• 专利附录
  • 专利说明
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    • 专利摘要:
    The present invention relates to the field of electronic devices, such as organic electronics, in which said device comprises a substrate and a multitude of layers, where at least one of said layers is an intermediate layer, in which said buffer layer comprises metal oxide nanoparticles comprising physioabsorbed metal salts as described in the specification. The invention further provides intermediate goods and materials suitable for the manufacture of such electronic devices, to specific manufacturing methods and specific uses.
    公开号:BR112017016097B1
    申请号:R112017016097-8
    申请日:2016-02-09
    公开日:2021-01-19
    发明作者:Norman Albert Lüchinger；Benjamin HARTMEIER；Yi Hou；Tobias STUBHAN；Christoph Brabec
    申请人:Avantama Ag；
    IPC主号:
    专利说明:

    [001] The present invention relates to the field of electronic devices, especially optoelectronic devices. The invention additionally provides intermediate goods and materials suitable for the manufacture of such devices, the invention also provides for specific manufacturing methods and for specific uses.
    [002] It is known to use buffer layers in organic electronics, such as organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPV) or perovskite solar cells, in order to increase the efficiency of the device and the time of life. These buffer layers include metal oxides, such as zinc, titanium, tungsten, nickel, niobium or doped metal oxides, such as Al-doped ZnO ("AZ") or Cu-doped NiO. Generally, such metal oxides in particulate form are known. Normally, the oxide buffer layers mentioned above are manufactured by thermal evaporation under high vacuum or by wet chemical methods (based on the precursor), requiring a high temperature annealing step; which is disadvantageous in terms of low cost and large area manufacturing processing.
    [003] It is also known that organic solar cells (OPV) offer a promising approach for flexible and low-cost photovoltaic technology with certified efficiencies in excess of 10%. Before widespread commercialization, production problems and large area stability have to be resolved. For reliable production over a large area with high throughput and low deviations, thick, stable, robust and printable buffer layers are prerequisites.
    [004] Generally, such metal oxides in particulate form are known. As discussed above, such oxidic layers are manufactured by thermal evaporation under a high vacuum; which is disadvantageous in terms of low-cost, large-area manufacturing processing. Such processes, using comparatively high temperatures, for example, by including an annealing step, are also disadvantageous if the layer prior to the buffer layer is temperature sensitive. The present inventors have thus identified the need to provide manufacturing processes for buffer layers, particularly metal oxide buffer layers, which are compatible with temperature sensitive materials / layers.
    [005] It is also known that Cs2CO3 significantly influences the working function of metal oxides in buffer layers. In certain applications, this is considered a disadvantage, since the desired properties of metal oxides interfere with the properties of Cs2CO3. The present inventors have thus identified the need to provide layers of metal oxide buffer with low or even zero amounts of Cs2CO3.
    [006] Luechinger et al. (WO2014 / 161100) describe organic electronic devices, such as OLEDs and organic solar cells, comprising buffer layers with surface-modified metal oxide nanoparticles. In addition, the advantages of solution-processable buffer layers are described. Although simple in manufacturing, through its entire solution process, the devices revealed in it show comparatively low performance.
    [007] Kim et al. (Adv. Mater., 2014, DOI: 10.1002 / adma.201404189) describe perovskite organic solar cells comprising layers of NiO and Cu-doped NiO buffer. Due to their manufacturing process, the buffer layers are dense, that is, not particulate. The devices show performances above 15% PCE. However, it is considered a disadvantage that the metal oxide layers are applied by a wet chemical method (based on the precursor) and thus need to be thermally cured at very high temperatures. Consequently, these devices are more difficult to manufacture, since the remaining layers of the solar cells cannot withstand these high temperatures and thus need to be coated after the deposition of the buffer layer.
    [008] Liu et al. (Chem. Of Mater., 2014, DOI: 10.1021 / cm501898y) describe OLEDs comprising transport layers from the NiO orifice. Again, due to their manufacturing process, the buffer layers, described in this document, are dense and not particulate. It is further described that these precursor-based layers need to be cured at temperatures of at least 275 ° C and even as high as 500 ° C. Again, this is considered to be obstructive to the successful production of electronic devices based on organic material.
    [009] Kim et al. (Nanoscale Research Letters 2014, 9, 323) discu has the effect of ZnO: Cs2CO3 on the performance of organic photovoltaics. As in that document, the function of ITO work is reduced from 4.7eV to 3.8eV due to the modification by Cs2CO3. Such modification of the job function can, depending on the application, be beneficial or harmful.
    [0010] Yang et al. (US2010 / 0012178) describe processable solution materials for electronic and electro-optical applications. For this purpose, the electro-optical device comprises an interfacial layer that is a mixture of metal oxide and at least one other material that provides at least a decrease in the function of the work or an increase in the electrical conductivity in relation to the metal oxide alone . Other materials being present in quantities of at least 10% and up to 120% and thus significantly influence the properties of the metal oxide.
    [0011] Dong et al. (RSC ADV 2014, 4, 60131) reveal the use of Cs2CO3 as a surface modification material for hybrid perovskite solar cells.
    [0012] It is, therefore, an objective of the present invention to mitigate at least some of these disadvantages of the prior art. In particular, it is an object of the present invention to provide compositions suitable for forming a thin film on a plurality of substrates. It is an additional objective to provide methods for making thin films by avoiding vapor-phase processes and to provide a better electrical device and intermediate goods. It is also an objective to supply high performance optoelectronic devices and components. It is also an objective to supply optoelectronic devices, and their components, which are simple to manufacture.
    [0013] These objectives are achieved through a device as defined in claim 1 and an intermediate good as defined in claim 10 and the uses as defined in claim 13. Other aspects of the invention are disclosed in the specification and independent claims, preferred modalities are disclosed specifications and dependent claims.
    [0014] The present invention will be described in detail below. It is understood that the different modalities and preferences and intervals, as provided / disclosed in this specification, can be combined. In addition, depending on the specific modalities, the selected definitions, modalities or intervals may not apply.
    [0015] Except where otherwise specified, the following definitions should apply in this specification:
    [0016] The terms "a / o", "one / a" and similar terms used in the context of the present invention are to be interpreted so as to cover both the singular and the plural, unless otherwise stated in this document or clearly contradicted In addition, the terms "including", "containing" and "comprising" are used here in their open and non-limiting sense. The term "containing" should include both "comprising" and "consisting of".
    [0017] The percentages are given as% by weight, unless otherwise stated in this document or clearly contradicted by the context.
    [0018] The term "electronic device" is known in the field. In the context of the present invention, any device comprising thin functional films is included, including inorganic LEDs or inorganic compounds or inorganic solar cells; more specifically organic electronics as defined below.
    [0019] The term "optoelectronic device" is known in the field and denotes electronic devices that generate, detect or control light. Consequently, such devices convert an electrical signal to an optical signal or vice versa.
    [0020] The terms "organic electronics", "organic electronic devices", "OLED", "OPV" are known in the field and refer to electronic devices comprising a "substrate" and a plurality of layers, where at least one layer it is a "buffer layer" as defined below. In organic electronics, at least one layer comprises organic substances, essential for the correct functioning of these devices. Depending on the remaining layers, their structure and connection, these devices serve a wide variety of effects, such as an OLED, an OPV cell, an organic photo detector or a perovskite solar cell. The term LED includes both organic LEDs (OLEDs) where the active layer comprises electro-luminescent organic materials (polymers or small molecule), and quantum dot LEDs (QLEDs), where the active layer comprises electro-luminescent quantum dots.
    [0021] The term "buffer layer" denotes an interface layer in electronic devices, usually in devices as discussed here. Buffer layer is the general term for layers with a selective charge function such as orifice transport (HTL), orifice injection (HIL), orifice extraction (HEL), electron transport (ETL), electron injection (EIL) or electron extraction (EEL). In the context of the present invention, the term buffer layer generally represents different specific functions. A buffer layer is often also referred to as a selective charge layer or charge transport layer (CTL). Consequently, the term buffer layer includes both electron selective layers and orifice selective layers.
    [0022] The term "substrate" indicates the layer to which the functional layers are applied. The substrate can be transparent or non-transparent. Suitable materials include organic materials, such as polymers and inorganic materials, such as glass.
    [0023] The term "physisorption" is known in the field and is defined as the adsorption in which the forces involved are intermolecular forces (van der Waals or electrostatic forces) and which do not involve a significant change in the electronic orbital patterns of species involved (see: "International Union of pure and Applied Chemistry" (http://goldbook.iupac.org/P04667.html). In the context of the present invention, it denotes the adsorption of a molecule or ion on a surface by electrostatic attractions or van der Waals. In contrast to a physioabsorbed molecule, it does not alter its chemical properties through adsorption, therefore, by physisorption neither covalent bonds are formed or broken nor are ionized or deionized atoms.
    [0024] The term "scattered particles" is known and describes the materials that disperse light efficiently. Typically, dispersion particles have a high refractive index (such as> 2.0, preferably> 2.3) and a particle size in the wavelength range of visible light (such as 100 - 1000 nm, preferably 200 - 500 nm).
    [0025] The term "opacity" is known; the opacity of a thin film is physically defined as the intensity of the diffuse transmission divided by the total transmission through the thin film. Opacity can be measured with an integrated sphere.
    [0026] The term "active layer" denotes a layer that is photoactive and converts light into electrical energy (absorbs light; for example, solar cells) or converts electrical energy into light (light emitter; for example, LED ). In the context of the present invention, the active layers contain one or more active substances.
    [0027] In a specific modality, the active layer of a solar cell consists of a fullerene-based compound such as PCBM (receptor) and a second active material (donor).
    [0028] In an additional specific modality, the active layer of an LED comprises organic materials, such as polymers or small molecules, as discussed in GeffrOy et al. (Polym Int. 55: 572 - 582 (2006)).
    [0029] In an additional specific modality, the active layer of an LED comprises electroluminescent quantum dots, such as Perovskite crystals as disclosed, for example, in Kovalenko et al. (Nanoletters 2014, DOI: 10,1021 / nl5048779).
    [0030] The term "active material" denotes materials that are photographic and have electron receptor or electron donor properties. This includes photoactive polymers, small photoactive molecules, photoactive quantum dots, photoactive metallic organic perovskites as used here.
    [0031] The terms "perovskite" and "perovskite materials" are known in the field and are materials that exhibit the same crystalline structure as CaTiO3. They refer, in general, to crystalline materials according to the ABX3 structure, with A and B being two of the cations of very different sizes; normally, A has a coordination number of 12 with respect to X, while B has a coordination number of 6 with respect to X. In the context of the present invention, perovskite materials, for example, include metallic organic halide materials such as iodide lead-methyl-ammonium (CH3NH3PbI3) or tin-methyl-ammonium iodide (CH3NH3SnI3).
    [0032] The term "nanoparticles" is known and refers particularly to solid or crystalline amorphous particles having at least one dimension in the size range of 1 - 100 nm. Preferably, the nanoparticles are approximately isometric (like spherical or cubic nanoparticles). The particles are considered to be approximately isometric, if the aspect ratio (longest: shortest) of all 3 orthogonal dimensions is 1 - 2. In an advantageous embodiment, nanoparticles have an average primary particle size of 2 - 60 nm, preferably 5 - 30 Nm (measured by the N2 adsorption method (BET) and calculated using the following formula d = 6 / (p * ABET), where d is equal to particle size, p is equal to density material and ABET is equal to the specific surface area measured).
    [0033] The term "nanoparticle layer" denotes a film composed of nanoparticles. The thickness of the nanoparticle layer can vary over a wide range, but is usually 3 - 1000 nm, preferably 10 - 300 nm. If dispersion particles are not present, the range is typically 3 - 1000 nm, such as 3-30 nm for self-assembled monolayers. If dispersion particles are present, the range is typically 100 - 20,000 nm, preferably 1000 to 10,000 nm. A layer of the nanoparticles can be composed of a monolayer of nanoparticles, thus having a thickness equal to the size of nanoparticles used and thus defining a lower limit of thickness. A layer of nanoparticles can be composed of nanoparticles with a single size or with a bimodal or multimodal size distribution. It is believed that bimodal or multimodal size distributions result in a higher packing density of the nanoparticle layer. In addition, the porosity volume of a nanoparticle layer is usually less than 95%, preferably less than 70%.
    [0034] The term "metal oxide nanoparticles" includes (i) pure oxide nanoparticles, (ii) doped oxide nanoparticles, (iii) mixed metal oxides and (iv) core-capsule nanoparticles, the core being and the capsule are composed of different oxides.
    [0035] The term "AZO" is known in the field and includes zinc oxides doped with aluminum which means that aluminum is atomically dispersed in a zinc oxide structure (solid solution).
    [0036] The term "solvent" is known in the field and in the context of the present invention particularly includes water and polar organic solvents such as alcohols, glycolic ethers, nitriles, ketones, ethers, esters, aldehydes, sulfoxides (such as dimethylsulfoxide (DMSO)), formamides (such as diemylformamide (DMF)) and acetamides (such as dimethylacetamide (DMA)). The above organic solvents can be substituted or unsubstituted and include cyclic, linear and branched derivatives. There may also be unsaturated bonds in the molecule. The organic solvents above usually have 1 - 12 carbon atoms, preferably 1 - 7 carbon atoms.
    [0037] The terms "dispersant" and "dispersing agent" are known in the field and have essentially the same meaning. In the context of the present invention, these terms denote a substance, other than a solvent, which is used in colloidal suspensions to improve particle separation and to prevent the formation of agglomerates or settling. In the context of the present invention, the terms "dispersant" and "dispersing agent" are used for metal salts, stabilizing the suspensions of the nanoparticles disclosed here.
    [0038] The term "suspension" is known and refers to a heterogeneous fluid of an internal phase (i.p.) which is a solid phase and an external (e.p.) which is a liquid. In the context of the present invention, a suspension typically has a kinetic stability of at least 1 day (measured according to complete particle sedimentation). In an advantageous embodiment, the invention provides a composition with a (hydrodynamic size D90 of less than 100 nm) with a shelf life of more than 7 days, particularly more than 2 months. The external phase generally comprises one or more solvents, such as water, alcohols and ketones and the like.
    [0039] The term "solution processing" is known in the field and denotes the application of a coating or thin film to a substrate through the use of a solution-based starting material (= liquid). In the context of the present invention, solution processing refers to the manufacture of organic electronics and intermediate goods comprising thin nanoparticle films by using one or more liquid suspensions; normally the suspension application (s) is / are conducted at ambient pressure.
    [0040] The present invention will be better understood by reference to the figures.
    [0041] Figure 1 describes the various aspects of the present invention. In summary, the invention describes electronic devices from the group of organic electronics (DEV; IV.I - IV.III; 1st aspect of the invention) having specific buffer layer (s); intermediate goods (INT; III, 2nd aspect) suitable for the manufacture of organic electronics above; compositions in the form of a suspension (SUSP; II, 3rd aspect) suitable for the manufacture of intermediate goods by wet phase processing. These compositions can be obtained through the combination of known starting materials, such as the MOx nanoparticles (N.P .; I.I), metallic salts (anion I.II and cation I.III) and solvents (SOLV; I.IV).
    [0042] Figure 2 shows a schematic configuration of different types of intermediate goods (INT; III), useful for the manufacture of organic electronics. According to Figures III.A -III.D different sequences are shown where
    [0043] (10) denotes a substrate [which may be transparent or non-transparent as well as organic (for example, polymer) or inorganic (for example, glass)],
    [0044] (20) denotes an electrode [which can be transparent or non-transparent],
    [0045] (30) denotes a first layer of buffer,
    [0046] (40) denotes an active layer [including, for example, a polymer, small molecule or perovskite active material],
    [0047] (50) denotes a second layer of buffer [with opposite polarization compared to the first layer of buffer],
    [0048] (60) denotes a second electrode [which may be independent of the first transparent or non-transparent electrode],
    [0049] The second layer of buffer 50 may have a composition according to the present invention, or it may have a different composition, as materials of the art. The inventive intermediates can include new layers or consist of layers as shown in this figure.
    [0050] Figure 3 schematically compares the internal structure of a layer of buffer 30 or 50 on an electrode 20 depending on its manufacture. Figure 3A shows the structure as obtained by a nanoparticle deposition process, thus showing the phases of particulate metal oxide 2 and air in the form of pores 3 according to the present invention. Figure 3B shows the structure obtained by processes based on the precursor or vacuum deposition, thus showing a phase of continuous / dense metal oxide 2 and air in the form of a varying amount of defects such as cracks or holes 3. Depending on the process of actual deposition, the amount of defects in 3B can vary significantly.
    [0051] Figure 4 shows a schematic illustration of a single metallic oxide particle (I.I) as shown in Figure 3, with the metallic salt (cation I.III and anion I.II) adsorbed on its surface. Without being bound by theory, it is believed that the positively charged metal cations (I.III) will be physioabsorbed on the surface of negatively charged particles (II) and that the negatively charged anion (I.II) is present linked to the cation (as shown ). In the event that the metal oxide particle is dispersed in a liquid phase, for example, the inventive suspensions, the anion can also be spatially separated (not shown).
    [0052] Figure 5 shows electron micrographs of atomic force (10 x 10 micrometers) of films obtained according to example 5, left: this invention, right according to the prior art.
    [0053] In a first aspect, the invention relates to an electronic device, specially selected from the group of optoelectronic devices, where said device comprises a substrate and a plurality of layers, where at least one of said layers is a buffer layer, in which the buffer layer comprises the metal oxide nanoparticles, where on the surface of said metal nanoparticle salts as described here are physioabsorbed.
    [0054] In more general terms, the invention relates to layers of buffer in an electronic device, said layers of buffer having a specific and beneficial composition containing nanoparticles of metal oxide as described. The inventive buffer layers present have been found to provide beneficial properties for electronic devices because: (i) in the post-treatment (for example, plasma cleaning or annealing temperatures> 150 ° C) it is necessary to allow a manufacturing process of all solutions; (ii) only a very small amount of dispersing agent is required, leading to high performance of electronic devices.
    [0055] This aspect of the invention will be explained in more detail below.
    [0056] The terms electronic devices and optoelectronic devices are defined above.
    [0057] In one embodiment, the device is selected from the group of organic solar cells (OPV, including perovskite solar cells), organic light-emitting diodes (OLED), organic photodetectors and quantum dot LEDs (QLED) ; particularly OPV and OLED, very particularly OPV.
    [0058] In another embodiment, the invention relates to an OPV device with tandem architecture.
    [0059] In yet another embodiment, the invention relates to an OPV device with tandem architecture through which an inventive layer of the present invention is part of the recombination layer.
    [0060] In one embodiment, the buffer layer is selected from the group consisting of orifice transport layers (HTL), orifice injection (HIL), orifice extraction (HEL), electron transport (ETL), electron injection (EIL) and electron extraction (EEL), preferably HTL, HIL, HEL.
    [0061] In one embodiment, the buffer layer is located on top of hydrophobic or hydrophilic organic materials, preferably PEDOT: PSS, photoactive polymers (absorbers or emitters) or small photoactive molecules (absorbers or emitters).
    [0062] In yet another embodiment, the buffer layer is located on top of a hydrophilic inorganic material, preferably ITO or silver (including a dense vacuum deposited Ag layer or a layer of porous Ag nanowires processed by the solution).
    [0063] In one embodiment, the electrode at the top and / or bottom of the device is a silver, copper or nickel electrode, particularly an Ag, Cu or Ni nanowire electrode. The nanowires of such electrodes can be incorporated into hydrophilic or hydrophobic organic materials as defined above, particularly in PEDOT: PSS.
    [0064] In one embodiment, the upper and lower electrodes are both made of metal nanowires. This mode provides transparent or semi-transparent electronic devices. The threads of such electrodes can be incorporated into the hydrophilic or hydrophobic organic materials as defined above, particularly in PEDOT: PSS.
    [0065] In one embodiment, the upper and / or lower electrode is PEDOT: PSS pure.
    [0066] In an additional modality, the upper and / or lower electrode is a combination of PEDOT: PSS with a regular metal collector grid (such as an Ag, Cu or Ni collector grid).
    [0067] Metal oxide nanoparticles: The term metal oxide nanoparticles is defined above.
    [0068] In one embodiment, the nanoparticles are selected from the group consisting of pure metal oxides, preferably NizSy (including NiO), ZnzSy (including ZnO), TizOy, WzOy, VzOy, MozOy, YzOy, TazOy, CuzOy, ZrzOy, SnzOy, InzOy and NbzOy. A particularly preferred pure metal oxide is NiO. An additional particularly preferred pure metal oxide is ZnO. An additional particularly preferred pure metal oxide is CrzOy.
    [0069] In one embodiment, the nanoparticles are selected from the group consisting of mixed metal oxides, preferably zinc containing mixed metal oxides, more preferably zinc and indium and gallium oxide (IGZO), zinc and indium oxide ( IZO), zinc oxide and tin (ZnSnO3). Another preferred mixed metal oxide is BaSnO3.
    [0070] In one embodiment, the nanoparticles are selected from the group consisting of doped metal oxides, preferably NizOy, ZnzOy, TizOy, WzOy, VzOy, MozOy, YzOy, TazOy, CuzOy, ZrzOy, SnzOy, InzOy and InzOy and NbzOy, with the utmost preference NizOy, ZnxOy, TizOy, InzOy and SnzOy. Suitable dopants and amounts of dopants are known in the field. The term doped metal oxide refers to MOx compositions where the metal (M) is replaced by one or more metals (= "doping"). The doping atoms are incorporated into the crystalline structure of MYSx forming substitutionally or interstitially a single homogeneous phase (a "solid solution"). Specific examples include ITO (tin and indium oxide; typical of 90% In2O3: 10% SnO2), ATO (tin oxide doped with antimony; typical 90% SnO2: 10% Sb2O3) and AZO (zinc oxide doped with aluminum; typical 97% ZnO: 3% Al2O3). In the context of the present invention, separate multi-phase systems (for example, MOx + Fe2O3) are not considered doped oxides. The doping of oxides can allow the fine adjustment of the properties of the inventive thin films, such as electrical conductivity, working function and / or optical absorbance.
    [0071] In a preferred embodiment, said metal oxides are doped with 0.001 - 30% by weight, preferably 0.01 - 15% by weight, more preferably 0.1 - 10% by weight (with respect to the metal), by one or more metals.
    [0072] In a preferred embodiment, said doping atoms are selected from the group consisting of transition metals, alkali metals and alkaline earth metals.
    [0073] Metal salt: According to the present invention, metal salts are physioabsorbed on the surface of nanoparticles. The term physioabsorbed is defined above. It is evident that physisorption only occurs on the surface of nanoparticles. Without being bound by theory, metal salts are believed to act as a dispersant. In the context of the present invention, metal salts are therefore called dispersants. The amount of metal salts absorbed on the surface can vary over a wide range. Adequate amount of metal salts is in the range of 0.02-6 mol%, preferably 0.1-4 mol%, more preferably 0.2-2 mol% of the molar fraction of the metal salt cation for metal atoms / ions in the nanoparticle. These quantities depend on the specific surface exposed by the nanoparticles and can be determined by the qualified person.
    [0074] In one embodiment, the metal salt is of the formula (I) Mza + Ryb- (I)
    [0075] being that
    [0076] M represents a metal cation,
    [0077] R represents the corresponding salt anion,
    [0078] a is 2, 3, 4 or 5, preferably 2 or 3
    [0079] b is 1, 2 or 3, preferably 1 or 2
    [0080] z is 1 or a real number below 1, but excluding 0,
    [0081] y is z * a / b
    [0082] The metal cation (M) is preferably Zn, Al, Y, Pb, Bi, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Mg, Ca, Sr or Ba and is with maximum preference Zn, Al or Y.
    [0083] The ion (R) salt is preferably acetate, formate, citrate, oxalate, nitrate or halide and is more preferably acetate or nitrate.
    [0084] In a preferred embodiment, the metal atom / ion of the dispersing salt differs from the metal atom / ion which is present in high concentration in the nanoparticles.
    [0085] In a preferred embodiment, the metal atom / ion of the dispersing salt differs from any atom / metal ion in the nanoparticle which is present in a concentration greater than 0.1% by weight (in relation to the nanoparticle composition).
    [0086] The metal salts described here are commercial items. Such metal salts can be made by any method known in the art.
    [0087] In one embodiment, the invention provides a buffer layer with a composition as described here in which said layer consists of metal oxide nanoparticles and a dispersant as described here.
    [0088] In one embodiment, said metallic oxide nanoparticles are coated with a type of dispersant as defined here.
    [0089] In an alternative embodiment, said metal oxide nanoparticles are coated with one or more types of dispersant as defined here. In this embodiment, an individual nanoparticle is coated with said two or more types of dispersant or a first group of nanoparticles is coated with a first dispersant, a second group of nanoparticles is coated with a second dispersant and so on.
    [0090] In another embodiment, the invention provides a buffer bed with the following composition: 70 - 99.9% by weight, preferably 80 - 99.5% by weight, more preferably 90 - 99% by weight of metal oxide nanoparticles and 0.1-30% by weight of metal salt, preferably 0.5-20% by weight of metal salt, more preferably 1-10% by weight of metal salt. These ratios are preferably measured by secondary ion mass spectrometry (SIMS) techniques (for example, TOF-SIMS).
    [0091] In an advantageous embodiment, the invention provides a buffer layer as described here containing 70 - 99.9% by weight, preferably 80 - 99.5% by weight, more preferably 90 - 99% by weight of nanoparticles NiO and 0.1-30% by weight, preferably 0.5-20% by weight, more preferably 1-10% by weight of dispersant.
    [0092] In an advantageous embodiment, the invention provides a buffer layer as described here containing 70 - 99.9% by weight, preferably 80 - 99.5% by weight, more preferably 90 - 99% by weight of nanoparticles of ZnO and 0.1-30% by weight, preferably 0.5-20% by weight, more preferably 1-10% by weight of dispersant.
    [0093] In an advantageous embodiment, the invention provides a buffer layer as described here containing 70 - 99.9% by weight, preferably 80 - 99.5% by weight, more preferably 90 - 99% by weight of nanoparticles AZO and 0.1-30% by weight, preferably 0.5-20% by weight, more preferably 1-10% by weight of dispersant.
    [0094] In an advantageous embodiment, the invention provides buffer beds as described here comprising:
    [0095] NiO nanoparticles and Y (NO3) 3 salt of formula (I); or
    [0096] ZnO nanoparticles and Y (NO3) 3 salt of formula (I); or
    [0097] AZO nanoparticles and Y (NO3) 3 salt of formula (I).
    [0098] In another embodiment, the invention provides an electronic device as described here where said layers of buffer have a film thickness of 3 - 1000 nm, preferably 10 - 500 nm. In one embodiment, monolayers, usually 3-30 nm thick, are also provided. The thickness can be determined by profilometry, atomic force microscopy or electron microscopy.
    [0099] In another embodiment, the invention provides an optoelectronic device as described herein in which the oxide nanoparticles have a primary particle diameter of 1 - 100 nm, preferably 3 - 50 nm (measured by nitrogen absorption, diffraction of X-rays or transmission electron microscopy).
    [00100] In another embodiment, the invention provides an electronic device as described here where said oxide nanoparticles have a bimodal or multimodal size distribution. It is believed that bimodal or multimodal size distributions result in higher particle packing densities, resulting in a lower level of porosity.
    [00101] In another embodiment, the invention provides an electronic device as described here where said buffer layers have an average surface roughness below 100 nm, especially below 30 nm (determined by electron microscopy, force microscopy) atomic or profilometry).
    [00102] In another embodiment, the invention provides an electronic device as described here where said buffer layer comprises, in addition to the nanoparticles as described here, dispersed particles. Consequently, the buffer layers of the present invention can additionally include the dispersion of particles, usually with a refractive index> 2.3 and being relatively large, usually with a particle size of 100 - 500 nm. The presence of such dispersion particles provides controlled opacity for an electronically functional buffer layer. The use of such layers of buffer with light diffusing properties (opacity) is for extraction of light (coupling out of light) in OLED devices or for coupling within light in solar cells, which increases the efficiency of any device (more light enters the solar cell or more light is extracted from an OLED). Typical compositions of dispersion particles are BaTiO3, SrTiO3, TiO2. Typical concentrations of dispersion particles in the dry buffer layer vary from 5 - 50% by weight.
    [00103] In another embodiment, the invention provides an electronic device as described here in which said buffer layer has an electrical conductivity of 10-8 to 103S / cm, preferably 106 to 102, more preferably 10-3a 10 (determined by 4-point conductivity measurement).
    [00104] In a more specific embodiment, the invention provides an electronic device as described here in which said buffer layer comprises dispersion particles and has an electrical conductivity of 10-1 to 103S / cm.
    [00105] In another embodiment, the invention relates to an OLED where ETL or EIL (i) is obtained by a method as described here or (ii) consists of metal oxide nanoparticles coated with a dispersant as described here .
    [00106] In another embodiment, the invention relates to an OLED where HTL or HIL (i) is obtained through a method as described here or (ii) consists of metal oxide nanoparticles coated with a dispersant as described here .
    [00107] In another embodiment, the invention relates to an OLED in which the device cell comprises the sequence electrode / HIL / HTL / active layer / ETL / EIL / electrode.
    [00108] In another embodiment, the invention relates to an OLED where the ETL layer consists of a nanoparticle monolayer coated with a dispersant as described here.
    [00109] In another embodiment, the invention relates to an organic solar cell (OPV) where ETL (i) is obtained through a method as described here or (ii) consists of metal oxide nanoparticles coated with a dispersant as described here.
    [00110] In another embodiment, the invention relates to a perovskite solar cell where HTL (i) is obtained by a method as described here or (ii) consists of metal oxide nanoparticles coated with a dispersant as described on here.
    [00111] In another embodiment, the invention relates to an organic photo-detector where ETL (i) is obtained using a method as described here or (ii) consists of metal oxide nanoparticles coated with a dispersant as described on here.
    [00112] In another embodiment, the invention relates to an electronic device where ETL (i) is obtained by a method as described here or (ii) consists of metal oxide nanoparticles coated with at least one type of a dispersant as described here.
    [00113] Use: In another embodiment, the invention relates to the use of metal oxide nanoparticles coated with metal salts as described here for the manufacture of an electronic device as described here, specially selected from the group of OLEDs, OPVs, perovskite solar cells, sand photodetector QLEDs.
    [00114] In a second aspect, the invention relates to an intermediate good ("a component") comprising a sheet-shaped substrate coated with a plurality of layers in which at least one of said layers, preferably a layer of buffer, comprise nanoparticles with physioabsorbed metal salts as defined in the first aspect of the invention.
    [00115] This aspect of the invention will be explained in more detail below.
    [00116] Intermediate good ("component"): As outlined above, there is a need for the manufacture of organic electronics by solution-based processes. Consequently, a component is manufactured by the appropriate solution-based processes, such as coating or printing; the material thus obtained is then finished to obtain the final device (the organic electronic).
    [00117] In one embodiment, the invention provides a component as defined here, where said layers have the substrate / electrode / HTL / active layer / ETL / electrode sequence. ("normal architecture").
    [00118] In an additional embodiment, the invention provides a component as defined here, where said layers have the substrate / electrode / ETL / active layer / HTL / electrode sequence. ("inverted architecture").
    [00119] In an additional embodiment, the invention provides a component as defined here, where said layers comprise the electrode / ETL / active layer / HTL sequence. This intermediary can also be the basis of a tandem cell.
    [00120] In an additional embodiment, the invention provides a component as defined here, wherein said layers comprise the electrode / HTL / active layer / ETL sequence. This intermediary can also be the basis of a tandem cell.
    [00121] In an additional embodiment, the invention provides a component as defined here, where said layers comprise the electrode / HTL / ETL / electrode sequence.
    [00122] In an additional embodiment, the invention provides a component as defined here, where said layers comprise the electrode / ETL / HTL / electrode sequence.
    [00123] In an additional embodiment, the invention provides a component as defined here, where said layers have the sequences:
    [00124] (a) Transparent electrode / HTL / active layer / ETL
    [00125] (b) Non-transparent electrode / HTL / active layer / ETL
    [00126] (c) Transparent electrode / ETL / active layer / HTL
    [00127] (d) Non-transparent electrode / ETL / active layer / HTL
    [00128] in which the transparent electrode is selected from the group consisting of: PEDOT: PSS, metallic nanowires (including silver nanowires, copper nanowires, nickel nanowires), metallic grids, graphene, carbon nanotubes and ITO; and so that the non-transparent electrode is selected from the group consisting of a dense silver layer, dense aluminum, dense copper, dense gold, a thick (opaque) carbon nanotube layer and a thick (opaque) graphene-based layer.
    [00129] In an additional embodiment, the invention provides a component as defined here, where no additional layer is present.
    [00130] In another embodiment, the invention provides an electronic device as described here where the buffer layer has a thickness of 3 to 1000 nm, preferably 10 to 500 nm.
    [00131] In another embodiment, the invention provides a component as defined here where the buffer layer has an average surface roughness of 30 nm.
    [00132] In an additional embodiment, the invention provides a component as defined here, where the buffer layer has a metal salt content in the range of 0.1 to 30% by weight, preferably 0.5 to 20% by weight , more preferably 1 to 10% by weight.
    [00133] In an additional embodiment, the invention provides a component as defined here, the substrate is as defined above.
    [00134] Use: In an additional embodiment, the invention provides the use of metal oxide nanoparticles comprising physioabsorbed metal salts as described here for the manufacture of an intermediate good ("component") as defined here.
    [00135] In a third aspect, the invention relates to a composition in the form of a suspension, said composition containing nanoparticles of metal oxide, solvent (s) and a dispersant selected from the group of metal salts as described here . The use of such suspensions for the manufacture of thin films, such as buffer layers, is new and object of the present invention. In addition, certain suspensions are new and thus also the subject of the present invention. This aspect of the invention will be explained in more detail below.
    [00136] New uses: The invention provides the use of a suspension, comprising nanoparticles of metal oxide coated with a dispersant as described here and a polar solvent, (i) for the manufacture of an intermediate good ("component") as defined here or (ii) for the manufacture of an electronic device as described here; said device specially selected from the group consisting of OLEDs, OPVs, perovskite solar cells, photodetectors and QLEDs.
    [00137] For these uses, suitable suspensions (II) comprise 0.2 to 50% by weight, preferably 1 to 20% by weight of nanoparticles (1) as described herein; 0.005 to 10% by weight, preferably 0.01 to 5% by weight of metal salt (2) as described herein; 20 to 99.795% by weight, preferably 30 to 98.99% by weight of solvent (4) as defined above, preferably water, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, methanol, acetonitrile, ethylene glycol, carbonate propylene, acetone, 2,2,3,3-tetrafluoro-1-propanol, more preferably methanol, acetonitrile, 2,2,3,3-tetrafluoro-1-propanol and water.
    [00138] New suspensions: In addition, certain suspensions defined above are new and thus object of the present invention. The term suspension is defined above.
    [00139] In one embodiment, the invention provides a composition in the form of a suspension comprising (i) nanoparticles selected from the group of metal oxide nanoparticles and (ii) one or more solvents and (iii) one or more dispersants from the group of metal salts as described here.
    [00140] Nanoparticles: The amount of nanoparticles in the inventive composition can - depending on the intended use - vary over a wide range, but is usually in the range of 0.2 to 50% by weight (preferably 1 to 20 % by weight) of the composition.
    [00141] Advantageously, the suspended nanoparticles have a D90 hydrodynamic size of less than 100 nm (measured by dynamic light scattering or centrifugal sedimentation techniques).
    [00142] Advantageously, the nanoparticles are synthesized by a gas phase pyrolysis process, preferably the flame spray synthesis.
    [00143] Dispersants: Suitable dispersants are discussed above and particularly include the metal salts of formula (I). Without being bound by theory, it is believed that the dispersants in the inventive suspension are partially physioabsorbed on the surface of the nanoparticles and partially dissolved in the solvent.
    [00144] Solvents: Suitable solvents include polar solvents as discussed above, and are preferably selected from the group consisting of water, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, methanol, acetonitrile, ethylene glycol, propylene carbonate, acetone and 2, 2,3,3-tetrafluoro-1-propanol. Particularly preferred are polar solvents selected from the group consisting of methanol, acetonitrile, 2,2,3,3-tetrafluoro-1-propanol and water. It is understood that the term solvent also comprises the combinations of the solvents mentioned above.
    [00145] In a fourth aspect, the invention relates to the manufacture of inventive compositions, intermediate goods and devices disclosed here and to the inventive compositions, intermediate goods and devices obtained according to these methods. This aspect of the invention will be explained in more detail below.
    [00146] Manufacture of suspensions: The manufacture of suspensions is a known procedure. The coating of nanoparticles is also a known procedure. These procedures can be applied to the starting materials of the inventive suspensions.
    [00147] In one embodiment, the solvent and the nanoparticles are combined, for example, by mixing, ultrasonication or ball milling. To the initial suspension obtained, dispersants (ie metal salts) are added. The coating takes place at room temperature or by heating and mixing.
    [00148] In an alternative embodiment, the solvent and dispersants (that is, the metal salts) are combined, for example, by mixing. To the initial solution, the obtained nanoparticles are added. The coating takes place at room temperature or by heating and mixing.
    [00149] Manufacture of intermediate goods: The intermediate goods according to the present invention can be obtained by solution processes. This is considered a significant advantage, since it allows the manufacture of all layers by simple technologies applicable to large areas and continuous processing.
    [00150] In one embodiment, the invention provides a method for manufacturing an intermediate good as defined here, where the buffer layer is manufactured comprising the steps of (a) applying a suspension to a coated substrate or substrate, said suspension comprising the nanoparticles of metal oxide coated with a dispersant and a solvent and removing the solvent from said position and (b) removing the solvent from the obtained thin film and (c) optionally treating the dry layer at an elevated temperature.
    [00151] Step (a) Application of a suspension: Many processes are known to apply a liquid composition to a substrate to result in a wet thin film; one skilled in the art is in a position to select them properly. Coating, particularly roll to roll coating, slotted die, spraying, ultrasonic spraying, dipping, spool to spool, per blade are suitable, for example; or by printing, especially inkjet, block, offset, engraving, canvas, notch, sheet to sheet printing. These processes are generally considered to be advantageous for large-scale production, when compared to vacuum-based processes. Depending on the composition used in step (a), this step can be repeated (that is, it can be performed several times). This method is considered advantageous for thinning the final film thickness.
    [00152] Step (b) Drying and film formation: Many processes are known to remove a liquid from a thin wet film from a coated substrate; one skilled in the art is in a position to select them properly. They are suitable, for example, drying at room temperature or elevated temperature. Drying can take place in air, in a shielding gas, such as nitrogen or argon. Especially suitable are gases with a low moisture content (eg nitrogen, dry air, argon).
    [00153] Step (c): Temperature of the cleaning step: A cleaning step in the form of an annealing temperature can optionally be carried out at temperatures below 150 ° C. In an advantageous embodiment, the nanoparticle film dried in step (c) is quenched at 80 ° C to 150 ° C in air or a shielding gas.
    [00154] In an advantageous mode, all layers of the intermediate good are manufactured by coating or printing.
    [00155] Manufacture of devices: The manufacture of devices from the intermediate goods described above is known to you, but has not yet been applied to the specific intermediate goods of the present invention.
    [00156] Consequently, the invention provides a method for manufacturing an electronic device as defined here comprising the steps of (a) providing an intermediate good as defined here (b) bringing the layers of said good into contact with an electrical circuit, ( d) finish the product obtained.
    [00157] Product per process: Due to the buffer layer obtained according to the inventive method, electronic devices and intermediate goods are also new. Due to the excellent stability and performance obtained according to the inventive method, the suspensions are also new.
    [00158] The invention thus provides a suspension obtained by a method comprising the step of combining the nanoparticles of metal oxide, dispersant (s) and solvent (s).
    [00159] The invention thus provides an intermediate good obtained by a method comprising the steps of applying a suspension to a coated substrate or substrate, said suspension comprising (i) nanoparticles of metal oxide coated with a dispersant and (ii) a solvent and remove the solvent from said composition and optionally treat the dry layer at an elevated temperature.
    [00160] The invention thus provides an electronic device obtained by a method comprising the steps of providing an intermediate good as defined here, putting the said good in contact with an electrical circuit, finishing the obtained product.
    [00161] To further illustrate the invention, the following examples are provided. These examples are provided without the intention of limiting the scope of the invention. Example 1: Nickel oxide (NiO) nanoparticles were synthesized by flame spray synthesis. For the preparation of the precursor, 269.2 g of Ni acetate tetrahydrate (Sigma Aldrich) was added to 1080 g of 2-hexanoic acid (Aldrich) and dissolved by heating the mixture for 1 hour at 150 ° C. To the solution obtained, 540g of tetrahydrofuran (Sigma Aldrich) was added and mixed well. The precursor was then fed (7 ml min-1, HNP Mikrosysteme, micro ring gear pump mzr-2900) to a spray head, dispersed by oxygen (15 l min-1, PanGas tech.) And ignited by a flame of methane and pre-mixed oxygen (CH4: 1.2 l min-1, O2: 2.2 l min-1). The gas exhalation was filtered through a glass fiber filter (Schleicher and Schuell) by a vacuum pump (Busch, Seco SV1040CV) at about 20 m3 h-1. The oxide nanopowder obtained was collected from the glass fiber filter.
    [00162] The size of the average crystallite was measured with a Rigaku MiniFlex 600, a Detector SC-70, measured from 10 ° to 70 ° in 0.01 ° step size using the Scherrer equation. The average crystallite size of the SrTiO3 particles was 10 nm.
    [00163] For the preparation of suspensions, 5% by weight of NiO nanopowder (as described above), 0.1% by weight of yttrium (III) nitrate hexahydrate (Aldrich) and 94.9% by weight of methanol (Merck) were dispersed by ball milling for 1 hour. The suspension finally prepared is black and stable for more than 1 week (no visible supernatant after 1 week).
    [00164] For the manufacture of the device, the ITO substrates endowed with a standard were subsequently ultrasonically cleaned with acetone and isopropanol for 10 minutes each. On the clean ITO substrate, a dense and smooth layer of the NiO suspension described above was deposited by the centrifuge coating at a speed of 4000 and followed by annealing at 140 ° C for 15 minutes in the air leading to a dry film thickness of ~ 30 nm. The following steps were carried out in a nitrogen glove box: PbI2 and CH3NH3I mixed with a molar ratio of 1: 1 with a concentration of ~ 40% were stirred in a mixture of dimethylformamide and dimethylsulfoxide (2: 1 v / v) at 60 ° C for 12 h. The precursor perovskite solution as prepared was filtered with a 0.45 μm PTFE syringe filter and coated on the ITO / NiO substrate at a speed of 4 thousand r.p.m for 35 s. During the last 5 s of the entire centrifugation process, the substrate (about 2.5 cm x 2.5 cm) was treated with melting molding and deposition in chlorobenzene (CB). The substrate was dried on a hot plate at 100 ° C for 10 min. A 2% by weight PCBM solution in CB was coated by centrifugation on the ITO / NiO / MAPbI3 substrate at 1200 r.p.m for 30 s. Finally, a counter-electrode of 100-nm thickness Ag was deposited through a shade mask by thermal evaporation.
    [00165] Characterization of the device: J-V characteristics of all devices were measured using a unit of measurement from the source of BoTest. Lighting was provided by a Newport Sol1A solar simulator with AM1.5G spectrum and light intensity of 100mWcm-2, which was determined by a calibrated crystalline Si-cell. During the characterization of the device, a shadow mask with an opening of 10.4 mm2 was used. The EQE spectra were recorded by an EQE measurement system Enli Technology (Taiwan) (QE-R), and the light intensity at each wavelength was calibrated with a single crystalline Si photovoltaic cell standard. The cell prepared as described above achieved a photoconversion efficiency (PCE) of 13.98% with a short circuit current of 19.22 mA / cm2, an open circuit voltage of 1.10 V and a fill factor of 66.2%. Example 2: 5% by weight of the NiO nanopowder in experiment 1, 0.5% by weight of diethylphosphate-ethyl-triethoxysilane (ABCR) and 94.5% by weight of isopropanol (BASF) were dispersed by ball milling for 1 hour. The suspension finally prepared is black and stable for more than 1 week (no supernatant visible after 1 week).
    [00166] The devices produced as described in experiment 1 achieved a photoconversion efficiency (PCE) of 1.60% with a short-circuit current of 3.30 mA / cm2, an open circuit voltage of 1.08 V and a fill factor of 44.9%. Example 3: A variety of combinations of different types of nopowder, metal salts and solvents were used for the preparation of suspensions. 5% by weight of nanopowder, 0.25% by weight of metallic salt and 94.75% by weight of solvent were dispersed by ball milling for 15 minutes. The nanopowders were prepared similarly to experiment 1 or were commercially available. The metal salts as well as the solvents were all commercially available. The suspensions prepared by this method were evaluated after 3 days. The suspensions were considered unstable if there was a phase separation so that there was a transparent supernatant of 30% or more in height in relation to the total height of filling of the suspension and were considered stable if less than 30% in height. The results are shown in the Table below:

    Example 4: 5% by weight of the NiO nanopowder in experiment 1, various amounts of yttrium (III) nitrate hexahydrate (Aldrich) and methanol (Merck) were dispersed by ball milling for 15 minutes. Stability similar to Example 3 was evaluated. The following results were found: Suspension containing 0.005% by weight and 0.025% by weight of yttrium (III) nitrate hexahydrate were found to be non-stable (corresponding to 0.1 and 0.5% by weight, respectively), while a suspension containing 0.05% by weight or more of yttrium (III) nitrate hexahydrate (corresponding to 1% by weight) was found to be stable. Example 5: Comparative example between the present invention and Kim et al. (Nanoscale Research Letters 2014, 9, 323).
    [00167] Experimental:
    [00168] 5% by weight of nanoparticles (ZnO; synthesized by flaming spray pyrolysis) are dispersed in the solvent (ethanol or methanol) in the presence of 5% by weight of dispersant (metal salt: Cs2CO3 (according to Kim) or YNO3x6H2O (the present invention), total dispersant concentration: 0.25%). The suspensions are prepared in analogy to Example 4. The film coating was carried out with a 5000rpm centrifuge cover. The particle size was determined with LUMISIZER by dissolving to 0.5% by weight ZnO in methanol. The results are provided below and in Figure5. Results: Table 1: Ethanol solvent

    * average hydrodynamic particle size in dispersion (D50; nm) Conclusion:
    [00169] The data provided in this example convincingly shows that the nanoparticles coated with CS2CO3 [corresponding to the metallic salts of formula (I) where a = 1] are unsuitable for preparing stable suspensions and also result in films with high roughness.
    [00170] The data provided in this example also show that the same nanoparticles coated with Y (NO3) 3 [corresponding to the metallic salts of formula (I) where a = 3] are suitable for preparing stable suspensions with polar solvents and also result in films with low roughness.
    [00171] Optoelectronic devices comprising the inventive nanoparticles are superior when compared to devices comprising the known nanoparticles.
    权利要求:
    Claims (17)
    [0001]
    1. Optoelectronic device, characterized by the fact that said device comprises a substrate and a plurality of layers, wherein at least one of said layers is a buffer layer, wherein said buffer layer comprises from 70 to 99.9% by weight of metal oxide nanoparticles, in which the metal oxide nanoparticles comprise the physioabsorbed metal salts of the formula (I) in an amount of 1 to 10% by weight, Mza + Ryb- (I), where M represents a cation of metal selected from the group consisting of Zn, Al, Y, Pb, Bi, Co, Fe, Mn, Cr, V, Ti, La, Mg, Ca, Sr or Ba, R represents the corresponding salt anion, a is 2, 3, 4 or 5; b is 1, 2 or 3; z is 1 or a real number below 1, but excluding 0, y is z * a / b; and where the molar fraction of the metal salt cation for the metal atoms / ions in the nanoparticles is 0.02 to 6 mol%.
    [0002]
    2. Device according to claim 1, characterized by the fact that it is selected from the group consisting of perovskite solar cells, OPV cells, OLEDs, QLEDs and organic photodetectors.
    [0003]
    3. Device according to claim 2, selected from the group of OPV and perovskite solar cells, characterized by the fact that said plurality of layers is organized in normal architecture or inverted architecture; or selected from the group of LEDs where the active layer comprises organic materials (OLED) or where the active layer comprises quantum dots (QLED).
    [0004]
    4. Device according to any one of the preceding claims, characterized by the fact that said buffer layer is selected from the group consisting of orifice transport layers (HTL), orifice injection (HIL), extraction of orifice (HEL), electron transport (ETL), electron injection (EIL) and electron extraction (EEL).
    [0005]
    5. Device according to any one of the preceding claims, characterized by the fact that said metal oxide nanoparticles are selected from the group consisting of ■ pure metal oxides, preferably NiO, ZnO, WzOy, MozOy TizOy, YzOy, TazOy , NbzOy, CuO, CrzOy and VzOy; ■ mixed metal oxides, preferably IGZO, IZO, ZnSnO3 and BaSnO3; ■ doped metal oxides, preferably AZO, ITO and ATO.
    [0006]
    6. Device, according to any of the preceding claims, characterized by the fact that said metal oxide nanoparticles are selected from the group consisting of NiO, ZnO, ZnO doped with Al ("AZO"), TiO2 and TiO2 doped.
    [0007]
    7. Device according to any one of the preceding claims, characterized by the fact that R represents an organic anion, preferably selected from acetate, formate, citrate, oxalate; or an inorganic anion, preferably selected from nitrate, halide.
    [0008]
    8. Device according to any one of the preceding claims, characterized by the fact that Mza + is Zn2 +, Al3 + or Y3 + Mza + Ryb- is zinc acetate, aluminum acetate, yttrium acetate, zinc nitrate, aluminum nitrate or yttrium nitrate.
    [0009]
    9. Device according to any one of the preceding claims, characterized by the fact that said substrate is selected from (a) an organic material; or (b) an inorganic material; or (c) a combination of (a) and (b).
    [0010]
    10. Intermediate good comprising a sheet-shaped substrate coated with a plurality of layers; wherein at least one layer is a buffer layer (HEL, EEL, HIL); wherein said layers (a) have the substrate / electrode / HTL / active layer / ETL / electrode sequence ("normal architecture"); or (b) have the substrate / electrode / ETL / active layer / HTL / electrode sequence ("inverted architecture"); or (c) comprise the electrode / ETL / active layer / HTL sequence; or (d) comprise the electrode / HTL / active layer / ETL sequence; or (e) comprise the electrode / HTL / ETL / electrode sequence, (f) comprise the electrode / ETL / HTL / electrode sequence, characterized by the fact that said buffer layer (s) contain nanoparticles metal oxide as defined in any one of claims 1, 5 to 8.
    [0011]
    11. Intermediate good, according to claim 10, characterized by the fact that: the buffer layer is free of dispersion particles and has a thickness between 3 to 1000 nm or the buffer layer comprises dispersion particles and has a thickness between 100 to 20000 nm; and / or ■ the buffer layer has an average surface roughness below 30 nm; and / or ■ the electrode is selected from the ITO, silver, copper, nickel or PEDOT group: PSS; and / or ■ at least one of the electrodes is based on silver nanowires ■ no additional layers are present.
    [0012]
    12. Composition in the form of a suspension, characterized by the fact that it comprises (a) 0.2 to 50% by weight of metallic oxide nanoparticles selected from the group consisting of • pure metal oxides, preferably NiO, ZnO, WzOy, MozOy TizOy, YzOy, TazOy, NbzOy, CuO, CrzOy and VzOy; • mixed metal oxides, preferably IGZO, IZO, ZnSnO3 and BaSnO3; • doped metal oxides, preferably AZO, ITO and ATO; (b) 0.005 to 10% by weight of metal salts as defined in claim 1; (c) 20 to 99.795% by weight of polar solvents, preferably selected from the group consisting of water, DMSO, DMF; dimethylacetamide, methanol, acetonitrile, ethylene glycol, propylene glycol, acetone, tetrafluoro-propanol.
    [0013]
    13. Use of a composition in the form of a suspension comprising (a) metal oxide nanoparticles as defined in re-vindication 5 or 6; (b) metal salts Mza + Ryb-, as defined in any one of claims 1, 7 or 8; (c) a polar solvent as defined in claim 12; characterized in that it is for the manufacture of an intermediate good as defined in any of claims 10 or 11; or for the manufacture of an electronic device as defined in any one of claims 1 to 9.
    [0014]
    14. Method for manufacturing an intermediate good as defined in either of claims 10 or 11, characterized in that the buffer layer is manufactured comprising the steps of (a) applying a suspension to a coated substrate or substrate, said suspension comprising metal oxide nanoparticles, particularly as defined in claim 1, and (ii) a polar solvent, particularly as defined in claim 12, and (b) removing the solvent from said composition and (c) optionally treating the dry layer to a elevated temperature.
    [0015]
    15. Method according to claim 14, characterized by the fact that (a) the suspension of step (a) is applied by coating or printing; and / or (b) the solvent from step (b) is removed under air or a shielding gas with a low moisture content; and / or (c) the nanoparticle film dried in step (c) is quenched at 50 ° C to 150 ° C in air or a shielding gas.
    [0016]
    16. Method according to either of claims 14 or 15, characterized in that all layers are manufactured by coating or printing.
    [0017]
    17. Method for the manufacture of an electronic device as defined in any one of claims 1 to 9, characterized by the fact that it comprises the steps of (a) providing an intermediate good as defined in king-vindication 10 or 11; (b) placing the layers of said material well in contact with an electrical circuit, (c) finishing the product obtained.
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    同族专利:
    公开号 | 公开日
    KR102120534B1|2020-06-09|
    US20180033984A1|2018-02-01|
    KR20170117466A|2017-10-23|
    EP3257091A1|2017-12-20|
    EP3257091B1|2019-03-13|
    CN107251256A|2017-10-13|
    WO2016128133A1|2016-08-18|
    AU2016218562A1|2017-09-07|
    CA2974044A1|2016-08-18|
    BR112017016097A2|2018-04-03|
    US10003037B2|2018-06-19|
    JP2018506857A|2018-03-08|
    RU2017131626A|2019-03-12|
    SG11201706566XA|2017-09-28|
    CN107251256B|2019-09-03|
    JP6503080B2|2019-04-17|
    ZA201705904B|2018-12-19|
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    法律状态:
    2020-05-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/02/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP15000421.6|2015-02-12|
    EP15000421|2015-02-12|
    PCT/EP2016/000220|WO2016128133A1|2015-02-12|2016-02-09|Optoelectronic devices comprising solution-processable metal oxide buffer layers|
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