ELECTROLUMINESCENT DEVICE AND A WAY TO FABRICATE IT

Abstract: An electroluminescent device has a preferably transparent or translucent material constituted substrate, a first electrode layer (11) applied on this, a light emitting layer (12, 13) applied on this and the substrate (10) and displaying a light emitting ability and constituted by a conjugated polymer or a polymer mixture and a second electrode layer (14) applied on top of the light emitting layer (12, 13), the electroluminescent device being provided with connections (15, 16) to the two electrode layers. According to the invention a light emitting layer (12, 13) includes a separately fabricated, integral, light emitting layer (13). Preferably this layer (13) is pre-treated, in particular tensioned in one direction in order to orient the major part of the polymeric chains in the polymeric material in this direction. At the preferable embodiment the light emitting layer is constituted by several partlayers (12, 13). At the fabrication of such an electroluminescent device is used a manner, in which at least a part (13) of the light emitting layer (12, 13) is applied by transferring it from a carrier or a support, on which this layer (13) first has been made, the transfer from the carrier for the lamination with the underlying of the electroluminescent device preferably is executed first since this part (13) of the light emitting layer (12, 13) has been subjected to a pretreatment, in particular a strectching in a direction for orientation of the polymer chains in the polymer material in this direction.

Description: ELECTROLUMINESCENT DEVICE AND A WAY TO FABRICATE IT This invention concerns electroluminescent devices and a way of fabricating these, in par¬ ticular devices which have conjugated polymers as emitting layer. Electroluminescent devices of the type, which this invention concerns, have frequently been reported. As example of this one can mention PCT/WO 90/13148, PCT/WO 9203490, PCTAVO 92/03491 , PCT/WO 93/14177, PCT/WO 94/03030, PCT/WO 94/03031 and US- A-5 317 169. These devices have been developed to a considerable extent and new useful fields of application has been found, since the report made by J H Burroughes et al [Nature 347, 539-541 (1991)]. Thus different researchers have described improvements which have resulted in that these devices emits light of any colour throughout the entire visible spec¬ trum [G. Grem et. al. , Advanced Materials 4, 36-37 (1992); D Braun et. al., Applied Physics letters 58, 1982-1984 (1991); and C Zhang et. al. , Journal of Electronic Materials 22, 413-417 (1993)]. N. C. Greenham et. al. have reported on high quantum efficiency devices in Nature 365, 628-630 (1993), while Goran Gustafsson et. al. reported on the possibility of fabricating large area and flexible light emitting devices. Conjugated polymers, being organic macromolecules, have offered new possibilities, which earlier have not been obtainable. One advantage using conjugated polymers as materials in light emitting devices is that the layers can bee processed and constructed using solvents! see the PCT publications above and A. Assadi et. al., Applied Physics Letters 53, 1995 (1998) and J. H. Burroughes et. al., Nature 335, 137 (1988)]. Another advantage is that small chemical modifications of the polymers results in a tunability of the band gap (the colour of the emitted light)[ B. H. Xui, Macromolecules 26, 4457 (1993) and R. E. Gill et. al. Advanced Materials 6, 132 (1994)]. If one would like to fabricate devices, which consists of more than one emitting layer or which consists of one or more barrier layers, one has, to prevent the already existing layers from being damaged during the fabrication of the next layer placed on top there on, needed to add different layers from different solvents which not destroy the underlying layer/layers. This problem is particularly obvious, if one would like to fabricate devices which consists of layers with thickness in the range of 20-100nm. This restriction of the fabrication proce¬ dure is sometimes unfortunate, since it limits the freedom of choice when combining differ¬ ent types of conjugated polymers for the different layers. One purpose with this invention is thus to provide a new type of electroluminescent device and a way to fabricate such a device without restricting the type of solvents when choosing the different layers in the devices. Another purpose with this invention is to fabricate multi¬ layer light emitting devices which offer more freedom of choice to combine different poly¬ mers to achieve emission of any colour. A further purpose with this invention is that in such a device and in such a way of fabrication it will be possible in a intermediate step treat one or several specific layer or layers without affecting the other layers. The chains of conjugated polymers is randomly oriented in the bulk material. Through ori¬ entation of the chains it is possible to achieve an anisotropic structure with strong anistropic properties, almost one dimensional properties. This possibility to achieve anisotropic prop- erties have been studied through the investigation of photoluminescence of oriented polymer films [ D. D. C. Bradeley et. al. , "Infrared characterisation of Oriented Poly- (phenylenevinylene)", Polymer 27, 1709 (1986) and T. W. Hagler et. al. , Physical Review B 44, 8652 (1991)] and through the study of conductivity of electrons. All of these studies has been done on thick polymer layers, which because of their thickness as unsuitable for or at least show disadvantages to use electroluminescent devices or in light emitting diodes of a kind which can be utilised in displays. Despite that it is known, that it is possible to orient the luminescent polymers, none has up to now been able to use the stretching technique together with the construction of the lumi¬ nescent diodes with extremely thin luminescent layers of conjugated polymers. The reason for this is that the layers are not self-supporting and that they, because of this, need to be applied directly onto a carrier or a support, onto which one has already applied at least a first electrode or a first charge injection layer. It has not been possible to stretch the carrier or the support together with the emitting layer. The reason for this is that the electrode or the charge injection layer would be damaged or disturbed during such treatment. As far as it is known all electroluminescent devices, which has been fabricated utilising conjugated polymers, have had isotropic properties, i. e. the polymer chains has been oriented ran¬ domly. There exists requirements for electroluminescent devices or electroluminescent diodes, which emits polarised light, for example in connection with displays in computer screens. Another advantage with this invention is to fabricate light emitting devices consisting of a thin layer of conducting polymers which are oriented, sandwiched between two electrodes with or without injection-barrier layers, which emits polarised light. Another advantage of the invention is to achieve an effective way for the building of such devices. These and the other purposes are obtained in accordance with the claim 1. The device is preferably made accordance with claim 12. The subclaims defines preferable development of the invention. When making use of the invention an electroluminescent device is achieved, that has a sup¬ porting structure or substrate, preferably fabricated from transparent or translucent material a first electrode layer applied on this, a light emitting layer of a conjugated polymer dis¬ playing a light emitting ability applied on the first electrode layer and the substrate, and a second electrode layer applied on top of the light emitting layer, the electroluminescent de¬ vice also being provided with connections to the two electrode layers. In accordance with the invention the light emitting layer includes a separately made and a continuos light emitting layer. Preferably this layer is pre-treated, particular stretched in one direction for the orientation of the main part of the chains in the polymer material in this direction. In a further development the light emitting layer consists of more than one part layer. The invention can also be utilised in electroluminescent devices were the injec¬ tion properties are enhanced through the addition of a enhancing layer the transport of the charge carriers which is placed between the electrode and the light emitting layer or layers. At the fabrication of this electroluminescent device in accordance with the invention a method is utilised, where at least one part of the light emitting layer is added by transferring it from a carrier. The light emitting layer is first created on this carrier, the transfer from the carrier to underlying layer being carried out after the pre-treatment of this layer, in par¬ ticular stretch orientation of the polymer chains. At the fabrication of field effect transistors it is already known to build a very thin layer of a conjugated polymer on top of a foil layer and then stretch the foil together with the poly¬ mer layer to orient the polymer chains [P. Dyreklev, "Aligned Polymer Chain Field Effect Transistors", Solid State Communications, vol. 82, 5,317-320 (1992)], but in this case the polymer film never gets separated from the barrier foil. In this article studies of the ani¬ sotropic mobility of poly(3-octyltiofen) are presented for the undoped state. The mobility was estimated using a field effect transistor, which had been added by the carrier with the polymer film. The anisotropy increased with increased orientation up to the value of 4. In the article properties concerning rest dopants, anisotropy in the conjugation length, internal anisotropy in the charge transport along and in between the chains and also crystallinity and monodispers conjugation length was discussed. In the article it is mentioned, on page 317, that it is possible to add the polymer film to the carrier and to orient the film through stretching of the carrier and the polymer film. A degree of orientation as high as 0.82 was reported with these kind of films on different substrates, where patterned metal electrodes are included. This has provided the possibility of fabricating field effect transistors of stretch oriented polymers. In this article it has been described that poly(3- octylphenylthiophene) was added to a carrier of polyethylene-foil (PE), but as described at page 318 row 10-17, it was possible to remove both the carrier and the polymer film and add them to the structure once again but at a different orientation direction in other words, the active layer of conjugated polymer was never separated from the carrier foil. The invention differs from the above mentioned technique since the polymer film is sepa¬ rated from the carrier. The carrier, in this invention, is just used as a temporary carrier where some intermediate treatment occur. After the treatment the polymer film is then transferred to the final device or substrate. In the following examples the invention has been executed using glass slides as substrates for the electroluminescent device. The invention can off course be combined with other types of substrates, flexible substrates and large area substrates. When the invention is utilised for the fabrication of devices, which emits polarised light, it is possible to achieve a high degree of polarisation, ratios between light intensity parallel to the polymer chain orientation direction and light intensity peφendicular to the orientation direction, when the polymer film is elongated twice compared to the initial length. At this elongation a polarisation degree of 3.1 is achieved between the electroluminescence inten¬ sity parallel and peφendicular to the orientation direction. The emission spectra parallel and peφendicular to the stretching direction is not changed very much. Quantum efficiencies of 0.1 % have been reached in devices where the invention has been utilised. In this device and in accordance with other electroluminescent devices based on conjugated polymers of the same type an emitting layer is sandwiched between two electrodes. In this invention this emitting layer may consist of more than one part, and also the combination of emitting layers and charge injection/charge barrier layers. As the device is biased, the elec¬ trodes inject charges into the device and into the emitting layer. The charges, electrons and holes, recombine through the formation of an excited state, an exciton, which emits the energy as light To achieve high quantum efficiency, photons emitted per electrons injected, the positive electrode is a high work function material and the minus electrode a low work function material. In this invention ITO (indium tin oxide) and calcium are used as a high and a low work function material respectively. Other known kinds of material can also be used as electrodes in these devices, one example is described for instance by Goran Gus- tafsson[G. Gustafsson, "Flexible light emitting diodes from soluble conducting polymers, vol. 357, 11 June 1992, page 477-479]. Here polyaniline is used as the hole injecting elec¬ trode on a poly(ethylenetereftalate) (PET) where poly(2-metoxy-5-(2'-ethyl-hexoxi)-l,4- phenylenevinylene) (MEH-PPV) has been utilised as the emitter and calcium has been util¬ ised as the electron injecting layer. Besides polyaniline it is possible to use poly(3,4- etylenedioxithiophene) as the hole injecting electrode in this invention. The light emitting layer or sub layer can be constructed of just one polymer material. It is also possible to make this emitting layer or the sub layer of a polymer blend, copolymers or blockcopolymers or blends of such polymers. In such a blend at least one polymer has to be luminescent. When this separately built layer is fabricated a known spin coating method is primarily used of the kind mentioned below. But it is also possible to fabricate such a layer through casting from solution or by melting. Also dip forming and smearing of the this thin layer is a pos¬ sibility. As mentioned earlier, one of the advantages with this invention is that the separately built layer can be exposed to a pre treatment or a treatment as an intermediate step, before it is be laminated to the rest of the substrate. Such a intermediate step could be stretching in order to orient the polymer chains in the stretching direction. Another possible pre- or in¬ termediate treatment is a chemical treatment of the polymer layer in order to modify its properties or chemical structure. The most promising use of the electroluminescent devices, according to the invention, is as displays with large area. They can be used as they are or in combination with other known devices, for examples together with liquid crystals (LCD). The possibility to fabricate stretch oriented, polarised light emitting layers and this also on non stretched substrates makes it possible to combine known fabrication steps with solvent based coating of the polymer film and the colour tunability with a polarisation filter. The device could then be used as a back light for conventional LCD screens. As mentioned in the examples the invention has been tested on three different materials, poly(3-(4-octylphenyl)-2,2'bithiophene) (PTOPT), poly(3-(4-octylthiophene)) (POPT) and poly(3-octylthiophene) (POT). The invention is aimed to transfer any kind of thin film polymer material from a carrier. In its broad aspects the invention is useful for any of the materials that are above mentioned in the PCT-publications and other publications, which all are included in this description as references. Within the frame of the invention there is a special use of substituted polythiophenes- and poly(p-phenylenevinylene)- based polymers, a poly(p-phenylene) or a substituted poly(thiophenylenevinylene) as emitters in the invention. In the performed examples polyethylene foil(GLAD DowBrands Europe GmbH, Dϋssel- dorf, Germany) was used as the carrier. Also other types of temporarily carriers can be used as long as the carrier material has properties, which allow the polymer film to leave the carrier after some treatment. The polymer film is then transferred to a permanent sub¬ strate. In the following examples the electroluminescent intensity has been measured using a photo diode (Hamamatsu, 1010-BR). The EL intensity is presented in 10'^A. Some non-limiting examples of the invention will bellow be described with reference to the following figures, where Fig. 1 shows the chemical structure of poly [3-(4-octylphenyl)-2,2'bithiophene] Fig. 2 shows a cross-section through an electroluminescent device according to the inven¬ tion Fig. 3 shows the current (A) as a function of voltage (V) and the electroluminescence in¬ tensity as a function of voltage (V). The current is depicted with filled squares and values along the left vertical axis and the electroluminescence intensity is depicted with filled cir¬ cles and values along the right vertical axis. The voltage values are given along the horizon¬ tal axis. Fig. 4 the intensity of the electroluminescence is depicted as a function of the wave length (nm). A solid line shows the intensity in the parallel direction and a dashed line the intensity in the peφendicular direction. Fig. 5 the normalised electroluminescence intensity is shown as a function of the wave length where the solid line corresponds to the parallel direction and the dashed line to a peφendicular direction Fig. 6 the electroluminescent intensity is depicted as a function of the angle to the direction of stretching. In the performance examples all the steps has been carried at room temperature and in am¬ bient atmosphere, if nothing else is described. In the examples the following abbreviations are used for the polymers: POPT: poly(3-(4-octylthiophene)) PTOPT : poly (3-(4-octylphenyl)-2 , 2 ' bithiophene) POT: poly(3-octylthiophene) PCHMT: poly(3-cyclohexyl-4-methylthiophene) PE: polyethylene The polymer film thickness, discussed in the performed examples, have been estimated by measuring the optical absoφtion of the films. The thickness has then been calculated using data where film thickness have been related to the thickness measured by a surface profilo- meter. The examples show that it is possible to fabricate polarised light sources of a separately made, stretch oriented polymer layer, which is laminated onto the other parts of a diode. The examples show also that by using the same method it is possible to fabricate diodes without any mechanical treatment the polymer layer. The fabricated device, with stretch oriented layers, where PTOPT is the emitting layer, showed a quantum efficiency of 0.1 % and a turn on voltage of 2V. Similar results have been reached using other types of materi¬ als. Other materials with better orientation properties will increase the polarisation degree in these devices. Comparing devices with or without a stretch oriented layer did not show any decreased performance properties, when using the invention and stretching the polymer layer. EXAMPLE 1 In this performed example, an electroluminescent device was fabricated, in which the light emitting layer was of one layer structure and was made as a separate layer, which after fab¬ rication was laminated to the other part of the electroluminescent device's layer. POPT was dissolved in chloroform(CHCl3 pro analysis) to the concentration 5 g POPT per litre CHCI3. A PE-foil with a thickness of approximately 10 μm (trade mark GLAD ® ) was mounted on a circular plastic substrate (polystyrene petri dish), the puφose of which is to keep the PE-foil planar and make mounting in a photo resist spinner facility possible. The plastic substrate with the PE-foil was mounted in the photo resist spinner facility, with the PE-foil pointing upwards. Hexane (n-hexane, C6H14, purum) was applied on the PE-foil, and the plastic substrate with the PE-foil was rotated at 1000 φm for 30 s. The PE-foil was dried on its plastic substrate in an oven at 40°C for 10 min. The dried PE-foil on its plastic substrate was than again mounted in the photo resist spinner facility. The POPT so¬ lution was applied on the PE-foil, which the was rotated at 1000 φm for 30 s. After this amount of time, the solvent was evaporated. The thickness of the POPT layer was deter¬ mined to be 50 nm. The two layer film of POPT and PE prepared in this way, was stretched mechanically to a length, which was 1.5 times the initial length. The substrate, which had a first electrode layer, for fabrication of the electroluminescent device, was purchased on the market from Balzers, Switzerland under the trade mark BAL- TRACON. This substrate consisted of glass with the thickness 2 mm and had on one of its sides a coating of indium tin oxide (ITO) with the thickness 100 nm. This substrate was cut to a square slab with the side 15 mm. Photoresist was applied on the ITO-layer, so that the photoresist layer covered an area 5 x 15 mm^ at one edge of the glass slab. The photoresist was dried in an oven at 100°C for 4 min. After the drying, the area of the ITO layer not covered by photoresist, was etched by an etch solution, which consisted of 50% H2O, 50% HC1 and a few drops of HNO3. The etching was made during a time of 10 min. Then, the photoresist layer was removed, in a manner well known to the specialist, by rinsing in a cleaning solution, specially designed for this puφose, during 20 min. After that the sub- strate was rinsed in another cleaning solution, specially designed for this puφose, and then rinsed in acetone and finally rinsed in ethanol. The etched and from photoresist freed substrate with remaining ITO-layer was heated to 60 °C on a heating rod made of copper. Then the two layer structure of POPT and PE was placed on the substrate, in a way such that the POPT layer was turned towards the ITO- layer of the substrate. The two-layer structure was then pressed onto the substrate using a rubber roll. Simultaneously the temperature was raised to 80-90°C. At this temperature the PE-foil was detached from the POPT-layer, which remained on the substrate. On top of the POPT-layer, a second electrode layer was vacuum evaporated in the follow¬ ing way. On the substrate with the POPT-layer, a shadow mask was mounted, which had holes corresponding to the desired electrode pattern. The substrate with the shadow mask was introduced into the evaporation chamber of an evaporation equipment. This was evacuated to a pressure p < 10 ~ 6 torr. After that, first calcium and then aluminium (purity 99,5 %) was applied in the form of layers, onto the POPT layer. The obtained calcium layer thickness was 20 nm, and the obtained aluminium layer thickness was 100 nm. Connections were then made in a usual way to both the electrodes, and it was found that the electroluminescent device, fabricated in this way, during applicating of the voltage 6 V emitted red and near-infrared light, visible in daylight. The intensity ratio was 1.6 between the light emitted parallel to the stretching direction, and light emitted peφendicular to the stretching direction. EXAMPLE 2 In this example an electroluminescent device, consisting of two organic layers which emit¬ ted polarised light, was fabricated. The substrate, which had a first electrode layer, and which was aimed to be used for the construction of the electroluminescent device in the first example was also used here. The substrate was etched and the photoresist was removed. After this the substrate was spin coated with a layer of PTOPT. This was done by spinning a solution of PTOPT on top of the substrate. The solution consisted of PTOPT in chloroform (8 mg/ml). The spin rate was lOOOφm. A carrier, a PE foil with a thickness of 10mm, was washed with n-hexane (C6H14) at lOOOφm (spinning) during 30s. Then the carrier was transferred to an oven and was dried at 40 °C for lOmin. The carrier was then mounted to a holder and these two were then placed on the spinner. The carrier was then covered with a first layer of PTOPT, utilising the spin coating technique. PTOPT was dissolved in chloroform(CHCl3) (8 mg/ml). The PTOPT solution was then applied onto the carrier and the carrier was rotated during 30s at lOOOφ. After that the solvent(CHCl3) had left the film, which now had a thickness of 50nm. Then the foil together with the PTOPT film was its double length. The substrate with the ITO electrode and the PTOPT layer was heated to 60 °C. Then the elongated foil with the stretched oriented PTOPT layer on top was added to the sub- strate/ITO/PTOPT structure, stretch oriented PTOPT to PTOPT. The two layer structure was pressed gently to the substrate structure by a rubber-roller. At the same time the tem¬ perature was increased to 80°C-90°C. After this the PE foil was removed and the stretch oriented film remained on the substrate (substrate/ITO/PTOPT/stretched PTOPT) On top of the PTOPT layers a second electrode was deposited by vacuum evaporation in the same way as in example 1. The calcium layer was 20nm and the aluminium layer was lOOnm. Connections were made to the two electrodes. The device structure in this example is show in Fig. 2 and consists of a substrate 10, an ITO electrode 11 one edge of the substrate, a first (bottom) PTOPT layer fabricated through spin coating, a second (separate) PTOPT layer 13 made through spin coating in combina¬ tion with stretch orienting and transferring and a metal electrode 14 consisting of calcium and with an aluminium protecting layer. There are also connections 15 and 16 attached to the two electrodes 11 and 14. Measurements were carried out with the device, and the result is shown in Fig. 3 - 6 and in the tables 1 and 2. The behaviour of the electroluminescent device was verified through measurements of the current versus voltage and the polarisation behaviour of the emitted light with respect of the spectral distribution and the electroluminescence intensity. A broad emission with peaks at 630nm and at 680nm was detected when the voltage was applied. The electroluminescence intensity was higher parallel to the stretch direction compared to the peφendicular direc¬ tion. The polarisation ratio was 2,4. The colour of the emitted light is best described as red-orange and the intensity was high enough for the emission to be clearly observable in indoor light. The normalised emission spectra in Fig. 5 differs very little but a small shift towards lower energy occur for the light emitted parallel to the stretch direction. This was also expected since the effective conjuga¬ tion length is increased when stretching the polymer material, which leads to a decrease of the band gap. The IV characteristics for this device are very similar to the same kind of polymer light emitting diode, utilising PTOPT as the emitter, but where the polymer layer is not oriented. This shows that it is possible to use this transferring procedure without los¬ ing the performance of the device, i.e. having a proper polymer film. The external quantum efficiency of this device varied from 0.01 % at 3V to 0.1 % at 9V. The measurements of the polarisation properties was carried out in the following way: A polarisation filter was placed between the polymer light emitting diode and a photo detector. The polarisation filter was the rotated while the intensity was measured for some angles. The result of this is given in Fig. 6. This polarisation behaviour corresponds to similar measurements of photoluminescence for oriented MEH-PPV (T W Hagler et al, Physical Review B 44, 8652 (1991)). The achieved polarisation ratio of 2.4 indicates that the emis¬ sion mostly occur in the stretch oriented layer. On the basis of this the polarisation ratio has to be over 10 in the oriented layer to achieve a polarisation ratio of 2.4 if the emission was equally distributed over the entire polymer volume. All measurements were carried out at room temperature, in ambient atmosphere and on one and the same diode. EXAMPLE 3 Example 2 was repeated, but POPT was now used as the emitting layer instead of PTOPT. Connections were achieved in the same way for the electrodes, and POPT was used for the stretching instead of PTOPT. The PE/POPT structure was elongated 1.5 times the initial length. The thickness of the POPT layer was lOOnm before the stretching procedure. Then the device was connected to wires and voltage applied. The device emitted polarised light with colour of red-near infrared. The light was bright enough to be visible in indoor light at 6V. The intensity parallel to the stretching direction was 1.6 times higher than the intensity parallel to the stretching direction. The turn on voltage and the quantum yield was not estimated. EXAMPLE 4 Example 2 once again repeated but here POT was utilised as the emitting material. The elongation of the PE/POT structure was here 2,5 times. The thickness of the POT film was lOOnm before the stretching procedure. After that the device was connected to wires and then the voltage applied, the device emit¬ ted polarised light with colour of red-orange. The light was bright enough to be visible in indoor light at 6V. The electroluminescent intensity parallel to the orientation direction was 3.1 times higher than the intensity peφendicular to the orientation direction. The turn on voltage and the quantum efficiency was not estimated. EXAMPLE 5 In this performed example an electroluminescent device was fabricated, where a charge transport layer of PCHMT was inserted between the emitting layer and one electrode. PTOPT was solved in chloroform (5mg/ml). A PE foil with a thickness of 10mm (GLAD) was mounted on a circular plastic holder(polystyrene), with the puφose to fix the PE foil in a planar geometry during processing. The holder with the PE foil was mounted to the spin¬ ner. The PE surface was cleaned with hexane(n-hexane), when the PE foil was rotated by the spinner at lOOOφm for 30s. The foil was then dried in an oven at 40 C for 10 min. The holder with the PE foil was then again mounted on the spinner. The PTOPT solution was then spin coated at 1000 φm for 30s on the PE foil. After this time the polymer is com¬ pletely dry, no solvent left. The thickness of the PTOPT film was 500nm. This same substrate, which had a first electrode layer, that was used in example 1 for the construction of the electroluminescence device in example 1 was also utilised here. The substrate was mounted with the ITO surface up. A PCHMT solution (lOmg/ml in chlo¬ roform (CHCI3)) was applied to the substrate. The spinner was started and the substrate was rotated at lOOOφm for 30s. After this time the solvent had evaporated. This resulted in a film thickness of lOOnm. After this the two layer substrate was mounted to a holder and the PE/PTOPT was added to the PCHMT surface, PTOPT against PCHMT. The PE/PTOPT film was then pressed to the substrate with a rubber roller at the same time as the temperature was increased to 80C- 90C. At this temperature the PE foil was removed and the PTOPT film remained on the PTOPT film. On top of the PTOPT layer a second electrode was then vacuum evaporated in the following way. The substrate was mounted to a shadow mask. The substrate with the shadow mask was then transferred to the vacuum chamber. The chamber reached a pressure of p < 10 " ^Torr. Then a coating of calcium was applied by vacuum evaporation to a thickness of 20nm. Then a coating of lOOnm of aluminium was applied in the same way. Connections for the electrodes were made in the same way as before. The electrolumines¬ cent device were emitted light with a red-orange colour. It was possible to observe the light in ordinary indoor light at an applied voltage of 30V. The turn on voltage was 20V. The quantum efficiency was not estimated. TABLE 1. Datapoints for diagrams in figure 3. TABLE 2 Datapoint for diagrams in figure 6. Datapoint Angle to stretch Relative EL-intensity direction (°) 0 0.0000 1.0000 1 10.000 0.99038 2 20.000 0.94519 3 30.000 0.87212 4 40.000 0.78173 5 50.000 0.68654 6 60.000 0.58942 7 70.000 0.50673 8 80.000 0.46346 9 90.000 0.43942

Claims: Claims 1. Electroluminescent device, comprising a supporting substrate (10) and a first electrode layer (11) applied on this, a light emitting layer (12, 13) applied on the first electrode layer and the substrate, the light emitting layer (12, 13) being constituted by a conju¬ gated polymer with a light emitting capability, on the light emitting layer is applied a second electrode layer (14), the electroluminescent device also being provided with con¬ nections (15, 16) to the two electrode layers, characterised in that at least a part (13) of the light emitting layer (12, 13) is laminated with the substrate (10) and the first elec¬ trode layer (11) applied thereon as aN integral, separately built up layer (13) of a poly¬ mer or a mixture of polymers. 2. Electroluminescent device according to claim 1 characterised in that the substrate is constituted by transparent or translucent material. 3. Electroluminescent device according to claim 1 or 2, characterised in that at least a part (13) of the light emitting layer (12, 13) is constituted by a polymeric material that has its polymer chains oriented essentially in one direction by this part (13) of the light emitting layer (12, 13) being extended in this direction. 4. Electroluminescent device according to claim 3 characterised in that a light emitting layer (12, 13) is constituted by at least two part layers (12, 13) of which a first, the layer (12) situated closest to the substrate (10) is constituted by the conjugated polymer or polymer mixture and of which a second, further away from the substrate situated part layer (13) is constituted by the same conjugated polymers or polymeric mixture or an other conjugated polymer or mixture of polymers and is laminated with the underlying part layer (12) or layers. 5. Electroluminescent device according to any of the claims 1-4, characterised in that the second part layer (12) that is in direct contact against the substrate (10) and the first electrode layer situated thereon is applied directly thereon and that this or the part layer (13) lying above have been applied by lamination of separately fabricated part layers. .6. Electroluminescent device according to any of the claims 1-5, characterised in that the light emitting layer (12, 13) or at least one of its part layers is constituted by a conju¬ gated polymer or a mixture of polymers with oriented polymer chains. 7. Electroluminescent device according to any of the previous claims, characterised in that conjugated polymer is a substituted poly(thiophene), a polymer based on a possibly substituted poly(p-phenylenevinylene), a substituted poly(p-phenylene) or a possibly substituted poly(thiophenevinylene) . 8. Electroluminescent device according to claim 7 characterised in that a light emitting layer (12, 13) is constituted by poly[3-(4-octylphenyl)-thiophene], poly [3-(4- octylphenyl)-2,2'-bithiophene], poly(3-alkylthiophene), poly(3-cyclohexyl-4- methylthiophene) or poly(3-cyclohexylthiophene). 9. Electroluminescent device according to claim 8 and one of the claims 3-7 characterised in that one of the part layers is constituted by a poly(p-phenylvinylene) and a second part layer by a poly(cyanoterephtalylidene). lO.Electroluminescent device according to any of the previous claims, characterised in that one of the electrode layers is an electron injecting electrode layer and is constituted by a metal, metal alloy, doped semiconductor or a doped polymer with a high work function. 11.Electroluminescent device according to any of the claims 1-10 characterised in that one of the electrode layers is a hole injecting electrode layer and consists of a metal, metal alloy, metal oxide, doped semiconductor or doped polymer with a high work function. 12.Electroluminescent device according to any of the claims 1-11 characterised in that the first electrode layer (11) is a thin film of polyaniline, poly(3,4-ethylenedioxythiophene) or indium tin oxide as hole providing contact and that the second electrode layer (14) is a thin layer of calcium, aluminium, magnesium, indium, natrium, lithium, scandium or silver or mixtures thereof as electron providing metal contact. 13.Electroluminescent device according to any of the previous claims, characterised in that the substrate (10) is constituted by a glass, poly(etheneterephtalate)- or poly(ethene) sub¬ strate. 14.Method for the fabrication of an electroluminescent device, at which a substrate (10) is coated with a first electrode layer (11), a light emitting layer (12, 13) of a light emitting ability showing conjugated polymer or polymer mixtures, and a second electrode layer (14), thereafter connections (15, 16) to the two electrode layers (11, 14) are achieved, at which method the light emitting layer or a part of this (12, 13) is made on a support and by means of this is brought together with the substrate (10), characterised in that the light emitting layer (13) made separately on the support is deposited on the substrate (10) by the removal of the support. Iδ.Method according to claim 14 characterised in that the substrate is constituted by a transparent or translucent material. 16.Method according to claim 14 or 15 characterised in that as support is used a foil con¬ stituted by or having a surface layer of a material, which has a release property in rela¬ tion to the light emitting layer (13). 17. Method according to claim 14, 15 or 16 characterised in that as support is used a foil of poly(ethenterephtalate)- or poly(ethene). Iδ.Method according to claim 14-17 characterised in that as substrate (10) is used a glass, poly(etheneterephtalate)- or poly(ethene) substrate. 19.Method according to claim 14-18 characterised in that the light emitting layer (13) is made on the support by casting, smearing, dip coating or spin coating. 20.Method according to claim 14-19 characterised in that the coating of the substrate (10) and the thereon existing first electrode layer (11) with the light emitting layer (12, 13) is conducted in at least two steps for the making of one of two or several part layers (12, 13) constituted light emitting layers, in which the different part layers are constituted by the same or different polymeric materials. 21.Method according to claim 20, characterised in that the first part layer (12) of the light emitting layer (12, 13) lying directly on the substrate (10) and the there on existing first electrode layer (11) is made directly on this support and that the layer or layers of the light emitting layer (12, 13) lying on the outside of this are applied by first being made on the support and then by means of this, is laminated together with the electrolumines¬ cent device to be. 22.Method according to claim 14-21 characterised in that the light emitting layer or part- layer (13) made on the support are subjected to a pre-treatment, before it is laminated with underlying parts of the electroluminescent device to be. 23.Method according to claim 22 characterised in that the pre-treatment of the light emit¬ ting layer or partlayers (13) made on the support are executed by stretching of this and the support in the direction orienting the polymeric chains of the polymeric material in this direction, before this light emitting layer or part layer (13) is laminated with under¬ lying parts of the electroluminescent device. 24.Method according to claim 14-23 characterised in that as a conjugated polymer is used a substituted poly(thiophene), a polymer based on a possibly substituted poly(p- phenylenevinylene), a substituted poly(p-phenylene) or a possibly substituted poly(thiophenevinylene). 25. Method according to claim 24 characterised in that the light emitting layer (12, 13) is constituted by a possibly substituted poly(p-phenylenevinylene), a substituted poly(p- phenylene) or a possibly substituted poly(thiophenevinylene). 26.Method according to claim 24 or any of the claims 14-22, characterised in that one part layer (12) is constituted by a poly(p-phenylenevinylene) and second part layer (13) by a poly(cyanoterephtalylidene). 27.Method according to any of the claims 14-26 characterised in that one of the electrode layers is constituted by an electron injecting electrode layer and made of metal, metal alloy, doped semiconductor or doped polymer with a low work function. 28.Method according to any of the claims 14-27 characterised in that one of the electrode layers is made of a hole injecting electrode layer and constituted by metal, metal alloy, metal oxide, doped semiconductor or doped polymer with a low work function. 29.Method according to any of the claims 14-28 characterised in that the first electrode layer (11) is constituted by a thin film of polyaniline, poly(3,4-ethylenedioxythiophene) or indium tin oxide as a hole providing contact and that a second electrode layer (14) is constituted by a thin layer of calcium, aluminium, magnesium, indium, natrium, lithium, scandium or silver or mixtures thereof as electron providing metal contact.

Inventors: BERGGREN ROLF MAGNUS, DYREKLEV TORD PETER, INGANAES OLLE WERNER, BERGGREN, ROLF, MAGNUS, DYREKLEV, TORD, PETER, INGANAES, OLLE, WERNER
Applicants: BERGGREN ROLF MAGNUS, DYREKLEV TORD PETER, FORSKARPATENT I LINKOEPING AB, INGANAES OLLE WERNER, BERGGREN, ROLF, MAGNUS, DYREKLEV, TORD, PETER, INGANAES, OLLE, WERNER
Application year: 1995
Main classification: H05B33
IPC codes: C09K11, H01L51, H05B33