Method of manufacturing a layer for an optoelectronic or electronic component, layer for an optoelectronic or electronic component and optoelectronic or electronic component

Abstract

The invention relates to a method for producing a layer for an optoelectronic or electronic component, a layer for the method and a layer produced by the method and an optoelectronic or electronic component. In the method, a layer is provided with an organic charge transport material or organic charge injection material doped with at least one UV-sensitive dopant. The layer is irradiated with UV radiation in at least one area of the layer. The UV radiation deactivates the at least one UV-sensitive dopant of the layer in the region that is irradiated with the UV radiation, so that the electrical conductivity of the organic charge transport material or organic charge injection material and thus also the electrical conductivity of the layer in the region that is irradiated with the UV radiation is reduced.

Description

[0001] Method of manufacturing a layer for an optoelectronic or electronic component, layer for an optoelectronic or electronic component and optoelectronic or electronic component

[0002] The invention relates to a method for producing a layer for an optoelectronic or electronic component, a layer produced by the method and an optoelectronic or electronic component. In the method, a layer is provided with an organic charge transport material or organic charge injection material doped with at least one UV-sensitive dopant. The layer is irradiated with UV radiation in at least one area of the layer. The UV radiation deactivates the at least one UV- sensitive dopant of the layer in the region that is irradiated with the UV radiation, so that the electrical conductivity of the organic charge transport material or organic charge injection material and thus also the electrical conductivity of the layer in the region that is irradiated with the UV radiation is reduced.

[0003] Optoelectronic devices, such as displays, spectrometers or spatial-resolution photo sensors, have arrays of optoelectronic components. Ideally, the optoelectronic components in these arrays should not interfere with each other. In real devices, however, crosstalk regularly occurs between neighboring optoelectronic components. In photodetectors, for example, charge carriers of the neighboring photodetectors, generated by photons, can leak into a neighboring photodetector as leakage currents, which are erroneously measured there as a crosstalk signal.

[0004] In US10 / 417,310, a signal processing method is proposed in which the crosstalk in a signal from a photodetector is corrected using signals from the neighboring photodetectors and previously determined amplification factors. However, such methods do not eliminate the crosstalk, i.e. the leakage currents between photodetectors, but are only subsequent signal corrections. They also require a high computational capacity and must be adapted to the respective components.

[0005] The present invention is therefore based on the task of overcoming these disadvantages in the prior art and of providing a method by which a layer for an optoelectronic or electronic component can be produced with a defined, in particular reduced, electrical conductivity of the layer, at least in a spatial region. Furthermore, the invention relates to the use of the method for reducing the cross talk in an optoelectronic or electronic component, for charge shielding on electrodes in an optoelectronic or electronic component or for reducing the absorption or resonant wavelength in an optical resonator of an optoelectronic component, a layer produced by the method according to the invention and an optoelectronic or electronic component with such a layer.

[0006] Kailuweit & Uhlemann | Patentanwalte The problem is solved by a method according to claim 1 , the use of the method and a layer and an optoelectronic or electronic component according to the subsidiary claims. Advantageous embodiments and further embodiments are described in the dependent claims.

[0007] In the method of manufacturing a layer for an optoelectronic or electronic component, a layer for an optoelectronic or electronic component is provided which comprises or consists of an organic charge transport material or an organic charge injection material, wherein the organic charge transport material or the organic charge injection material is doped with at least one UV-sensitive, preferably molecular, dopant. The organic charge transport material or organic charge injection material may be a hole transport material or injection material or an electron transport material or injection material. Additionally, the charge transport material can also be a charge injection material.

[0008] In the method, the layer is irradiated with ultraviolet electromagnetic radiation (UV radiation) in at least one region of the layer and the at least one UV-sensitive dopant is deactivated by the irradiation with the UV radiation in the region that is irradiated with the UV radiation. As a result of the deactivation, the electrical conductivity of the charge transport material or charge injection material with the UV-sensitive dopant and thus also the electrical conductivity of the layer is permanently reduced, i.e. lowered or decreased, in the area irradiated with the UV radiation. An area is to be understood as a spatial area.

[0009] The process can therefore be used to specifically change the electrical conductivity of the layer in the area that is irradiated with UV radiation, for example by adjusting it to a defined value (target value). In particular, this allows areas with reduced electrical conductivity (areas irradiated with UV radiation) and areas with unchanged or less reduced electrical conductivity (non-irradiated or less irradiated areas) to be created, so that the layer can be specifically divided or structured into spatial areas with different electrical conductivity and thus into different functional, spatial areas using the method.

[0010] Irradiation with UV radiation is preferably carried out parallel to the normal direction of the layer, i.e. perpendicular to the surface of the layer, but can also be carried out at an angle to the normal of the layer. The layer is preferably completely irradiated by the UV radiation in the direction of irradiation, so that the UV-sensitive dopant is deactivated in the entire irradiated volume of the layer in the direction of irradiation. Accordingly, irradiation in a region is understood to mean irradiation that takes place in sections or regions in relation to a direction orthogonal to the direction of irradiation.

[0011] In embodiments, the organic charge transport material or organic charge injection material may comprise an organic chromophore. The organic charge transport material or organic

[0012] Kailuweit & Uhlemann | Patentanwalte charge injection material may be a material selected from the group consisting of phthalocyanines (such as zinc phthalocyanine, copper phthalocyanine or iron phthalocyanine), pyrans, e.g. bispyranilides (abbreviated as TPDP), fulvalenes, e.g. tetrathiofulvalene (abbreviated as OMTTF) and aromatic amines. Tetrathiofulvalene (abbreviated as OMTTF) and aromatic amines, e.g. N,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine (abbreviated as MeO-TPD), or 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (abbreviated as m- MTDATA), spirofluorenes, e.g. 2,7-bis[N,N-bis(4-methoxy-phenyl)amino]9,9-spirobifluorenes (abbreviated as Spiro-MeO-TPD) or 2,2',7,7'-tetra(N,N-di-p-tolyl)amino-9,9-spirobifluorene (abbreviated as Spiro-TTB), the bisthiopyranilidenes, the bipyridinylidenes, the diketopyrrolopyrroles and the polythiophenes, e.g. Poly(2,5-bis(3-alkylthiophene-2-yl)- thieno[3,2-b]thiophenes (abbreviated as pBTTT) or consist of this material.

[0013] Preferably, the organic charge transport material or the organic charge injection material is a material selected from the group of triarylamine derivatives in which two triarylamine redox centers are connected via a variable pi bridge, in particular a triarylamine derivative in which free para positions are protected against subsequent electrochemical reactions by methoxy groups. The organic hole transport material or organic hole injection material MeO-TPD or Spiro-TTB is particularly preferred.

[0014] The UV-sensitive dopant is a dopant which is physically and / or chemically altered by irradiation with UV radiation in such a way that it is deactivated, i.e. fewer charge carriers are available for electrical charge transport. In the process, the electrical conductivity of the organic charge transport or charge injection material doped with the UV-sensitive dopant can decrease with respect to the UV-sensitive dopant by more than a factor of 2, preferably by more than a factor of 5, particularly preferably by more than a factor of 10, as a result of the UV irradiation. The UV-sensitive dopant can, for example, be a material selected from the group of fullerenes or cyano-quinodimethane derivatives. Preferably, the UV-sensitive dopant can be selected from Ceo-fullerene, 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviated as F4- TCNQ), chloranil and 1 ,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane (abbreviated as Fe-TCNNQ).

[0015] In embodiments, the organic charge transport material or organic charge injection material may be doped with at least one UV-insensitive, preferably molecular, dopant in addition to the UV-sensitive dopant. A UV-insensitive dopant is a dopant that is not deactivated or degraded by irradiation with UV radiation, meaning the charge carrier transport in the organic landing transport or charge injection material remains essentially unchanged. Essentially unchanged means that the electrical conductivity of the organic charge transport material or charge injection material doped with the UV-insensitive dopant decreases in relation to the UV-

[0016] Kailuweit & Uhlemann | Patentanwalte insensitive dopant by a factor of at most 2, preferably by a factor of at most 1 .5, particularly preferably by a factor of at most 1.25. Doping with the UV-insensitive dopant ensures that the electrical conductivity of the layer does not fall below a threshold determined by the UV- insensitive dopant during UV irradiation or is reduced. The additional doping with an insensitive dopant therefore offers a further possibility to specifically influence the electrical conductivity of the layer.

[0017] Advantageously, the UV-insensitive dopant can be a material selected from the group of 3- radialenes disclosed in EP 2 180 029 A1 and KR 2017 0 074 170 A. The p-dopant as described in WO 2021 / 048 044 A on page 62, line 10ff, according to formula (1):

[0018] Formula (1), is especially suitable as an UV-insensitive dopant.

[0019] The UV-sensitive dopant may have a concentration of 0.5 wt% to 20 wt% of the organic charge transport material or organic charge injection material, preferably 5 wt% to 17.5 wt% of the organic charge transport material or organic charge injection material. The UV-insensitive dopant may have a concentration of 0.5 wt.% to 20 wt.% of the organic charge transport material or organic charge injection material, preferably 5 wt.% to 17.5 wt.% of the organic charge transport material or organic charge injection material.

[0020] The layer can be provided on a carrier layer or a layer stack of an optoelectronic or electronic component. Carrier layers can be, for example, layers of glass or silicon, but also polymer films, e.g. made of polyimide. The layer can be provided or formed in a thermal deposition process, a chemical or physical vapor deposition process, a sputtering process, a deposition process from solutions, a dip coating process, a spin coating process, a casting process, a rod coating process, a roller coating process or a printing process.

[0021] The thickness of the layer before irradiation with UV radiation is preferably in the range between 0.1 nm and 1 pm, depending on both the material of the layer and the structure of the optoelectronic or electronic component. In the case of layers for charge-transfer photodiodes (CTPD), for example, the thickness can be in the range from 10 nm to 1 pm, while for

[0022] Kailuweit & Uhlemann | Patentanwalte photodiodes with direct material absorption in mixed layers or planar heterojunctions it can be in the range from 0.1 nm to 100 nm.

[0023] Irradiation with UV radiation typically takes place in a wavelength range from 180 nm to 450 nm, preferably from 180 nm to 300 nm. The degree of deactivation of the UV-sensitive dopant depends on the radiation intensity and the duration of irradiation with UV radiation. In the process, the electrical conductivity of the layer can therefore be changed or reduced with the UV radiation as a function of the radiation intensity and the duration of the irradiation, i.e. as a function of the radiation dose.

[0024] The radiation intensity and / or irradiation duration of the UV radiation can be adapted to the layer thickness of the coating, the concentration of the UV-sensitive dopant, the concentration of the UV-insensitive dopant and / or the electrical conductivity to be achieved. Typical irradiation times with mercury lamps can be 50 minutes to 180 minutes, but with an excimer laser as the radiation source they can also be less. Preferably, the irradiation can be carried out with a dose of at least 80 J / cm2, preferably at least 100 J / cm2, more preferably at least 500 J / cm2, particularly preferably with a dose of at least 1000 J / cm2. In particular, the dose can be selected such that the electrical conductivity of the layer in relation to the UV-sensitive dopant is reduced or decreased by at least 10% per hour of irradiation time, preferably by at least 20% per hour of irradiation time, particularly preferably by at least 50% per hour of irradiation time. Radiation sources for irradiation with UV radiation can be, for example, mercury lamps or excimer lasers, in particular krypton, argon, or xenon fluoride lasers.

[0025] During the doping process, the UV-sensitive dopant is charged by accepting or releasing a charge carrier so that the layer comprising the UV-sensitive dopant can absorb electromagnetic radiation in the infrared range, typically in the near infrared range. By deactivating the UV-sensitive dopant, this absorption can decrease again and the refractive index and extinction coefficient of the layer can change accordingly. This means that deactivating the UV-sensitive dopant can also cause an optical modification of the coating in the spatial area that is irradiated with UV radiation, which can be described as light-induced bleaching.

[0026] In the process, the electrical conductivity of the layer and at least one absorption band of the layer can thus be reduced by deactivating the at least one UV-sensitive dopant in the region which is irradiated with the UV radiation. In particular, in the region which is irradiated with the UV radiation, the electrical conductivity of the layer in relation to the UV-sensitive dopant can be reduced to at most 50%, preferably to at most 10%, particularly preferably to at most 1% of the electrical conductivity without irradiation with the UV radiation and / or the at least one absorption band of the layer in a wavelength range between 400 nm and 2000 nm or 2500 nm

[0027] Kailuweit & Uhlemann | Patentanwalte inclusive can be reduced to at most 70%, preferably at most 50%, particularly preferably at most 10% of the absorption without irradiation.

[0028] UV irradiation can be used to change or reduce the optical resonance behavior in a defined manner, in particular the optical path length and the resonance wavelength, of an optical resonator formed with the coating. This not only makes it possible to compensate for deviations in the resonance behavior that occur, for example, due to production-related irregularities in the layer thickness or the resonator width, but also to produce resonators with defined, i.e. specific, resonance wavelengths.

[0029] Optoelectronic devices with an optical resonator are known, for example, from US 24 347 999 A or the work of Siegmund et al. in Nat. Commun. 8, 15421 (2017) are known. An optical resonator is formed, for example, by a hole-conducting charge carrier layer, a photoactive layer and an electron-conducting charge carrier layer, which are formed between two reflection surfaces arranged parallel to each other. Between the reflective surfaces, incident electromagnetic radiation is reflected several times in the optical resonator. If the optical path length between the reflective surfaces corresponds to an integer multiple of half the wavelength of the radiation, the wavelength of the radiation interferes constructively and is amplified. The optical resonance chamber forms an optical resonator for this constructively interfering wavelength, which is referred to as the resonance wavelength.

[0030] The resonance wavelength can be reduced by 1 nm to approx. 200 nm using this method. The wavelength range in which the resonance wavelength shifts depends on the respective organic charge transport or charge injection material and the layer thickness and can be in the visible light to infrared range, e.g. in a wavelength range from 400 nm to 2.5 pm. If the charge transport or charge injection material comprises a UV-insensitive dopant, its doping properties are essentially not deactivated by irradiation with UV radiation. The layer continues to be partially electrically conductive even after partial optical bleaching, i.e. it remains functional.

[0031] The layer can be a layer of an optoelectronic or electronic component, for example a semiconductor layer of a photodetector, a solar cell, an OLED, a spectrometer, a display device or an organic transistor, in particular also a layer of an optical resonator. The process can therefore also be used advantageously for the production of layers in optical resonator.

[0032] In embodiments, it may be provided that the irradiation with the UV radiation is carried out as a function of a specific electrical conductivity, a layer thickness, an absorption intensity, a transmission intensity, a Raman shift and / or Stokes shift of the layer or of the optoelectronic or electronic component comprising the layer. The aforementioned parameters can be determined or measured on the layer or the optoelectronic or electronic component, i.e. in-situ,

[0033] Kailuweit & Uhlemann | Patentanwalte after the layer or the component has been provided or formed. Alternatively, the parameters can also be determined on a reference layer or a reference component that was produced using the same process as the layer or the respective component. The irradiation can be carried out depending on a difference between the measured or determined parameter and a predetermined value (target value) of the parameter.

[0034] If the irradiation with the UV radiation is carried out after the production of an organic electronic device formed with the layer, the irradiation can also be carried out as a function of a resonator width and / or the resonance wavelength of the optical resonator. As an alternative to irradiation after production of the optical resonator, irradiation with UV radiation can also be carried out during production of the optical resonator.

[0035] The UV radiation can be spatially and temporally constant, i.e. have a homogeneous radiation intensity and irradiation duration. However, spatial intensity distributions and / or spatial distributions of the irradiation duration, i.e. locally different irradiation times, can also be provided. These distributions can, for example, be selected in such a way that the layer is divided or structured into areas with a higher electrical conductivity and areas with a lower electrical conductivity by irradiation with the UV radiation; i.e. the distributions can have areas that are not irradiated or are irradiated with a lower radiation intensity and / or a lower irradiation duration, and areas that are irradiated with a higher radiation intensity and / or a higher irradiation duration. In particular, the distributions can be designed in such a way that a matrix or array is formed from areas that remain unirradiated or are irradiated with a lower radiation intensity and / or a lower irradiation duration, and areas that are irradiated with a higher radiation intensity and / or a higher irradiation duration.

[0036] In embodiments, regions with higher radiation intensity and / or higher irradiation duration may be arranged around at least one non-irradiated region or at least one region with lower radiation intensity and / or lower irradiation duration. With such an irradiation, the layer can be structured in such a way that the lateral electrical conductivity between neighboring areas with a higher electrical conductivity is reduced. Areas with a higher electrical conductivity can thus be electrically insulated from each other by areas with a lower electrical conductivity.

[0037] The areas with higher electrical conductivity, i.e. the areas that were not irradiated or were irradiated with lower radiation intensity and / or lower irradiation duration, can for example be photoactive areas of an optoelectronic component, e.g. an optoelectronic component of a measuring device or imaging device with several neighboring optoelectronic components, such as photodiodes, OLEDs or solar cells. By reducing the lateral electrical conductivity between the components, leakage currents or crosstalk between neighboring areas or components are suppressed.

[0038] Kailuweit & Uhlemann | Patentanwalte In embodiments, the areas with higher electrical conductivity, i.e. the areas that are not irradiated or are irradiated with lower radiation intensity and / or lower irradiation duration, can be electrodes, for example. By reducing the electrical conductivity around these areas, the electrodes can be shielded against charges with the same polarity. The areas with reduced electrical conductivity can therefore be formed as so-called hole-blocking or electron-blocking areas. The method can therefore be used to form a layer that is a charge-blocking layer, at least in the area or areas that are irradiated with UV radiation. The electrodes can in particular be electrodes of an organic transistor. The method can therefore be used particularly advantageously for the production or structuring of organic transistors, which has been very complex to date compared to silicon-based transistors.

[0039] In embodiments, it may be provided that the distributions of the radiation intensity and / or the duration of the UV radiation are designed such that areas of the layer in which the layer thickness of the layer is more than a predetermined or specified layer thickness (target value) are irradiated with a higher radiation intensity and / or a higher irradiation duration than areas in which the layer thickness is less than the predetermined or specified layer thickness. The distributions can, for example, have a gradient in the radiation intensity or-duration, so that inhomogeneous optical properties, which result, for example, from a production-related gradient in the layer thickness of the coating, are compensated for.

[0040] Particularly preferably, the method can be carried out for a plurality of layers or areas of a layer. The layers or areas can be layers or areas of one or more optoelectronic and / or electronic components, whereby the layers or areas can be arranged, for example, on a common carrier layer or a common layer stack. The layers or areas can also be formed as a common layer or in a common layer of the component or components. The layers or areas can be irradiated with the same or different wavelengths, irradiation intensities and / or irradiation durations of the UV radiation.

[0041] In embodiments, in particular in groups of layers or in groups of spatial regions of a layer, the electrical conductivities and absorptions of the layers or regions, and in the case of optical resonators also the resonance wavelengths, can each be reduced to specific electrical conductivities, absorption values and / or resonance wavelength values which differ from one another, in particular within the group.

[0042] The groups (pixels) can be arranged in arrays. For example, they can be evenly spaced from each other in at least one spatial direction. The layers or areas of a pixel, which are also referred to as subpixels, can be arranged in a pen-tile pixel geometry. For example, arrays of optoelectronic components functioning in the same way in groups can be produced for spectrally and / or spatially resolving measuring devices or imaging devices, in particular for the

[0043] Kailuweit & Uhlemann | Patentanwalte visible light range and the near infrared range. The method can be used in particular to produce hyperspectral photodetectors, i.e. the method can be used to produce hyperspectral photodetectors. Alternatively, the process can also be used to produce pixels for display devices from OLEDs.

[0044] In summary, the method according to the invention can therefore be used, among other things, for reducing crosstalk, for electrode shielding or for reducing the absorption or the resonance wavelength of an optical resonator.

[0045] The invention also relates to a layer produced according to the method described and to an optoelectronic or electronic component with at least one layer produced according to the method described. In particular, the component can be a multicolor photodetector (hyperspectral photodetector). However, the invention is not limited to photodiodes or photodetectors, but the method of deactivation or light-induced bleaching can also be carried out to produce other optoelectronic or electronic components, such as OLEDs, in which a layer is formed in accordance with the invention.

[0046] In the following, the invention will be illustrated with reference to Fig. 1 to Fig. 6. The invention is not limited to the embodiments shown and described, but also includes embodiments having the same effect in the sense of the invention. Furthermore, the invention is not limited to the specifically described combinations of features, but can also be defined by a combination of the features, provided that the features are not mutually exclusive or a specific combination of features is not explicitly excluded.

[0047] It shows:

[0048] Fig. 1 : the change in electrical conductivity as a function of the irradiation time with UV radiation using the example of MeO-TPD layers doped with Fe-TCNNQ dopants,

[0049] Fig. 2: the change in electrical conductivity as a function of the duration of exposure to UV radiation using the example of a Spiro-TTB layer doped with 4 wt.% Fe-TCNNQ,

[0050] Fig. 3: an absorption spectrum for the example of a MeO-TPD layer with a 5.0 % mass concentration of Fe-TCNNQ before and after irradiation with UV radiation,

[0051] Fig. 4: an absorption spectrum for the example of a MeO-TPD layer with a 10.0 % mass concentration of Fe-TCNNQ before and after irradiation with UV radiation,

[0052] Fig. 5: an absorption spectrum for the example of a MeO-TPD layer with a 16.5 % mass concentration of Fe-TCNNQ before and after irradiation with UV radiation, and

[0053] Kailuweit & Uhlemann | Patentanwalte Fig. 6: the change in electrical conductivity as a function of the irradiation time with UV radiation using the example of MeO-TPD layers doped with dopant C60F36, C60F48, p-dopant according to formula (1) and using the example of Spiro-TTB layers doped with dopant Fe-TCNNQ.

[0054] Fig. 1 shows the principle of the method according to the invention using the example of MeO- TPD layers with Fe-TCNNQ- doping. The process is not limited to MeO-TPD layers with Fe- TCNNQ- doping and can also be carried out with other organic charge transport or charge injection materials that are doped with a UV-sensitive dopant and optionally a UV-insensitive dopant within the meaning of the invention.

[0055] Fe-TCNNQ is a UV-sensitive dopant whose doping property is deactivated by irradiation with UV radiation. By irradiating the layer with UV radiation, the electrical conductivity, i.e. the charge carrier transport, of the layer decreases permanently with increasing irradiation time, as shown in Fig. 1. The electrical conductivity of a layer that comprises an organic charge transport and / or organic charge injection material or consists of an organic charge transport and / or organic charge injection material that is doped with a UV-sensitive dopant, such as Fe- TCNNQ, can therefore be specifically reduced by means of UV irradiation, for example set to a predetermined value. If only individual spatial areas of a layer are irradiated with UV radiation, the layer can be structured into different functional areas by means of UV irradiation.

[0056] CredoxysO-Dopant according to formula (1):

[0057] In contrast to Fe-TCNNQ, the p-dopant according to formula (1) is a UV-insensitive dopant that remains substantially unchanged upon exposure to UV irradiation compared to a UV-sensitive dopant. Therefore, the electrical conductivity of a layer comprising or consisting of an organic charge transport or charge injection material with a UV-insensitive dopant remains substantially unchanged upon irradiation with the UV radiation with respect to the electrical conductivity of the UV-insensitive dopant. Thus, by additionally doping the material with a UV- insensitive dopant, on the one hand, the electrical conductivity of the material itself can be increased and, on the other hand, an electrical conductivity can be specified which is not undercut by the UV irradiation.

[0058] Doping with a UV-insensitive dopant offers a further possibility to influence the electrical conductivity of the material or the layer that this charge transport or charge injection material has.

[0059] Accordingly, in the method for producing a layer for an optoelectronic or electronic component, a layer comprising or consisting of an organic charge transport material or an organic charge injection material is provided, with the organic charge transport material or the organic charge injection material being doped with at least one UV-sensitive dopant and optionally at least one

[0060] Kailuweit & Uhlemann | Patentanwalte UV-insensitive dopant. The layer is irradiated with UV radiation in at least one region and the at least one UV-sensitive dopant of the layer is deactivated by the UV radiation in the region that is irradiated with the UV radiation. The electrical conductivity of the layer decreases as a result of the deactivation. The process can therefore be used to change the electrical conductivity of the layer in a targeted manner and adjust it to a defined value (target value) in the area that is irradiated, for example.

[0061] By irradiating regions with UV radiation, regions with reduced electrical conductivity, in which the doping properties of the UV-sensitive dopant have been deactivated, and regions with unchanged electrical conductivity, in which the doping properties of the UV-sensitive dopant have not been deactivated or the UV-sensitive dopant has not been degraded, can be created in the layer, so that the layer can be structured into different functional regions using the method. The electrical conductivities of the areas with higher and lower electrical conductivity can differ by a factor of at least 3, preferably a factor of at least 50, particularly preferably a factor of at least 300.

[0062] The organic charge transport material or organic charge injection material can be a material selected from the group of phthalocyanines, pyrans, fulvalenes, aromatic amines, bisthiopyranilidenes, bipyridinylidenes, diketopyrrolopyrroles, spirobifluorenes or polythiophenes. The at least one UV-sensitive dopant can be a dopant selected from the group of fullerenes, in particular Ceo fullerenes, the group of fluorofullerenes, in particular CeoFis, C60F48 or CeoFae, or the group of cyano-quinodimethane derivatives, in particular 7, 7,8,8- tetracyano-2,3,5,6-tetrafluoroquinodimethane, chloranil, and / or 1 , 3, 4, 5,7,8- hexafluorotetracyano-naphthoquinodimethane. The at least one UV-insensitive dopant can be a dopant selected from the group of 3-radialene. The p-dopant according to formula (1) is especially suitable as an UV-insensitive dopant. The UV-sensitive dopant and the UV- insensitive dopant can each have a concentration in the organic charge transport material or the organic charge injection material of from 0.5 wt.% to 20 wt.%, preferably from 5 wt.% to 17.5 wt.%.

[0063] Irradiation with UV radiation can take place in a wavelength range from 180 nm to 450 nm, preferably from 180 nm to 300 nm. The irradiation intensity and irradiation duration can be selected in such a way that the electrical conductivity of the layer with respect to the UV- sensitive dopant is reduced or decreased by at least 10% per hour of irradiation duration, preferably by at least 20% per hour of irradiation duration, particularly preferably by at least 50% per hour of irradiation duration. In addition to the electrical conductivity, the absorption of the layer, in particular at least one absorption band of the layer in a wavelength range between 400 nm and 2500 nm, can also be reduced. For example, the irradiation can be initiated over

[0064] Kailuweit & Uhlemann | Patentanwalte the course of three minutes with a mean power per unit area of 17.78 mW / cm2, corresponding to a dose of 3,200 mJ / cm2, followed by an irradiation over the course of 57 minutes with a constant power per unit area of 25 mW / cm2, corresponding to a dose of 85,500 mJ / cm2, resulting in a total dose of 88,700 mJ / cm2over the course of one hour.

[0065] The layer can be a layer of an optoelectronic or electronic component, in particular a layer of a photodetector, an OLED, an organic solar cell, a spectrometer, a display device or an organic transistor. Since the method can also be used to influence the optical properties of the layer, in particular the absorption and transmission, the layer can also be a layer of an optical resonator.

[0066] The irradiation with the UV radiation can be carried out as a function of a specific electrical conductivity, a layer thickness, an absorption intensity, a transmission intensity, a Raman and / or Stokes shift of the layer and / or as a function of a resonance wavelength of an optical resonator formed with the layer. In particular, the irradiation can be carried out depending on a difference between at least one of these parameters and a predetermined value (target value) of the parameter.

[0067] The irradiation can be constant in space and time. However, the UV radiation can advantageously also have an intensity distribution and / or distribution of the irradiation duration with areas in which the layer is not irradiated or is irradiated with a lower radiation intensity and / or a lower irradiation duration, and areas in which the layer is irradiated with a higher radiation intensity and / or a higher irradiation duration. The areas with a higher radiation intensity and / or a higher irradiation duration can each be arranged adjacent to an unirradiated area or an area with a lower radiation intensity and / or a lower irradiation duration.

[0068] The areas in which the layer is not irradiated or is irradiated with a lower radiation intensity and / or a lower irradiation duration can be photoactive areas of an optoelectronic component or electrodes of an optoelectronic or electronic component, such as an organic transistor. For the production of optical resonators, the areas in which the layer is irradiated with a higher radiation intensity and / or a higher irradiation duration can be areas of the optical resonators.

[0069] The method can thus be used, for example, to reduce crosstalk between optoelectronic or electronic components, for charge shielding of an electrode of an optoelectronic or electronic component or to reduce the resonance wavelength of an optical resonator in an optoelectronic component.

[0070] Particularly advantageously, the method can be carried out on several layers or several areas of a layer. The layers or regions can be layers or regions of one or more optoelectronic and / or electronic components, wherein the layers or regions can be arranged, for example, on a

[0071] Kailuweit & Uhlemann | Patentanwalte common carrier layer or a common layer stack of the optoelectronic or electronic component or can be formed as a common layer or in a common layer of the component or components. The layers or areas can be irradiated with the same or different wavelengths, irradiation intensities and / or irradiation durations of the UV radiation.

[0072] In particular, the irradiation can be carried out with a spatial intensity distribution and / or spatial distribution of different irradiation durations, with which the electrical conductivities and absorptions of the layers or regions - in the case of optical resonators also the resonance wavelengths - are each reduced in groups of layers or groups of regions of a layer to specific electrical conductivities, absorption values and / or resonance wavelengths, which differ from one another in particular within the group.

[0073] The intensity distribution and / or spatial distribution of irradiation durations can be selected in such a way that the layers, areas and / or groups (pixels) of layers or areas are arranged in arrays. For example, they can be evenly spaced from each other in at least one spatial direction. The layers or areas of a pixel, which are also referred to as subpixels, can be arranged in a pen-tile pixel geometry. The method can be used, for example, to produce arrays of optoelectronic components functioning in groups in the same way for spectrally and / or spatially resolving measuring devices or imaging devices, in particular for the visible light range and the near infrared range. The method can be used in particular to produce hyperspectral photodetectors, i.e. the method can be used to produce hyperspectral photodetectors. Alternatively, the process can also be used to produce pixels for display devices from OLEDs.

[0074] Fig. 2 illustrates the principle of the process using the example of the change in the electrical conductivity of Spiro- TTB layers doped with 4 wt.% Fe-TCNNQ, a UV-sensitive dopant. UV irradiation was carried out with a mercury lamp on glass layer stacks, 150 nm Spiro-TTB doped with 4 wt.% Fe-TCNNQ and 30 nm gold. The electrical conductivities are given in relation to an assumed, unchanged layer thickness (open symbols) and in relation to the actual, reduced layer thickness (closed symbols) in order to illustrate the effect of the dopants independently of the influence of the layer thickness.

[0075] When doping with the UV-sensitive dopant, the electrical conductivity with respect to the UV- sensitive dopant is greatly reduced by the UV irradiation with increasing irradiation time, typically by more than a factor of 2, preferably by more than a factor of 5, particularly preferably by more than a factor of 10. The electrical conductivity can, for example, be reduced to an electrical conductivity below 0.1 S / m, particularly preferably below 0.01 S / m. When doped with a UV-insensitive dopant, however, the electrical conductivity of the layer is largely maintained despite UV irradiation (not shown). The UV-insensitive dopant and its concentration can, for example, be selected in such a way that the electrical conductivity decreases by a factor of at

[0076] Kailuweit & Uhlemann | Patentanwalte most 2, preferably by a factor of at most 1 .5, particularly preferably by a factor of at most 1.25 during UV irradiation in relation to the UV-insensitive dopant. When doping with both a UV- sensitive dopant and a UV-insensitive dopant, the electrical conductivity of the doped charge transport or injection material can therefore be reduced by UV irradiation, ensuring the electrical conductivity does not fall below a lower threshold value, which depends on the concentration of the UV-insensitive dopant.

[0077] Fig. 3 to Fig. 5 show examples of absorption spectra for MeO-TPD layers doped with Fe- TCNNQ. With increasing irradiation time, the absorption in the wavelength range between 380 nm and 2500 nm decreases due to UV irradiation. The decrease is particularly noticeable at the absorption bands at 480 nm to 500 nm, 700 nm, and 1100 nm to 1200 nm, and also occurs in a wavelength range between 2000 nm and 2500 nm (not shown). The method can therefore also be used to change the optical properties of a layer. In particular, they can be specifically set to a predetermined target value depending on the irradiation intensity and / or irradiation duration.

[0078] The method can be used, for example, to specifically reduce or diminish the resonance wavelength of an optical resonator formed with the layer. In this way, for example, deviations in the resonance wavelength resulting from production-related deviations in the layer thickness of an optical resonator can be advantageously compensated and resonators with defined resonance wavelengths can also be produced. Optical resonators with different resonance wavelengths are used, for example, in spectrally and / or spatially resolving measuring devices or imaging devices. The method can be used in particular to produce hyperspectral photodetectors, i.e. the method can be used to produce hyperspectral photodetectors. Alternatively, the method can also be used, for example, to manufacture display devices from OLEDs.

[0079] Kailuweit & Uhlemann | Patentanwalte

Claims

Patent claims1. Method for producing a layer for an optoelectronic component, in which: a layer comprising an organic charge transport material or an organic charge injection material or consisting of an organic charge transport material or an organic charge injection material is provided, wherein the organic charge transport material or the organic charge injection material is doped with at least one UV- sensitive dopant, and the layer is irradiated with UV radiation at least in a spatial region of the layer, and the at least one UV-sensitive dopant of the layer is deactivated by irradiation with the UV radiation in the spatial region irradiated with the UV radiation, and thus the electrical conductivity of the layer in the region irradiated with the UV radiation is specifically changed or the optical resonance behavior of an optical resonator formed with the layer is changed or reduced in a defined manner.

2. The method according to claim 1 , characterized in that the organic charge transport material or the organic charge injection material is a material selected from the group consisting of phthalocyanines, pyrans, fulvalenes, aromatic amines, bisthiopyranilidenes, bipyridinylidenes, diketopyrrolopyrroles, spirobifluorenes or polythiophenes.

3. The method according to one of the preceding claims, characterized in that the organic charge transport material or organic charge injection material is N,N,N',N'-tetrakis(4- methoxyphenylj-benzidine or 2,2',7,7'-tetra(N,N-di-p-tolyl)amino-9,9-spiro bifluorene.

4. The method according to one of the preceding claims, characterized in that the at least one UV-sensitive dopant is a dopant selected from the group of fullerenes or cyano- quinodimethane derivatives.

5. The method according to any one of the preceding claims, characterized in that the at least one UV-sensitive dopant is selected from Ceo-fullerene, 7,7,8,8-tetracyano-2,3,5,6- tetrafluoroquinodimethane, chloranil, and 1 ,3, 4,5,7, 8-hexafluorotetracyano- naphthoquinodimethane.

6. The method according to one of the preceding claims, characterized in that the organic charge transport material or the organic charge injection material is doped with at least one UV-insensitive dopant.Kailuweit & Uhlemann | Patentanwalte7. The method according to one of the preceding claims, characterized in that the at least one UV-insensitive dopant is a dopant selected from the group of the 3-radialenes or the p- dopant according to formula (1):Formula (1).

8. The method according to one of the preceding claims, characterized in that the UV- sensitive dopant in the organic charge transport material or the organic charge injection material has a concentration of 0.5 wt.% to 20 wt.%, preferably from 5 wt.% to 17.5 wt.%, and / or the UV-insensitive dopant in the organic charge transport material or the organic charge injection material has a concentration of 0.5 wt.% to 20 wt.%, preferably from 5 wt.% to 17.5 wt.%.

9. The method according to one of the preceding claims, characterized in that the irradiation with the UV radiation takes place in a wavelength range from 180 nm to 450 nm, preferably from 180 nm to 300 nm.

10. The method according to one of the preceding claims, characterized in that the irradiation intensity and irradiation duration are selected in such a way that the electrical conductivity of the layer with respect to the UV-sensitive dopant is reduced or decreased by at least 10% per hour of irradiation duration, preferably by at least 20% per hour of irradiation duration, particularly preferably by at least 50% per hour of irradiation duration.11 . The method according to one of the preceding claims, characterized in that the deactivation of the at least one UV-sensitive dopant reduces the electrical conductivity of the layer and at least one absorption band of the layer with a wavelength between 400 nm and 2500 nm in the spatial region which is irradiated with the UV radiation.

12. The method according to one of the preceding claims, characterized in that the layer is a layer of an optoelectronic or electronic component, in particular a photodetector, an OLED, an organic solar cell, a spectrometer, a display device or an organic transistor.Kailuweit & Uhlemann | Patentanwalte13. The method according to claim 12, characterized in that the layer is a layer of an optical resonator of an optoelectronic component.

14. The method according to one of the preceding claims, characterized in that the irradiation with the UV radiation takes place as a function of a specific electrical conductivity, a layer thickness, an absorption intensity, a transmission intensity, a Raman and / or Stokes shift of the layer and / or as a function of a resonance wavelength of an optical resonator which is formed with the layer.

15. The method according to one of the preceding claims, characterized in that the UV radiation has an intensity distribution and / or distribution of the irradiation duration, the intensity distribution and / or distribution of the irradiation durations having spatial regions in which the layer is not irradiated or is irradiated with a lower radiation intensity and / or a lower irradiation duration, and spatial regions in which the layer is irradiated with a higher radiation intensity and / or a higher irradiation duration.

16. The method according to claim 15, characterized in that the spatial regions in which the layer is not irradiated or is irradiated with a lower radiation intensity and / or a lower irradiation duration are photoactive regions of an optoelectronic component.

17. The method according to claim 15, characterized in that the spatial regions in which the layer is not irradiated or is irradiated with a lower radiation intensity and / or a lower irradiation duration are electrodes of an optoelectronic or electronic component.

18. Use of the method according to any one of the preceding claims 1 to 17 for reducing the resonance wavelength of an optical resonator in an optoelectronic device, for reducing crosstalk between optoelectronic or electronic devices or for charge shielding an electrode of an optoelectronic or electronic device.

19. Layer produced by a method according to any one of claims 1 to 17.

20. An optoelectronic or electronic component comprising at least one layer according to claim 19.Kailuweit & Uhlemann | Patentanwalte

Images