO of injection and transport layer for electron > LUMO energy of light-emitting layer) (h) Condition for electron-side blocking layer(2') and emitting layer(4):
EVn The invention is described below in greater detail by means of examples. In the drawings,
Figure 1 shows a theoretically ideal doped OLED structure
Figure 2 a doped OLED without blocking layer, existing in practice,
Figure 3 a doped OLED with blocking layers
Figure 4 an OLED doped only on the hole side, with blocking layer there
A theoretically ideal structure is represented in Figure 1, consisting of an anode (EA), a highly p-doped hole injection and transport iayer (Evp, EcP, EFP), an electroluminescent layer (Evei, Ecei, EFei), a highly n-doped electron-injecting and transport layer (Evn, ECn, EFn) and a cathode. When voltage is applied (anode polarized positively), holes from the anode and electrons from the cathode are injected in the direction of the light-emitting layer. Since no barrier occurs (Evp > Evei) for holes at the interface of the p-doped layer to the light-emitting layer, nor for electrons at the interface of the n-doped layer to the light emitting layer (Ecn > ECei), and a higher barrier exists (Ecei EVp) at the interface of the light emitting layer to the p-doped and n-doped layer for electrons and holes respectively, the charge carriers (electrons and holes) collect in the light-emitting
layer, where they can efficiently form excitons and recombine radiantly. In reality, layer combinations with the parameters mentioned above are not yet to be found and perhaps will never be found, since these layers must bring together a great number of some opposing properties. A realizable layer structure looks like the one shown in Figure 2 (schematic band levels).
The organic acceptor thus far best known for p-doping of organic materials (tetra-fluoro-tetracyano-quinodimethane F4 - TCNQ) is capable, because of its band level ECpdot. of doping materials efficiently at a valence band level of about EvP = - 5.0...-5.3 eV. The material most used for producing electroluminescence, aluminum-tris-quinolinate (Alq3) has a valence band level of Evei = - 5.65 eV. Thus, the holes conducted into the p-doped layer are blocked at the interface to the electroluminescent layer (EvP > Evei)- The same applies to the interface between n-doped and light-emitting layer (Ecn EVn), as described earlier for the theoretically ideal case. However, the result of this is that when voltage is applied, charge carriers accumulate at the interfaces of the doped layers to the light-emitting layer. Upon accumulation of an opposite charge on two sides of an interface, increased non-radiant recombination processes occur due, for example, to
formation of exciplexes, which again reduces the efficiency of conversion of electrical into optical energy. Thus, with an LED having this layer structure, the operating voltage can be reduced by doping, but only at the cost of efficiency.
According to the invention, the disadvantage of the previous structures is avoided by OLEDs with doped injection and transport layers in combination with blocking layers. Figure 3 shows a suitable arrangement.
Between the hole-injecting and conducting layer and the light-emitting layer, there is here located an additional layer, the hole-side blocking layer. The most important conditions for the selection of this layer are: Evbiockp - Evel Ecei. so that electrons cannot leave the light-emitting layer. Similarly, and with the same arguments, the following must apply on the electron side: Ecwockn- Ecei > - 0.3 eV and Evbiockn Evei and Ecn longer present in the immediate vicinity of excitons in the light-emitting layer, so that quenching of luminescence by dopants is ruled out.
This arrangement is characterized by the following advantages:
A high charge-carrier thickness of both kinds in the light-emitting
layer even at low voltages
Outstanding injection of charge carriers from anode and cathode
into the p- and n-doping charge-carrier transport layers
Outstanding conductivities in the doped layers
Because of their small thickness only small voltage losses in the
blocking layers
No formation of exciplexes, because of spatial separation of charge
carriers of unlike polarity
No quenching by dopants Together, this results in high conversion efficiencies at low operating voltage for OLEDs having this layer structure. In this connection, mixed layers known in the literature, which increase the recombination efficiency of excitons, or likewise well-known phosphorescent material systems with their high quantum efficiency, may alternatively be used for the light-emitting layer.
According to the invention, layers doped on only one side (hole or electron side) may alternatively be used in combination with a blocking layer (only one) described above (Figure 4).
The layer sequence according to the invention necessarily results in a stepwise increase of the transport levels EA vice versa, a stepwise decrease of the transport levels EK As a preferred example, an accomplishment is to be indicated here, in which the combination of p-doped injection and transport layer and blocking layer is used only on the hole side. The OLED has the following layer structure:
1. Anode: indium tin oxide (ITO)
2. p-doped layer: 100 nm Starburst ATDATA 50:1 doped with F4-TCNQ
3. Hole-side blocking layer: 10 nm triphenyldiamine (TPD)
4. Electroluminescent and (in this case) conventional electron-conducting layer: 65 nm Alq3
5. Cathode: 1 nm LiF in combination with aluminum (LiF improves injection at the contact).
The mixed layer (2nd) was produced in a vacuum deposition process in mixed deposition. In principle, such layers may alternatively be produced by other methods, such as, for example, deposition on one another of the substances with subsequent possibly temperature-controlled diffusion of the
substances into one another; or by other deposition (e.g., spin-on deposition) of the already mixed substances in or outside a vacuum. The blocking layer was likewise deposited under vacuum, but may alternatively be produced differently, e.g., by spin-on deposition in or outside a vacuum.
The energy levels of the HOMO and LUMO energies are:
1. ITO work function EA ~ - 4.6 eV (highly preparation-dependent)
2. TDATA: EVp = - 5.1 eV, ECp « -2.6 eV
3. TPD: Evbiockp = - 5.4 eV, ECbiockP = - 2.3 eV
4. Alq3: EVei = - 5.65 eV, ECei = - 2.9 eV
5. Al: EK = - 4.3 eV
In this arrangement, the requirements EvbiockP-Evei Ecei (0.6 eV), as well as EVp > Evwockp (0.3 eV) are met. In this preferred embodiment, the LUMO of the hole=transport layer (TDATA ECp) is distinctly higher (0.3 eV) than the LUMO of the emitter layer (Alq3 ECei). This is not absolutely necessary but is advantageous, in order not to permit tunneling of electrons from the emitter layer into the hole-transport layer through the thin blocking layer. At 3.4 V, this OLED has a luminescence of 100 cd/m2, with an efficiency of 5 cd/A. With an undoped TDATA layer, 100 cd/m2 are obtained only at about 7.5 V. In an OLED as described above, but without a TPD blocking layer, the characteristic data are: 8 V for 100 cd/m2 and an efficiency poorer by a factor of 10!
This example shows how effective the combination of doped transport layer and blocking layer is with regard to optimization of operating voltage and light-emission efficiency.
An additional embodiment of the component according to the invention consists in that additional small quantities (0.1 - 50%) of an emissive colorant are mixed into the emitter layer (in the literature, this admixture is also called doping - but not doping in the sense of this patent - and admixtures therefore are called emitter dopants). These may, for example, be quinacridone in Alq3 in the example mentioned above or a triplet-emitter such as Ir(ppy) (tris(2-phenylpyridine)iridium) in matrix materials such as TCTA (tris(carbazolyl)-triphenylamine), BCP (bathocuproine), CBP (dicarbazole-biphenyi) and the like. For a triplet emitter, the concentration of the emitter dopant is usually greater than 1 %. For these combinations of material, the blocking layer must prevent exciplex formation between the blocking layer materials and the emitter dopants. Exciplex formation in electron-hole pairs on molecules of blocking layer material and matrix material may thus be possible, as long as majority charge carriers are able to pass over directly (i.e., even without exciplex formation from electron-hole pairs on blocking layer molecules and emitter dopant molecules) into states of the emitter dopant, and therefore exciplex formation on blocking layer molecules/ matrix molecules is then prevented. Therefore, the positions of HOMO and LUMO levels of the emitter dopant are important energy conditions for the connection of blocking layers to light-emitting layers:
a) Condition for hole-side blocking layer (3) and emitting layer with
emitter dopant (4):
Evbiockp - Eveidotand b) Condition for electron-side blocking layer (3rd) and emitting layer
with emitter dopant (4):
Ecbiockn - ECei > - 0.3 eV (LUMO energy of electron-side blocking layer -LUMO energy of emitter dopant in the light-emitting layer > - 0.3 eV).
List of reference characters and numerals
EA work function of anode
EvP highest occupied molecular energy level (in the valence band,
HOMO) of the injection and transport layer for holes
ECp lowest unoccupied molecular energy level (conduction band or
LUMO) of the injection and transport layer for holes
Ecpdot LUMO energy of p-doping material (acceptor)
EFP Fermi level of p-doped layer
Evbiockp HOMO energy of hole-side blocking layer
Ecbiockp LUMO energy of hole-side blocking layer
t^Fblockp Fermi level of hole-side blocking layer
Evei HOMO energy of light-emitting layer
Ecei LUMO energy of light-emitting layer
EFei Fermi level of light-emitting layer
Evbiockn HOMO energy of electron-side blocking layer
tCblockn LUMO energy of electron-side blocking layer
CFblockn Fermi level of electron-side blocking layer
Evn HOMO energy of injection and transport layer for electrons
Ecn LUMO energy of injection and transport layer for electrons
Evndot HOMO energy of n-doping material (donor)
EFH Fermi level of injection and transport layer for electrons
EK work function of cathode
1 - anode
2 - hole-transport layer
2' - electron-transport layer
3 - hole-side blocking layer
3" - electron-side blocking layer
4 - light-emitting layer
5 - cathode
6 - electron-transporting and light-emitting layer

WE CLAIM:
1. Light-emitting component comprising organic layers, in particular organic light-emitting diode, consisting of at least one doped charge-carrier transport layer (2), a light-emitting layer (4) and contact layers (1,5), characterized in that between the charge-carrier transport layer (2) and the light emitting layer (4) there is provided a blocking layer (3) of an organic material wherein the transport layer(2), Light Emitting layer(4) and blocking layer(3) must fulfill all the following conditions for their energy level:-
(a) Condition for p-doped hole-transport layer(2) and hole-side blocking
layer(3):
EVp>Evblockp [highest occupied molecular energy level(in the valance band, HOMO) of the injection and transport layer for holes>HOMO energy of the hole-side blocking layer],
(b) Condition for n-doped electron-transport layer(2') and electron-side
blocking layer(3'):
Ecn (c) Condition for hole-side blocking layer(3) and emitting layer(4): Evblockp-Evel (d) Condition for electron-side blocking layer(3") and emitting layer(4): Ecbiockn-Ecei> -0.3eV(LUMO energy of electron-side blocking layer-LUMO energy of light-emitting layer>-0.3eV)
(e) Condition for hole-side blocking layer(3) and emitting layer(4): EcbiockP> ECel(LUMO energy of hole-side blocking layer > LUMO energy of light-emitting layer)
(f) Condition for electron-side blocking layer(3') and emitting layer(4): Evbiockp (g) Condition for p-doped hole transport layer (2) and emitting layer (4): Ecp> Ecel (LUMO of injection and transport layer for electron > LUMO energy of light-emitting layer)
(h) Condition for electron-side blocking Iayer(2') and emitting layer(4):
Evn 2. Light-emitting component comprising organic layers as claimed in claim 1, wherein the component consists of a hole-injecting anode (1), a hole-transport layer (2) for hole conduction from a principal organic substance and acceptorlike doping substance, a first organic hole-side blocking layer (3), a light-emitting layer (4), a second organic electron side blocking layer (3'), an electron-transport layer (2') for the conduction of electrons from a principal organic substance and donor-like doping substance, and a cathode (5) for the injection of electrons.
3. Light-emitting component comprising organic layers as claimed in claim 1 or
2, wherein anode (1) and cathode (5) are metallic.
4. Light-emitting component comprising organic layers as claimed in claims 1 to
3, wherein the layer sequence of hole-transport layer (2), blocking layer (3)
and light-emitting layer (4) is repeatedly provided.
5. Light-emitting component comprising organic layers as claimed in claims 1 to
4, wherein the light-emitting layer consists of a plurality of layers.
6. Light-emitting component comprising organic layers as claimed in claims 1 to
5, wherein a contact-improving layer is in each instance provided between the
anode (1) and the hole-transport layer (2) and/or between the electron-
transport layer (2') and the cathode (5).
7. Light-emitting component comprising organic layers as claimed in claims 1 to
6, wherein the molar concentration of the admixture in the hole-transport layer
(2) and/or in the electron transport layer (2') lies in the range of 1:100,000 to
5:1, referred to the ratio of doping molecules to principal substance molecules.
8. Light-emitting component comprising organic layers as claimed in claims 1 to 7, wherein the layer thickness of the hole-transport layer (2) and/or of the electron-transport layer (2') and pf the blocking layers (3,3') lie in the region of 0.1 nm to 50µm.
9. Light-emitting component comprising organic layers as claimed in claim 8, wherein the blocking layer (3,3') is thinner than its corresponding adjacent doped layers.
10. Light-emitting component comprising organic layers as claimed in claims 1 to 9, wherein the blocking layer (3,3') is sized with respect to adjacent energy layers so that majority charge carriers are arrested predominantly at the charge-carrier transport layer/blocking layer interface and minority carriers at the light-emitting layer/blocking layer interface.
11. Light-emitting component comprising organic layers as claimed in 1 to 10. wherein the layer thickness of the blocking layer (3,3') is sized so that exciplex formation between charged molecules of the substances in the corresponding adjacent transport layer (2,2') and charged molecules of the electroluminescent layer and quenching of luminescence by dopants is prevented.
12. Light-emitting component comprising organic layers as claimed in claim 1. wherein the energy levels refer to a combined state of layers.
13. Light-emitting component comprising organic layers as claimed in any of the above claims substantially as described in the specification and illustrated in the accompanying drawings.

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Patent Number

233506

Indian Patent Application Number

736/DELNP/2003

PG Journal Number

14/2009

Publication Date

27-Mar-2009

Grant Date

30-Mar-2009

Date of Filing

13-May-2003

Name of Patentee

TATZBERG GMBH

Applicant Address

01307 DRESDEN GERMANY.

Inventors:

#	Inventor's Name	Inventor's Address
1	PFEIFFER, MARTIN	SCHARFENBERGER STR. 1, 01139 DRESDEN GERMANY.
2	BLOCHWITZ-NIEMOTH, JAN	LOUISENSTR. 8, 01099 DRESDEN GERMANY.
3	ZHOU, XIANG	ACKERMANNSTR. 19, 01217 DRESDEN GERMANY.
4	LEO, KARL	HERMANNSTR. 5, 01219 DRESDEN GERMANY.

PCT International Classification Number

H01L 51/20

PCT International Application Number

PCT/DE01/04422

PCT International Filing date

2001-11-20

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	100 58 578.7	2000-11-20	Germany