Ligands for nanoscale materials

Abstract

The present invention relates to a compound suitable as a ligand for binding to the surface of a semiconductor nanoparticle, wherein the compound comprises an anchor group, a linker group, and an organic functional group; a semiconductor nanoparticle having the ligand attached to the outermost particle surface; a composition, formulation, and method for manufacturing the semiconductor nanoparticle; and an electronic device.

Description

Technology Field

[0001] The present invention relates to a compound suitable as a ligand for binding to the surface of a semiconductor nanoparticle; a semiconductor nanoparticle having said ligand attached to the outermost particle surface; a composition, formulation, and method for manufacturing said semiconductor nanoparticle; and an electronic device. Background Technology

[0002] In the context of the present application, the term "electronic device" is understood to mean an "organic electronic device" containing an organic semiconductor material as a functional material. More specifically, these devices are understood to mean organic electroluminescent (EL) devices, particularly organic light-emitting diodes (OLEDs).

[0003] Soluble organic semiconductors have been thoroughly investigated for their potential use in electronic devices. In particular, there is high interest in solar cells and OLEDs. An advantage of using soluble molecules (small molecules or polymers) is that inkjet printing technology can be used to manufacture these devices. Regarding these inks, when using film deposition by inkjet printing, the challenge remains to find a suitable solvent or solvent mixture that has appropriate viscosity, surface tension, and boiling point to rapidly solubilize organic semiconductor materials in order to achieve homogeneous film formation.

[0004] Semiconductor nanocrystals (NCs) have attracted significant attention due to their ability to tune absorption and emission over a broad spectral range by altering their size, shape, and composition, thereby replacing fluorescent organic molecules or phosphorescent metal complexes commonly used in OLEDs to tune emission colors. In particular, Group II-VI and Group III-V semiconductor NCs are important due to their fluorescence, which covers the visible to near-infrared (NIR) spectrum and is attractive in various technological applications.

[0005] Semiconductor NCs are typically covered with a layer of organic molecules that act as ligands. These ligands function to passivate the surface of the semiconductor nanocrystal and enable it to dissolve in different media. For example, a common ligand, such as that disclosed in US 7,700,200 B2, consists of a polar anchor group that binds to the surface of the semiconductor nanocrystal and a hydrocarbon group that points outward from the surface. According to US 8,120,010 B2, the ligand may additionally contain functional groups selected from acid groups and electronegative electron-withdrawing groups.

[0006] However, since these hydrocarbon groups are insulators, they do not allow efficient charge transport within the emission layer (EML) and into the quantum material. The problem to be solved

[0007] Accordingly, the object of the present invention is to provide a compound suitable as a ligand for binding to the surface of a semiconducting nanoparticle, which improves the overall performance of an electronic device by allowing passivation of the nanocrystalline surface and solubility in solution, ensuring an improved surface binding process and increased ligand density on the surface, and enabling improved charge transport through the layer and into the quantum material.

[0008] In addition, the objective of the present invention is to provide a semiconductor nanocrystal that has a high fluorescence quantum yield, can realize high contrast, can improve charge transport in the semiconductor nanocrystal and within the semiconductor nanocrystal layer, and thereby improves the efficiency of electronic devices, particularly electroluminescent devices. means of solving the problem

[0009] The present invention provides a novel compound suitable as a ligand for binding to the outermost surface of semiconductor nanoparticles to achieve the aforementioned technical problem(s).

[0010] Accordingly, the present invention relates to a compound having a molecular weight of 1000 g / mol or less, comprising an anchor group AG capable of being bonded to the surface of a semiconductor nanoparticle, followed by an electronically inactive and conjugating interrupting linker group L, followed by an organic functional group FG in a given order.

[0011] As used in this specification, the term "anchor group" means an organic functional group that interacts with the surface of a semiconductor nanoparticle to bond the compound of the present invention to the surface of the semiconductor nanoparticle, for example, through covalent bonding or ionic bonding or dipole-dipole interaction, but not limited thereto.

[0012] Preferably, the anchor group AG is selected from the group consisting of thiol or its salt, phosphonic acid or its salt, carboxylic acid or its salt, selenol or its salt, sulfinic acid or its salt, mercaptoester or its salt, carbodithioic acid or its salt, boronic acid or its salt, amine and phosphine; more preferably, it is selected from the group consisting of thiol or its salt, phosphonic acid or its salt, carboxylic acid or its salt, boronic acid or its salt, and mercaptoester or its salt, and most preferably, the anchor group AG is selected from thiol or its salt, from phosphonic acid or its salt, or from mercaptoacetate or its salt.

[0013] Additionally, the compound according to the present invention comprises a linker group L that is a divalent group interconnecting an anchor group AG and an organic functional group FG through chemical bonding, is electronically inactive, and conjugating interrupting. As used herein, the term “conjugating interrupting” means that the linker group L is an organic group comprising at least one structural unit that interrupts the overlap of one p-orbital and another across an intervening σ bond within a conjugated system, i.e., a system of overlapping p-orbitals connected to delocalized π-electrons in the molecule. For example, the linker group may comprise at least one C atom having only σ bonds (i.e., four σ bonds) in the main chain (backbone) so that delocalization of π-electrons does not occur. As used herein, the term “electronically inactive” means that charge cannot be transported from one end of the linker group to the other end of the linker group by any transport mechanism other than tunneling. Preferably, the electronically inactive group used herein may have a band gap of 3 eV or more, more preferably 3.5 eV or more, even more preferably 4 eV or more, particularly preferably 5 eV or more, and most preferably 6 eV or more, where the term “band gap” means the energy gap between the HOMO (most occupied molecular orbital) and the LUMO (least occupied molecular orbital).

[0014] Preferably, the linker group L is selected from the group consisting of a straight-chain alkylene group having 1 to 20 carbon atoms, or a cyclic or branched alkylene group having 3 to 20 carbon atoms, wherein one or more non-contiguous methylene groups may be replaced with -O-, -S-, -C(=O)O-, -C(=S)S-, an aromatic ring, or a heteroaromatic ring.

[0015] The aromatic and heteroaromatic rings are preferably simple aromatic and heteroaromatic rings, more preferably 5- or 6-membered aromatic and heteroaromatic rings, respectively. The simple heteroaromatic ring comprises at least one heteroatom in the aromatic ring, preferably one or two heteroatoms, preferably heteroatoms selected from N, O, and S.

[0016] Additionally, the compound according to the present invention comprises an organic functional group FG connected to a linker group L. The organic functional group FG is preferably selected from the group consisting of an aromatic ring system having 6 to 60 aromatic ring atoms or a heteroaromatic ring system having 5 to 60 aromatic ring atoms, both of which are optionally, for example, a group R as defined below. 1 or R 4 It may be further substituted by. Preferred examples of aromatic or heteroaromatic ring systems as the FG group are selected from biphenyl, terphenyl, quarterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxen, isotruxen, spirotruxen, spiroisotruxen, and indenocarbazole. Particularly preferred examples of the FG group are selected from biphenyl, terphenyl, quarterphenyl, or fluorene, and more preferably from biphenyl.

[0017] A highly desirable example of a ring system suitable as a group FG is selected from the following aromatic groups:

[0018]

[0019] The dotted line in the formula indicates the binding position for linker group L, and the group is one or more groups R 1 It can be further substituted by. R 1 is defined below.

[0020] The compound according to the present invention is preferably of low molecular weight. As used herein, the term "low molecular weight" means a compound having a molecular weight of less than 2000 g / mol. Preferably, the compound according to the present invention has a molecular weight of 1000 g / mol or less. More preferably, it has a molecular weight of 900 g / mol or less, more preferably 800 g / mol or less, even more preferably 700 g / mol or less, and particularly preferably 600 g / mol or less. For example, the compound of the present invention has a molecular weight of 100 g / mol to 1000 g / mol, or 100 g / mol to 900 g / mol, or 100 g / mol to 800 g / mol, or 100 g / mol to 700 g / mol, or 100 g / mol to 600 g / mol.

[0021] The small molecules of the present invention can be easily manufactured and processed. In particular, the preparation of compounds and quantum materials containing ligands is very simple. The process is suitable for the commercial production (mass production) of ligands and quantum materials. Furthermore, fine-tuning of the ligands can be easily achieved, and the customization of quantum materials containing the ligands is convenient. Small molecules enable fine-tuning of the surface chemistry of quantum dots. Since the concentration of small molecules can be easily controlled, different types of ligands can be mixed on the surface of quantum dots. Additionally, small molecules can be easily dissolved in various commonly used organic solvents, allowing for easy processability. Polymeric materials generally do not offer these advantages. Therefore, the small molecules and quantum materials of the present invention are suitable for mass production.

[0022] More preferably, the organic functional group FG is selected from the group consisting of an electron injector, an electron transporter, a hole blocker, an n-dopant group, a host group, a matrix group, a wide band gap group, a fluorescence emitter group, a delayed fluorescence group, a phosphorescent group, an electron blocker, a hole transporter, a hole injector, or a p-dopant group.

[0023] Particularly preferably, the organic functional group FG has a fairly large energy gap ΔE between its singlet energy (S1) and triplet energy (T1). ST It represents. The energy gap of FG is preferably larger than the energy gap disclosed below for the delayed fluorescent material, that is, it is preferably greater than 0.2 eV, very preferably greater than 0.3 eV, and particularly preferably greater than 0.5 eV.

[0024] Preferably, FG is selected from the groups mentioned above but not from the delayed fluorescence groups, where ΔE ST The above-mentioned preference applies to .

[0025] More preferably, the organic functional group FG is an electron transport or hole transporter, but not specifically a delayed fluorescence group, that is, electron transporters and hole transporters have a fairly large energy gap ΔE between their singlet energy (S1) and triplet energy (T1). ST It indicates that the energy gap of electron and hole transporters is preferably greater than the energy gap disclosed below for the delayed fluorescent material, that is, it is preferably greater than 0.2 eV, very preferably greater than 0.3 eV, and particularly preferably greater than 0.5 eV.

[0026] Larger ΔE ST Having it improves performance data of electroluminescent devices, such as efficiency, voltage, lifespan, and color (e.g., purity or color gamut).

[0027] Species of these groups are well known in the prior art. In general, all species of these groups used according to the prior art and known to those skilled in the art of organic electroluminescent devices are suitable and can be used as organic functional groups FG.

[0028] A preferred wide band gap group can be derived from a material as disclosed in US 7,294,849, characterized by having a band gap of at least 3.5 eV. Accordingly, in a preferred embodiment, the wide band gap material is a material having a band gap (i.e., the difference between the LUMO and HOMO energy levels, where LUMO and HOMO are respectively defined as the lowest unoccupied molecular orbital and the highest occupied molecular orbital) of 3.0 eV or more, preferably 3.2 eV or more, very preferably 3.5 eV or more, particularly preferably 3.7 eV or more, and very particularly preferably 4.0 eV or more.

[0029] It is desirable for the wide band gap material to be a pure organic compound, that is, an organic compound without metals or metal ions. It is highly desirable for the pure organic compound to be an aromatic or heteroaromatic compound. Particularly preferably, the wide band gap material is a pure aromatic organic compound.

[0030] A preferred fluorescent emitter group can be derived from the compounds described below. A preferred fluorescent group is selected from the class of arylamines.

[0031] In the sense of the present invention, arylamines are understood to mean compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a condensed ring system, particularly preferably a condensed ring system having at least 14 aromatic ring atoms.

[0032] Preferred examples thereof are aromatic anthracenamine, aromatic anthracendiamine, aromatic pyreneamine, aromatic pyrenediamine, aromatic chrysenamine, or aromatic chrysendiamine. Aromatic anthracenamine is understood to mean a compound in which one diarylamino group is directly bonded to an anthracene group, preferably at the 9-position. Aromatic anthracendiamine is understood to mean a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably at the 9,10-position. Aromatic pyreneamine, pyrenediamine, chrysenamine, and chrysendiamine are similarly defined, wherein the diarylamino group is preferably bonded to pyrene at the 1-position or 1,6-position. Additional preferred fluorescent emitters are indenofluorenamine or indenofluorediamine (e.g., according to WO 2006 / 108497 or WO 2006 / 122630), benzoindenofluorenamine or benzoindenofluorediamine (e.g., according to WO 2008 / 006449), and dibenzoindenofluorenamine or dibenzoindenofluorediamine (e.g., according to WO 2007 / 140847), and indenofluorene derivatives containing a condensed aryl group disclosed in WO 2010 / 012328. Further preferred fluorescent emitters are benzanthracene derivatives as disclosed in WO 2015 / 158409, anthracene derivatives as disclosed in WO 2017 / 036573, fluorene dimers as in WO 2016 / 150544, or phenoxazine derivatives as disclosed in WO 2017 / 028940 and WO 2017 / 028941. Pyrenearylamines disclosed in WO 2012 / 048780 and WO 2013 / 185871 are likewise preferred. Likewise, benzoindenofluorenamine disclosed in WO 2014 / 037077, benzofluorenamine disclosed in WO 2014 / 106522, and indenofluorene disclosed in WO 2014 / 111269 or WO 2017 / 036574 are preferred.

[0033] Preferably, the delayed fluorescence group is an e-type delayed fluorescence group, i.e., an eosin-type delayed fluorescence group, wherein the energy levels S1 and T1 of the delayed fluorescence group are close to each other to enable thermally activated reverse intersystem crossing (RISC) from T1 to S1.

[0034] Those skilled in the art know many compounds and groups suitable for use for the purposes of the present invention.

[0035] Desirable delayed fluorescence groups are, for example, Tanaka et al., Chemistry of Materials 25(18), 3766 (2013), Ye Tao et al., Adv. Mater. 2014, 26, 7931-7958, Zhang et al., Nature Photonics advance online publication, 1 (2014), doi: 10.1038 / nphoton.2014.12, Serevicius et al., Physical Chemistry Chemical Physics 15(38), 15850 (2013), Youn Lee et al., Applied Physics Letters 101(9), 093306 (2012), Nasu et al., ChemComm, 49, 10385 (2013), MY Wong et al., Adv. Mater. 2017, 29, 1605444, Chem. Soc. Rev., 2017, 46, 915 and Nature Reviews Materials, 2018, Volume 3, Article Number 18020; Chem. Rec. 2018, 18, 1-14, WO 2011 / 070963, WO 2012 / 133188, WO 2015 / 022974, WO 2015 / 098975, WO 2013 / 154064, WO 2013 / 161437, WO It is disclosed in 2013 / 081088 and WO 2013 / 011954.

[0036] Preferably, the delayed fluorescence group is a pure organic (i.e., metal or metal ion-free) group, very preferably an aromatic or heteroaromatic group. Additionally, it is preferable that the delayed fluorescence group, which is an aromatic or heteroaromatic group, preferably an aromatic group, is substituted with one or more donor groups and one or more acceptor groups.

[0037] People skilled in the art have no difficulty identifying groups having donor or acceptor characteristics.

[0038] A donor group is understood to be an electron-donor group, that is, a group having +I and / or +M effects. Determining such parameters using the Hammett equation is also well known to those skilled in the art. Suitable and desirable donor groups are, for example, diaryl- or heteroarylamino groups, carbazole or indeno- or indolocarbazole groups and derivatives thereof, which are preferably bonded to the aromatic or heteroaromatic portion of the group through a nitrogen atom.

[0039] Acceptor groups are understood to be electron acceptors, that is, groups having -I and / or -M effects. Determining such parameters using the Hammett equation is also well known to those skilled in the art. Suitable and desirable acceptor groups are cyano groups, CF3, ketones, preferably aromatic ketones, phosphine oxides, and electron-poor heteroaromatic groups such as triazines, pyridines, pyrimidines, and pyrazines, which may also be substituted.

[0040] Desirable phosphorescent devices are also well known to those skilled in the art and are widely used in the field of organic electroluminescent devices.

[0041] Phosphorescent compounds are compounds that emit light or radiation through photoluminescence or electroluminescence, where the electronic transition represents a spin-ban transition. Therefore, the radiation is based on a transition from an excited triplet or pentat state, or from a mixed state possessing triplet or pentat characteristics.

[0042] Phosphorescent compounds (also called triplet emitters) preferably contain elements having an atomic number of at least 20, very preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80.

[0043] Preferably, the phosphorescent group is an organometallic group, and particularly preferably includes a transition metal.

[0044] Most preferably, the phosphorescent material comprises copper, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, particularly preferably copper, iridium, and platinum.

[0045] Very particularly desirable phosphorescent organometallic complexes are WO2015 / 091716 and WO00 / 70655, WO2001 / 41512, WO2002 / 02714, WO2002 / 15645, EP1191612, WO2005 / 033244, WO2005 / 019373, US2005 / 0258742, WO2006 / 056418, WO2007 / 115970, WO2007 / 115981, WO2008 / 000727, WO2009 / 050281, WO2009 / 050290, WO2011 / 051404, WO2011 / 073149, WO2012 / 121936, US2012 / 0305894, WO2012 / 170571, WO2012 / 170461, WO2012 / 170463, WO2006 / 121811, WO2007 / 095118, WO2008 / 156879, WO2008 / 156879, WO2010 / 068876, WO2011 / 106344, WO2012 / 172482, EP3126371, WO2015 / 014835, WO2015 / 014944, WO2016 / 020516, US2016 / 0072081, WO2010 / 086089, WO2011 / 044988, WO2014 / 008982, They are disclosed in WO2014 / 023377, WO2014 / 094961, WO2010 / 069442, WO2012 / 163471, WO2013 / 020631, US2015 / 0243912, WO2008 / 000726, WO2010 / 015307, WO2010 / 054731, WO2010 / 054728, WO2010 / 099852, WO2011 / 032626, WO2011 / 157339, WO2012 / 007086, WO2015 / 036074, WO2015 / 104045, WO2015 / 117718, and WO2016 / 015815, which preferably contain iridium and It is a platinum complex.

[0046] Additional preferred phosphorescent organometallic complexes represent polypodal ligands disclosed in WO2004081017, WO2005042550, US20050170206, WO2009 / 146770, WO2010 / 102709, WO2011 / 066898, WO2016124304, WO2017032439, WO2018019688, EP3184534, WO2018 / 011186, WO 2016 / 193243 and WO 2015 / 091716A1.

[0047] Additionally, preferred dinuclear phosphorescent organometallic complexes are disclosed in WO2011 / 045337, US2015, WO2016 / 079169, WO2018 / 019687, WO2018 / 041769, WO2018 / 054798, WO2018 / 069196, WO2018 / 069197, and WO2018 / 069273.

[0048] Copper complexes disclosed in WO2010 / 031485, US2013 / 150581, WO2013 / 017675, WO2013 / 007707, WO2013 / 001086, WO2012 / 156378, WO2013 / 072508, and EP2543672 are also preferred.

[0049] Examples of suitable phosphorescent complexes containing palladium are disclosed in WO2014 / 109814.

[0050] Any phosphorescent complex generally known to those skilled in the art and used in phosphorescent OLEDs is suitable for use for the purposes of this application.

[0051] Explicit examples of phosphorescent complexes are Ir(ppy)3 and its derivatives and the following structures.

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] Further explicit examples for phosphorescent complexes are iridium and platinum complexes containing carbene ligands, wherein heterogeneous and homogeneous, meridonal and faciale isomers of the complexes below may also be used.

[0060]

[0061] The following copper complex is also a suitable example for phosphorescent complexes.

[0062]

[0063] In addition to all structural units mentioned below as electron transport or hole transport groups, the preferred host or matrix group is a polypodal metal complex, quinoline-metal complex, aminoquinoline-metal complex, or benzoquinoline-metal complex, such as anthracene, benzanthracene, benzophenanthrene, phenanthrene, tetracene, coronene, chrysene, fluorene, spirofluorene, perylene, phthaloperylene, naphthaloperylene, decacycline, rubrene, oligoarylenevinylene (e.g., DPVBi = 4,4'-bis(2,2-diphenylethenyl)-1,1'-biphenyl), and 8-hydroxyquinoline (e.g., AlQ3 (= aluminum(III) tris(8-hydroxyquinoline)).

[0064] Desirable electron transporters are triazine, pyrimidine, pyridine, pyrazine, pyrazol, pyridazine, quinoline, isoquinoline, quinoxaline, quinazolin, thiazole, benzothiazole, oxazole, benzoxazole, benzimidazole, oxadiazole, phenoxazine, lactam, phenanthroline, and dibenzofuran.

[0065] Desirable hole transporters are carbazole, biscarbazole, indenocarbazole, indolocarbazole, amine, triarylamine, fluorenamine, and spirobifluorenamine.

[0066] Also preferably, the compound of the present invention has the following general formula (1):

[0067]

[0068] The following applies to the symbols and exponents in the expression:

[0069] X is -SH, -C(=O)OH, -NH2, -P(=O)(OH)(OH), -SeH, -P(R'R''), -S - Y + , -S(=O)OH, -S(=O)O - Y + , -C(=O)O - Y + , -OC(=O)R'''SH, -OC(=O)R'''S - Y + , -P(=O)(OH)(O - Y + ), -Se - Y + , -C(=S)SH, -C(=S)S - Y + , -B(OH)2, -B(OH)O - Y + , -B(O - Y + )2, -B(O - )2Z 2+ ,-P(=O)(O - Y + )(O - Y + ) or -P(=O)(O - )(O - )Z 2+ Selected from;

[0070] Y + is Na + , K + , Li + , ½ Cd 2+ , ½ Zn 2+ , ½ Mg 2+, ½ Ca 2+ , or ½ Sr 2+ , ⅓ In 3+ , ⅓ Ga 3+ Selected from;

[0071] Z 2+ is Cd 2+ , Zn 2+ , Mg 2+ , Ca 2+ , Sr 2+ Selected from;

[0072] R',R'' is selected from H, a linear or branched alkyl group having 1 to 20 carbon atoms, either identically or differently;

[0073] R''' is selected from linear or branched alkyl groups having 1 to 10 carbon atoms;

[0074] n is an integer from 0 to 20.

[0075] Therefore, in a compound represented by general formula (1), group X takes on the function of an anchor group AG as defined above, and the alkylene group / chain of the compound represented by general formula (1) (its length is defined by the exponent n) takes on the function of a linker group L as defined above.

[0076] More preferably, X is -SH, -S - Y + , -C(=O)OH, -C(=O)O - Y + , -B(OH)2, -B(OH)O - Y + , -B(O - Y + )2, -B(O - )2Z 2+ , -P(=O)(OH)(OH), -P(=O)(OH) (O - Y + ), -P(=O)(O - Y + )(O - Y + ), -P(=O)(O - )(O- )Z 2+ , -OC(=O)R'''SH, or -OC(=O)R'''S - Y + Selected from, most preferably X is + , -SH, -S - Y + , -P(=O)(OH) (OH), -P(=O)(OH)(O - Y + ), -P(=O)(O - Y + )(O - Y + ), -P(=O)(O - )(O - )Z 2+ , OC(=O)R'''SH, or -OC(=O)R'''S - Y + am.

[0077] The exponent n is an integer from 0 to 20; that is, when n is 0, the organic functional group FG and group X according to general formula (1) are linked only by the group -CH2-. Preferably, n is an integer from 0 to 10, very preferably from 0 to 6, particularly preferably from 0 to 4, very particularly preferably from 0 or 2, and most preferably n is 2.

[0078] In the above equation (1), cation Y + The notation “½ Cd used in this specification to define 2+ ”, or “½ Zn 2+ ”, or “⅓ In 3+ ” etc. Y + Ga is also a divalent cation, such as Cd 2+ , or Zn 2+ Etc., or trivalent cations, such as “⅓ In 3+It should be understood that this means it may represent etc. In this case, it shares its positive charge with two or three distinct monovalent anion groups X (i.e., one divalent or trivalent cation acts as a counterion for two and three distinct molecules of the compound of formula (1), respectively).

[0079] Also preferably, Y + is Na + , K + or Li + It is selected from. Also preferably Z 2+ is Cd 2+ , Zn 2+ , Mg 2+ Selected from.

[0080] According to a preferred embodiment, the organic functional group FG is an electron transporter ET, which is more preferably selected from an electron-deficient heteroaromatic group. A heteroaromatic group having six aromatic ring atoms, of which at least one, preferably two, and very preferably at least three nitrogen atoms, or a heteroaromatic group having five aromatic ring atoms, of which at least two are heteroatoms, preferably at least one of which is a nitrogen atom, is even more preferred. Particularly preferably, the electron transporter is selected from triazine, pyrimidine, pyridine, pyrazine, pyrazol, pyridazine, quinoline, isoquinoline, quinoxaline, quinazolin, thiazole, benzothiazole, oxazole, benzoxazole, benzimidazole, oxadiazole, phenoxazine, lactam, phenanthroline, and dibenzofuran.

[0081] The electron transporter ET preferably has a LUMO (lowest unoccupied molecular orbital) energy of less than -1.3 eV, very preferably less than -2.5 eV, and most preferably less than -2.7 eV.

[0082] Molecular orbitals, specifically the material's most occupied molecular orbital (HOMO) and least occupied molecular orbital (LUMO), their energy levels, and the energies of the lowest triplet state T1 and lowest excited singlet state S1, are determined through quantum chemical calculations. For calculations of metal-free organic materials, geometry optimization is first performed using the "Ground State / Quasi-Empirical Formula / Default Spin / AM1 / Charge 0 / Spin Singlet" method. Subsequently, energy calculations are performed based on the optimized geometry. This is carried out using the "TD-SCF / DFT / Default Spin / B3PW91" method with the "6-31G(d)" basis set (Charge 0, Spin Singlet). For metal-containing compounds, geometry is optimized via the "Ground State / Hartree-Fock / Default Spin / LanL2 MB / Charge 0 / Spin Singlet" method. Energy calculations are performed similarly to the method described above for organic materials, except that the "LanL2DZ" basis set is used for metal atoms and the "6-31 G(d)" basis set is used for ligands. The HOMO energy level HEh or the LUMO energy level LEh is obtained from the energy calculations in Hartree units. This is used to determine the HOMO and LUMO energy levels in electron volts, calibrated by cyclic voltammetry measurements, as follows:

[0083] HOMO(eV)=((HEh*27.212)-0.9899) / 1.1206;

[0084] LUMO(eV)=((LEh*27.212)-2.0041) / 1.385

[0085] These values ​​will be considered as the HOMO and LUMO energy levels of the material in the context of the present application.

[0086] The lowest triplet state T1 is defined as the energy of the triplet state having the lowest energy evident from the described quantum chemical calculations. The lowest excited singlet state S1 is defined as the energy of the excited singlet state having the lowest energy evident from the described quantum chemical calculations.

[0087] The method described in this specification is independent of the software package used and always provides the same result. Examples of programs frequently used for this purpose are "Gaussian09 W" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

[0088] More preferably, the electron carrier ET is a heteroaromatic group selected from the following groups.

[0089]

[0090] The dashed line in the formula indicates the bonding position for the linker group L, that is, the alkylene group linking the groups FG and X in Formula (1);

[0091] Q' is the same or different in each case, CR 1 Selected from and N;

[0092] Q'' is NR 1 Selected from , O and S;

[0093] R 1 In each case, H, D, F, Cl, Br, I, N(R) are identical or different 2 )2, CN, NO2, Si(R 2 )3, B(OR 2 )2, C(〓O)R 2 , P(〓O)(R 2 )2, S(〓O)R 2 , S(〓O)2R 2 , OSO2R 2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy, or thioalkoxy group having 3 to 40 carbon atoms (each of these having one or more R 2 It can be substituted by radicals, and one or more non-adjacent CH2 groups are R 2 C〓CR 2 , C≡C, Si(R 2 )2, Ge(R 2 )2, Sn(R 2 )2, C〓O, C〓S, C〓Se, C〓NR 2 , P(〓O)(R 2 ), SO, SO2, NR 2 , O, S or CONR 2 It can be replaced with and one or more hydrogen atoms can be replaced with D, F, Cl, Br, I, CN, or NO2), or having 5 to 60 aromatic ring atoms and in each case one or more R 2 An aromatic or heteroaromatic ring system capable of being substituted with radicals, or having 5 to 60 aromatic ring atoms and one or more R 2 An aryloxy, arylalkyl, or heteroaryloxy group capable of being substituted with a radical, or a combination of two or more of these groups or a crosslinkable Q group; wherein, two or more adjacent R 1 Radicals can together form a monocyclic or polycyclic, aliphatic or aromatic ring system, preferably two or more adjacent R 1 Radicals do not form a monocyclic or polycyclic, aliphatic or aromatic ring system together;

[0094] R 2 are the same or different in each case, and H, D, F, Cl, Br, I, N(R 3 )2, CN, NO2, Si(R 3 )3, B(OR 3)2, C(〓O)R 3 , P(〓O)(R 3 )2, S(〓O)R 3 , S(〓O)2R 3 , OSO2R 3 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy, or thioalkoxy group having 3 to 40 carbon atoms (each of these having one or more R 3 It can be substituted by radicals, and one or more non-adjacent CH2 groups are R 3 C〓CR 3 , C≡C, Si(R 3 )2, Ge(R 3 )2, Sn(R 3 )2, C〓O, C〓S, C〓Se, C〓NR 3 , P(〓O)(R 3 ), SO, SO2, NR 3 , O, S or CONR 3 It can be replaced with and one or more hydrogen atoms can be replaced with D, F, Cl, Br, I, CN, or NO2), or having 5 to 60 aromatic ring atoms and in each case one or more R 3 An aromatic or heteroaromatic ring system capable of being substituted with radicals, or having 5 to 60 aromatic ring atoms and one or more R 3 An aryloxy, arylalkyl, or heteroaryloxy group that can be substituted with a radical, or a combination of two or more of these groups; wherein two or more adjacent R 2 Radicals can together form monocyclic or polycyclic, aliphatic or aromatic ring systems;

[0095] R 3are, in each case, the same or different, an aliphatic, aromatic, and / or heteroaromatic hydrocarbyl radical having H, D, F, or 1 to 20 carbon atoms, wherein one or more hydrogen atoms may also be replaced by F; and also two or more R 3 Substituents can together form monocyclic or polycyclic, aliphatic or aromatic ring systems;

[0096] And at least one Q' is N.

[0097] The following definitions apply to chemical groups used as general definitions. They apply unless a more specific definition is given.

[0098] In the sense of the present invention, the aryl group contains 5 to 60 or 6 to 40 aromatic ring atoms, none of which are heteroatoms. The aryl group is understood here to mean a simple aromatic ring, e.g., benzene, or a condensed aromatic polycyclic ring, e.g., naphthalene, phenanthrene, or anthracene. In the sense of the present application, a condensed aromatic polycyclic ring consists of two or more simple aromatic rings condensed together.

[0099] In the sense of the present invention, the heteroaryl group contains 5 to 60 or 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms are preferably selected from N, O, and S. The heteroaryl group is understood here to mean a simple heteroaromatic ring, e.g., pyridine, pyrimidine, or thiophene, or a condensed heteroaromatic polycyclic ring, e.g., quinoline or carbazole. A condensed heteroaromatic polycyclic ring in the sense of the present application consists of two or more simple heteroaromatic rings condensed together.

[0100] An aryl or heteroaryl group, which in each case may be substituted by the radicals mentioned above and may be linked to an aromatic or heteroaromatic ring system through any desired position, is particularly benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazol, indazole, Imidazole, benzimidazole, naftimidazole, fenantrimidazole, pyridimidazole, pyrazineimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, fenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naftiridine, azacarbazole, benzocarbolin, fenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, It is believed to refer to groups derived from 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, and benzothiadiazole.

[0101] In the context of the present invention, an aryloxy group is understood to mean an aryl group as defined above, bonded through an oxygen atom. Similarly, the same applies to heteroaryloxy groups.

[0102] In the context of the present invention, an arylalkyl group is understood to mean an aryl group as defined above, to which an alkyl group defined below is bonded.

[0103] An aromatic ring system in the sense of the present invention comprises 6 to 60 or 6 to 40 carbon atoms in the ring system and does not include any heteroatoms as aromatic ring atoms. Accordingly, in the sense of the present application, an aromatic ring system does not include heteroaryl groups. In the sense of the present invention, an aromatic ring system is not necessarily required to contain only aryl groups; instead, it is intended to be understood as a system in which a plurality of aryl groups may also be connected by non-aromatic units, such as one or more optionally substituted C, Si, N, O, or S atoms. In such cases, the non-aromatic units preferably comprise less than 10% of atoms other than H, based on the total number of atoms other than H in the entire aromatic ring system. Accordingly, systems such as, for example, 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether, and stilbene are also intended to be regarded in the sense of the present invention as aromatic ring systems, which are systems in which two or more aryl groups are connected, for example, by linear or cyclic alkyl, alkenyl, or alkynyl groups, or by silyl groups. Additionally, systems in which two or more aryl groups are connected to each other through a single bond are also regarded in the sense of the present invention as aromatic ring systems, such as, for example, biphenyl and terphenyl.

[0104] Preferably, the aromatic ring system is understood to be a chemical group in which the aryl groups constituting the chemical groups are conjugated with one another. This means that the aryl groups are connected to one another through a single bond or through a connecting unit having a free pi electron pair capable of participating in conjugation. The connecting unit is preferably selected from a nitrogen atom, a single C=C unit, a single C≡C unit, a plurality of conjugated C=C units and / or C≡C units, -O- and -S-.

[0105] In the sense of the present invention, a heteroaromatic ring system contains 5 to 60 or 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O, or S. A heteroaromatic ring system is defined as the above aromatic ring system, but differs in that it must obtain at least one heteroatom as one of the aromatic ring atoms. Accordingly, this differs from an aromatic ring system according to the definition of the present invention, which cannot include any heteroatom as an aromatic ring atom.

[0106] An aromatic ring system having 6 to 60 or 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 60 or 5 to 40 aromatic ring atoms is, in particular, a group derived from the aryl or heteroaryl group mentioned above, or from biphenyl, terphenyl, quaternphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxen, isotruxen, spirotruxen, spiroisotruxen, and indenocarbazole.

[0107] For the purposes of the present invention, a straight-chain alkyl group having 1 to 40 or 1 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 40 or 3 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 or 2 to 20 carbon atoms, wherein individual H atoms or CH2 groups may also be substituted by the group mentioned above under the definition of a radical, preferably, radical methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, It is understood to mean ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexanyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethinyl, propynyl, butynyl, pentinyl, hexinyl, or octinyl. Considering the above definition, a straight-chain alkylene group having 1 to 20 carbon atoms, or a cyclic or branched alkylene group having 3 to 20 carbon atoms, is considered to mean the respective deradical of the radicals mentioned above.

[0108] The alkoxy or thioalkyl group having 1 to 40 or 1 to 20 carbon atoms is preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, It is believed to mean cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexeniltio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, hexinylthio, heptenylthio, or octenylthio.

[0109] According to a further preferred embodiment, the electron transporter ET is not directly bonded to the linker group L, i.e., the alkylene group linking the groups FG and X in Formula (1), but rather to the divalent group Ar interconnecting the linker group L and the electron transporter ET according to the following structure. J It goes through:

[0110]

[0111] The dotted line in the formula indicates the linker group L, that is, the bond to the alkylene group in formula (1), where the group ET is as described above and g is 0 or 1.

[0112] When the exponent g is 0, this is the Ar JThis means that the linker and the electron transporter ET are directly connected to each other, as shown in Equation (1).

[0113] Preferably, 2-valent Ar J is one or more radicals R 1 It is selected from an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted with Ar. J It is particularly preferable when selected from divalent groups derived from benzene, pyridine, pyrimidine, biphenyl, terphenyl, fluorene, spirobifluorene, furan, dibenzofuran, thiophene, and dibenzothiophene, each having one or more radicals R 1 It may also be substituted by. Particularly preferably, Ar J is a phenylene, biphenylene, or terphenylene group, and most preferably Ar J is a phenylene group.

[0114] Preferred examples of heteroaromatic electron transporter ETs are (regardless of whether g is 0 or 1 as shown above): pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-triazine, 1,3,5-triazine, quinoline, isoquinoline, quinoxaline, quinazoline, pyrazol, imidazole, benzimidazole, thiazole, benzothiazole, oxazole, or benzoxazole, each of which is R 1 It may also be substituted by. More preferably, the electron carrier is one or more R 1 The radical-substituted pyridine, pyrazine, pyrimidine, pyridazine, and 1,3,5-triazine.

[0115] A highly desirable heteroaromatic electron transporter ET is selected from the following devices (ET-12) to (ET-21):

[0116]

[0117]

[0118] Food R1 is as defined above, and the dotted line represents the linker group L, i.e., the alkylene group linking groups FG and X in Equation (1), or if present, the group Ar J Indicates the joint location for .

[0119] R in the electronic transporter ET 1 The substituents are preferably selected from the group consisting of H and aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, wherein in each case, one or more R 2 It may be substituted by radicals, where one or more radicals R 1 It is desirable that the electron transporter ET substituted by does not include an electron-rich aromatic or heteroaromatic ring or ring system.

[0120] Examples of highly particularly desirable heteroaromatic electron transporters ET are the following, which consist of one or more independent Rs as defined above. 2 It can be substituted with radicals, where the dotted bond indicates the bonding position for the linker group L, i.e., the alkylene group linking groups FG and X in Equation (1):

[0121]

[0122]

[0123]

[0124]

[0125] According to another preferred embodiment, the organic functional group FG is a hole transport group ET, which is more preferably selected from electron-rich heteroaromatic groups. Here, the term hole transport describes a functional group that enables a compound carrying this functional group in an electronic device (e.g., an electroluminescent device) to transport a positive charge as a majority charge carrier. A heteroaryl group having 5 to 60 aromatic ring atoms is more preferred, wherein the nitrogen atom is a preferred heteroatom. Particularly preferably, the hole transport group is selected from carbazole, biscarbazole, indenocarbazole, indolocarbazole, amine, triarylamine, fluorenamine, and spirobifluorenamine.

[0126] More preferably, the air transporter HT is the following.

[0127]

[0128] food

[0129] Ar L In each case, one or more radicals R, identically or differently 4 An aromatic ring system having 6 to 40 aromatic ring atoms that may be substituted with, and one or more radicals R 4 Selected from a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted with;

[0130] Ar 1 In each case, one or more radicals R, identically or differently 4 An aromatic ring system having 6 to 40 aromatic ring atoms that may be substituted with, and one or more radicals R 4 Selected from a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted with;

[0131] E is a single bond or -C(R4 )2-, -N(R 4 2 selected from )-, -O-, and -S- are gi;

[0132] k is 0 or 1, identically or differently, in each case; and when k=0, Ar L ...is not present, and the nitrogen atom and the linker group are directly connected;

[0133] In each case, m is 0 or 1, either identically or differently, and when m=0, there is no E and Ar 1 is not connected;

[0134] R 4 In each case, identically or differently, H, D, F, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 , selected from a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more radicals R 4 They may be connected to each other to form a ring; and the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems each have one or more radicals R in each case 5 It may also be substituted by, and one or more CH2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are -R in each case. 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5, -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), can be replaced by -O-, -S-, SO or SO2;

[0135] R 5 In each case, identically or differently, H, D, F, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , selected from a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more radicals R 5 They may be connected to each other to form a ring; and the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems each have one or more radicals R in each case 6 It may also be substituted by, and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups are -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), may be replaced by -O-, -S-, SO or SO2;

[0136] R 6...is selected, in each case identically or differently, from H, D, F, CN, alkyl groups having 1 to 20 carbon atoms, aromatic ring systems having 6 to 40 carbon atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more radicals R 6 The groups may be connected to each other to form a ring; the alkyl group, aromatic ring system and heteroaromatic ring system may be substituted by F and CN.

[0137] Gi Ar L is 2 is a group. Preferably, the group Ar L is one or more radicals R 4 It is selected from an aromatic ring system having 6 to 30 aromatic ring atoms that may be substituted with Ar. L Each is one or more radicals R 4 It is particularly preferred when selected from divalent groups derived from benzene, biphenyl, terphenyl, naphthyl, fluorenyl, indenofluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl, which may be substituted by. Most preferably, Ar L is one or more radicals R 4 It is a divalent group derived from benzene that may be substituted with .

[0138] According to additional embodiments, it is preferable that the exponent k is 0, which is the Ar L Since it does not exist, it means that the nitrogen atom of the amine and the linker group are directly connected to each other.

[0139] Especially desirable Ar 1is selected from, identically or differently, phenyl, biphenyl, terphenyl, quarterphenyl, naphthyl, fluorenyl, particularly 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzoflurenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzofuranyl benzothiophenyl, benzoffused dibenzofuranyl, benzoffused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, and their Each optionally has one or more radicals R 4 It can also be replaced with.

[0140] Preferably, the Ar 1 It is selected differently in each case.

[0141] Desirable Ar 1 ...is selected from the following formulas, either identically or differently.

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158] The gases in the food are in a free position. 4 It may be substituted, but preferably unsubstituted at these positions, and the dotted line indicates the bonding position for the nitrogen atom.

[0159] According to a preferred embodiment, the exponent m is 0, which is the base Ar 1 This means that it is not connected by E.

[0160] According to an alternative embodiment that may be desirable under specific conditions, the exponent m is 1, which is the Ar 1 This means that it is connected by E.

[0161] Gi Ar 1 Where is connected by E, preferably, Ar 1 Silver is selected from phenyl and fluorenyl, identically or differently, and each of which has one or more groups R 4 It may also be substituted by. Also, in such cases, the Ar 1 The mechanism E connecting is each mechanism Ar 1 On the phase, each group Ar, preferably phenyl or fluorenyl 1 On the surface, the Ar group for the amine nitrogen atom 1 It is preferable that it be located at an ortho-position for the bond. Additionally, preferably, in this case, the 6-ring having an amine nitrogen atom is, the group Ar 1 and E (E is C(R 4 )2, NR 4 It is formed as (if selected from , O and S); and if E is a single bond, a 5-ring is formed.

[0162] According to an alternative embodiment that may be desirable under specific conditions, the exponent m is 1, which is the Ar 1 This means that it is connected by E.

[0163] Gi Ar 1 Where is connected by E, preferably, Ar 1 Silver is selected from phenyl and fluorenyl, identically or differently, and each of which has one or more groups R 4 It may also be substituted by. Also, in such cases, the Ar 1 The mechanism E connecting is each mechanism Ar 1 On the phase, each group Ar, preferably phenyl or fluorenyl 1 On the surface, the Ar group for the amine nitrogen atom 1 It is preferable that it be located at an ortho-position for the bond. Additionally, preferably, in this case, the 6-ring having an amine nitrogen atom is, the group Ar 1 and E (E is C(R 4 )2, NR 4 It is formed as (if selected from , O and S); and if E is a single bond, a 5-ring is formed.

[0164] Gi Ar 1 If connected by E, moiety

[0165]

[0166] Particularly preferred embodiments of are selected from the following formulas.

[0167]

[0168]

[0169] Food particles are in a free position R 4It may be substituted with, but preferably not substituted at these positions, and the dashed line in the formula indicates the bonding position of the nitrogen atom to the linker group L, i.e., the alkylene group linking groups FG and X in Formula (1) (when k=0), or the group Ar L It represents the bond position for (when k=1).

[0170] A particularly desirable moiety for the hole transporter HT when m = 0

[0171]

[0172] follows the following equation.

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179] Food particles are in a free position R 4 It can be substituted, but preferably not substituted at these positions, and the dotted line in the formula represents the bonding position for the linker group L, that is, the alkylene group linking the groups FG and X in Formula (1).

[0180] Gi R 4 Preferably, the same or different, H, F, CN, Si(R 5 )3, selected from a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more radicals R 4They may be connected to each other to form a ring; and the alkyl group and the aromatic and heteroaromatic ring system in each case, one or more radicals R 5 It may also be replaced by.

[0181] Gi R 5 Preferably, the same or different, H, F, CN, Si(R 6 )3, selected from a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more radicals R 5 They may be connected to each other to form a ring; and the alkyl group and the aromatic and heteroaromatic ring system in each case, one or more radicals R 6 It may also be replaced by.

[0182] Preferred compounds according to Formula (1) are shown in Table 1 below:

[0183]

[0184]

[0185]

[0186]

[0187] The compound according to the present invention described above, comprising in its structure an anchor group (i.e., group AG), a conjugated conductive functional group (i.e., group FG), and a flexible, conjugated hindering group (i.e., group L) that separates the anchor group from the functional group, is suitable as a ligand for securing passivation of the nanoparticle surface and solubility of the nanoparticle in solution by binding to the surface of a semiconducting nanoparticle. Furthermore, it improves the overall performance of an electronic device by allowing an improved surface binding process and an increase in ligand density on the surface, and by enabling improved charge transport through the layer and into the quantum material.

[0188] semiconductor nanoparticles

[0189] The present invention also relates to semiconductor nanoparticles. According to the present invention, the semiconductor nanoparticle comprises a core, one or more shell layers, and at least one ligand attached to the outermost surface of one or more shell layers, and the at least one ligand is selected from compounds according to the present invention as described above.

[0190] In the context of this application, semiconductor / semiconductor nanoparticles or semiconductor / semiconductor nanocrystals are understood to mean semiconductor light-emitting nanoparticles. According to the present invention, as the inorganic portion of the semiconductor nanoparticles, a wide variety of known semiconductor light-emitting nanoparticles may be used as desired.

[0191] Additionally, the term "attachment" as used herein should be understood to include, but is not limited to, covalent bonds or ionic bonds or dipole-dipole interactions.

[0192] The type of shape of the semiconductor nanoparticles of the present invention is not particularly limited. Any type, for example, spherical, elongated, star-shaped, or polyhedral-shaped semiconductor nanocrystals may be used.

[0193] According to the present invention, the one or more shell layers of the semiconductor nanoparticles are preferably a single shell layer, a double shell layer, or a multi-shell layer having more than two shell layers, and most preferably a double shell layer.

[0194] As used herein, the term "shell layer" refers to a structure that covers the core wholly or partially. Preferably, the one or more shell layers cover the core wholly. The terms "core" and "shell" are widely known in the art and are commonly used in the field of quantum materials, such as in US 8221651 B2.

[0195] As used herein, the term "nano" refers to particles having at least one dimensional size, namely, a particle diameter of 0.1 nm to 999 nm, preferably 0.1 nm to 150 nm. The term nanoscale material refers to a material corresponding to that size.

[0196] The size of nanoparticles can be measured using a standard transmission electron microscope.

[0197] In a preferred embodiment of the present invention, the semiconducting luminescent nanoparticles of the present invention are quantum-sized materials, which are also referred to as quantum materials. The quantum-sized material or quantum material may be a quantum dot or a quantum rod, and preferably, the quantum-sized material or quantum material is a quantum dot.

[0198] As used herein, the term “quantum size” refers to the size of the semiconductor material itself, without ligands or other surface modifications, which can exhibit quantum confinement effects, as described in, for example, ISBN:978-3-662-44822-9. Generally, quantum size materials are said to be able to emit light of tunable, vivid, and vivid colors due to “quantum confinement” effects.

[0199] Preferably, the diameter of the overall structure of the quantum-sized material is 1 nm to 100 nm, more preferably 1 nm to 30 nm, and even more preferably 5 nm to 15 nm. Accordingly, the semiconductor nanoparticles of the present invention are preferably so-called quantum dots (QDs).

[0200] According to the present invention, the core of the semiconductor nanoparticle may vary. For example, CdS, CdSe, CdTe, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, GaAs, GaP, GaSb, HgS, HgSe, HgSe, HgTe, InAs, InP, InPS, InPZnS, InPZn, InPGa, InSb, AlAs, AlP, AlSb, Cu2S, Cu2Se, CuInS2, CuInSe2, Cu2(ZnSn)S4, Cu2(InGa)S4, TiO2 alloy, and any combination thereof may be used.

[0201] In a preferred embodiment of the present invention, the core of the semiconductor nanoparticle comprises one or more elements of Group 13 of the periodic table and one or more elements of Group 15 of the periodic table. Examples include GaAs, GaP, GaSb, InAs, InP, InPS, InPZnS, InPZn, InPGa, InSb, AlAs, AlP, AlSb, CuInS2, CuInSe2, Cu2(InGa)S4, and combinations thereof.

[0202] More preferably, the core comprises In and P atoms, for example, InP, InPS, InPZnS, InPZn, or InPGa.

[0203] According to a further preferred embodiment of the present invention, at least one of the shell layers comprises a first element of Group 12, Group 13, or Group 14 of the periodic table and a second element of Group 15 or Group 16 of the periodic table. Preferably, all shell layers comprise a first element of Group 12, Group 13, or Group 14 of the periodic table and a second element of Group 15 or Group 16 of the periodic table.

[0204] More preferably, at least one of the shell layers comprises a first element of Group 12 of the periodic table and a second element of Group 16 of the periodic table. For example, CdS, CdZnS, ZnS, ZnSe, ZnSSe, ZnSSeTe, CdS / ZnS, ZnSe / ZnS, and ZnS / ZnSe shell layers may be used. Even more preferably, all shell layers comprise a first element of Group 12 of the periodic table and a second element of Group 16 of the periodic table.

[0205] Particularly preferably, at least one shell layer is represented by the following formula (II), and

[0206] ZnS x Se y Te z, - (II)

[0207] In the equation, 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1, and more preferably 0≤x≤1, 0≤y≤1, z=0, and x+y=1.

[0208] ZnS, ZnSe, ZnSeS, ZnSeSTe, CdS / ZnS, ZnSe / ZnS, and ZnS / ZnSe shell layers are most preferably used.

[0209] Also preferably, all shell layers are represented by Equation (II).

[0210] For example, as semiconductor light-emitting nanoparticles for green and / or red emission use, CdSe / CdS, CdSeS / CdZnS, CdSeS / CdS / ZnS, ZnSe / CdS, CdSe / ZnS, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InP / ZnS / ZnSe, InPZn / ZnS, InPZn / ZnSe / ZnS, InPZn / ZnS / ZnSe, ZnSe / CdS, ZnSe / ZnS semiconductor light-emitting nanoparticles, or any combination of these may be used.

[0211] More preferably, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InP / ZnS / ZnSe, InPZn / ZnS, InPZn / ZnSe / ZnS, and InPZn / ZnS / ZnSe may be used.

[0212] In a preferred embodiment of the present invention, the shell layer of the semiconductor nanoparticle is a double shell layer.

[0213] The above-mentioned semiconducting luminescent nanoparticles are publicly available, for example, from Sigma-Aldrich and / or, for example, ACS Nano , 2016, 10 (6), pp 5769-5781, Chem. Motor. 2015, 27, 4893-4898, and International Patent Application Publication No. WO 2010 / 095140 A2.

[0214] According to the present invention, semiconductor nanoparticles preferably comprise at least two different ligands, preferably exactly two different ligands, attached to their outermost surface, wherein the ligands are selected from compounds according to the present invention as described above.

[0215] Also preferably, the semiconductor nanoparticle comprises a first ligand and a second ligand, both of which are selected from compounds according to the present invention as described above, wherein the first ligand comprises an organic functional group selected from electron transporters (i.e., having electron transport characteristics superior to hole transport characteristics), and the second ligand comprises an organic functional group selected from hole transporters (i.e., having hole transport characteristics superior to electron transport characteristics). Here, since the highest excited states of both the hole transport type ligand and the electron transport ligand have energies equal to or higher than the excited states of the quantum dots (most preferably 0.15 eV higher), the combination of the first ligand and the second ligand can form an excited state complex (so-called exciplex) as a supramolecular excited state having energy lower than the sum of the isolated charge groups. The energy of this exciplex (host) is energy transfer (e.g., F It can be transferred to semiconductor nanoparticles (guest) via FRET (Resonance Energy Transfer), thereby causing the emission spectrum of the host material (i.e., the exciplex of the first and second ligands) to overlap with the absorption band of the acceptor quantum dot (most preferably, the absorption band on the longest wavelength side of the absorption spectrum is 5000 M). -1 cm -1 Efficiency (e.g., quantum efficiency) can be further improved through energy transfer to the core via the exciplex.

[0216] One or even both of the electron and / or hole transport type moiety may exist in additional molecules in the emission layer, i.e., of the co-host type, rather than in the quantum dot, and the exciplex may be formed between the hole transport co-host of the quantum dot and the electron-transport ligand, or vice versa, or the exciplex may even be formed solely from transport units of both types provided by two or more co-hosts. In all these cases, energy can be transferred to a quantum dot that likewise satisfies the conditions mentioned above. FRET from the exciplex to the quantum dot core improves the performance characteristics of the electroluminescent device (particularly efficiency such as EQE).

[0217] Additional ligand:

[0218] The semiconductor nanoparticles according to the present invention may optionally include, in addition to at least one ligand selected from the compounds according to the present invention described herein, one or more different types of ligands (i.e., not selected from the compounds according to the present invention) attached to the outermost surface of the shell layer.

[0219] Accordingly, the outermost surface of the shell layer of the semiconductor light-emitting nanoparticle may be overcoated with a different type of surface ligand, together with / in addition to at least one ligand selected from the compounds of the present invention as described above, if desired.

[0220] Without being bound by theory, it is thought that such surface ligands can result in semiconducting luminescent nanoparticles being more easily dispersed in a solvent.

[0221] According to a preferred embodiment of the present invention, the total amount of a ligand selected from the compounds of the present invention attached to the outermost surface of one or more shell layers as defined above is in the range of 1 wt% to 99.9 wt%, preferably 30 wt% to 99.9 wt%, preferably 50 wt% to 99.9 wt%, and most preferably 70 wt% to 99.9 wt% of the total ligand attached to the outermost surface of the shell layer(s). The final composition of the ligand content attached to the outermost surface of one or more shell layers is determined by thermogravimetric analysis (TGA - Mettler Toledo TGA / DSC 3+).

[0222] Commonly used surface ligands include phosphines and phosphine oxides, e.g., trioctylphosphine oxide (TOPO), trioctylphosphine (TOP), and tributylphosphine (TBP); phosphonic acids, e.g., dodecylphosphonic acid (DDPA), tridecylphosphonic acid (TDPA), octadecylphosphonic acid (ODPA), and hexylphosphonic acid (HPA); amines, e.g., oleylamine, dedecylamine (DDA), tetradecylamine (TDA), hexadecylamine (HDA), and octadecylamine (ODA), oleylamine (OLA); thiols, e.g., hexadecanethiol, dodecanethiol, and hexanethiol; carboxylic acids, e.g., oleic acid, stearic acid, myristic acid, palmitic acid; acetic acid and any combination of these.

[0223] Examples of surface ligands are described, for example, in International Patent Application No. WO 2012 / 059931A.

[0224] A semiconductor nanocrystal according to the present invention comprising at least one ligand selected from the compounds of the present invention as described above, bonded to a surface, has a high fluorescence quantum yield, can realize high contrast, can improve charge transport in the semiconductor nanocrystal and within the semiconductor nanocrystal layer, thereby improving the efficiency of electronic devices, particularly electroluminescent devices.

[0225] composition

[0226] Particularly when used in electronic devices, the semiconductor nanoparticles according to the present invention may be combined with additional semiconductor nanoparticles or additional organic functional materials commonly used in electronic devices according to the prior art to form a composition. A wide variety of suitable organic functional materials are known to those skilled in the art of electronic devices.

[0227] Accordingly, the present invention further provides a composition comprising at least one first semiconductor nanoparticle according to the present invention as described above, and at least one additional organic functional material selected from an electron injection material, an electron transport material, a hole blocking material, an n-dopant, a host material, a matrix material, a wide band gap material, a fluorescence emitter material, a delayed fluorescence material, a phosphorescence emitter material, an electron blocking material, a hole transport material, a hole injection material, and a p-dopant.

[0228] Preferably, the composition comprises at least one first semiconductor nanoparticle according to the present invention and at least two different organic functional materials, preferably exactly two different organic functional materials as defined above, and the functional materials are more preferably selected from a matrix material, an electron transport material and a hole transport material.

[0229] Delayed fluorescence materials, such as delayed fluorescence emitters or delayed fluorescence hosts, are well known in the art and are disclosed, for example, in Ye Tao et al., Adv. Mater. 2014, 26, 7931-7958, MY Wong et al., Adv. Mater. 2017, 29, 1605444, WO 2011 / 070963, WO 2012 / 133188, WO 2015 / 022974, and WO 2015 / 098975. Typically, delayed fluorescence materials are characterized by exhibiting a fairly small energy gap between the singlet energy (S) and the triplet energy (T1). Preferably, ΔE ST is less than 0.5 eV, very preferably less than 0.3 eV, and particularly preferably less than 0.2 eV, where ΔE ST represents the energy difference between the singlet energy (S1) and the triplet energy (T1).

[0230] In the present invention, a wide band gap material is understood to mean a material as disclosed in US 7,294,849, which is characterized by having a band gap of at least 3.5 eV, wherein the term “band gap” means the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Such systems are well known in the art and exhibit particularly advantageous performance characteristics in electroluminescent devices.

[0231] The term "phosphorescent emitting compound" typically includes compounds in which the emission of light is caused by a spin-banning transition, e.g., from an excited triplet state or a state having a higher spin quantum number, e.g., from a pentat state. Preferably, the term phosphorescent emitting compound refers to a compound that emits radiation from a triplet state.

[0232] Suitable phosphorescent emitting compounds are, in particular, those already described above.

[0233] A preferred fluorescently emitting compound is selected from the class of arylamines. In the context of the present invention, arylamines or aromatic amines are understood to mean compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system having at least 14 aromatic ring atoms, more preferably. Preferred examples of these are aromatic anthracenamine, aromatic anthracendiamine, aromatic pyreneamine, aromatic pyrenediamine, aromatic chrysenamine, or aromatic chrysendiamine. Aromatic anthracenamine is understood to mean a compound in which a diarylamino group is directly bonded to an anthracene group, preferably at the 9th position. Aromatic anthracendiamine is understood to mean a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably at the 9,10th position. Aromatic pyreneamines, pyrenediamines, chrysenamines, and chrysendiamines are similarly defined, wherein the diarylamino group is preferably bonded to pyrene at the 1 or 1,6 position. More preferred releasing compounds are indenofluorenamines or -fluorenediamines (e.g., according to WO 2006 / 108497 or WO 2006 / 122630), benzoindenofluorenamines or -fluorenediamines (e.g., according to WO 2008 / 006449), and dibenzoindenofluorenamines or -diamines (e.g., according to WO 2007 / 140847), and indenofluorene derivatives having a fused aryl group disclosed in WO 2010 / 012328. Likewise preferred are pyrenearylamines disclosed in WO 2012 / 048780 and WO 2013 / 185871.Likewise, benzoindenofluorenamine disclosed in WO 2014 / 037077, benzofluorenamine disclosed in WO 2014 / 106522, extended benzoindenofluorene disclosed in WO 2014 / 111269 and WO 2017 / 036574, phenoxazine disclosed in WO 2017 / 028940 and WO 2017 / 028941, and fluorene derivatives bound to a furan unit or a thiophene unit disclosed in WO 2016 / 150544, or other materials used according to the prior art are preferred.

[0234] Useful host or matrix materials that are preferably used in combination with fluorescent emitting materials include materials of various classes. Preferred matrix materials include oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), in particular oligoarylenes containing fused aromatic groups, oligoarylenevinylenes (e.g., DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (e.g., according to WO 2004 / 081017), hole-conducting compounds (e.g., according to WO 2004 / 058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (e.g., according to WO 2005 / 084081 and WO 2005 / 084082), atrope isomers (e.g., according to WO 2006 / 048268), and boronic acid derivatives (e.g. It is selected from the class of (according to WO 2006 / 117052) or benzanthracene (e.g., according to WO 2008 / 145239). Particularly preferred matrix materials are selected from the class of oligoarylenes, oligoarylenevinylenes, ketones, phosphine oxides, and sulfoxides, comprising naphthalene, anthracene, benzanthracene, benzophenanthrene, and / or pyrene, or atrope isomers of these compounds. Very particularly preferred matrix materials are selected from the class of oligoarylenes, comprising anthracene, benzanthracene, benzophenanthrene, and / or pyrene, or atrope isomers of these compounds. In the context of the present invention, oligoarylene will be understood to mean a compound in which at least three aryl or arylene groups are bonded to each other.Anthracene derivatives disclosed in WO 2006 / 097208, WO 2006 / 131192, WO 2007 / 065550, WO 2007 / 110129, WO 2007 / 065678, WO 2008 / 145239, WO 2009 / 100925, WO 2011 / 054442 and EP 1553154, pyrene compounds disclosed in EP 1749809, EP 1905754 and US 2012 / 0187826, benzanthracenylanthracene compounds disclosed in WO 2015 / 158409, indenobenzofuran disclosed in WO 2017 / 025165, and WO 2017 / 036573 Phenanthryl-anthracene, or other materials used according to prior art, are also preferred.

[0235] A preferred host or matrix material used in combination with a phosphorescent emitting material is, for example, an aromatic ketone, aromatic phosphine oxide, aromatic sulfoxide, or sulfone according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627, or WO 2010 / 006680; a triarylamine, carbazole derivative, for example, CBP (N,N-biscarbazolylbiphenyl), or a carbazole derivative disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, or WO 2008 / 086851; an indolocarbazole derivative, for example, according to WO 2007 / 063754 or WO 2008 / 056746; for example, WO Indenocarbazole derivatives according to 2010 / 136109, WO 2011 / 000455, or WO 2013 / 041176, e.g., EP 1617710, EP 1617711, EP 1731584; azacarbazole derivatives according to JP 2005 / 347160, e.g., bipolar matrix materials according to WO 2007 / 137725, e.g., silanes according to WO 2005 / 111172, e.g., azaborol or boronic esters according to WO 2006 / 117052, e.g., triazine derivatives according to WO 2010 / 015306, WO 2007 / 063754, or WO 2008 / 056746, e.g., EP Zinc complexes according to 652273 or WO 2009 / 062578, for example, diazacilol or tetraazcilol derivatives according to WO 2010 / 054729, for example, diazaphosphol derivatives according to WO 2010 / 054730, for example, bridged carbazole derivatives according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107, WO 2011 / 088877 or WO 2012 / 143080, for example, triphenylene derivatives according to WO 2012 / 048781, or for example,It is a lactam according to WO 2011 / 116865 or WO 2011 / 137951, or other material used according to the prior art.

[0236] Additionally, preferably, the composition comprising at least the first semiconductor nanoparticle further comprises a plurality of host or matrix materials (so-called "mixed matrix systems"), preferably two or three different host or matrix materials, more preferably two different host or matrix materials. More preferably, in this case, one of the two different materials is a host or matrix material having hole transport characteristics, i.e., a material that contributes significantly to hole transport, and the other is a host or matrix material having electron transport characteristics, i.e., a material that contributes significantly to electron transport. One source of more detailed information regarding mixed matrix systems is application WO 2010 / 108579.

[0237] Additionally, preferably, according to the present invention, a wide variety of known transparent matrix materials suitable for electronic devices may be used.

[0238] According to the present invention, the term “transparent” means that at least about 60% of incident light is transmitted at a thickness used in an optical medium of an electronic device, such as an optical film, a color filter, a color conversion film, a remote phosphor tape, etc., and at a wavelength or wavelength range used during the operation of said optical medium. Preferably, this is greater than 70%, more preferably greater than 75%, and most preferably greater than 80%.

[0239] Preferably, the transparent matrix material is a transparent polymer. For example, the transparent polymer for the transparent matrix material is selected from poly(meth)acrylate, epoxy, polyurethane, and polysiloxane.

[0240] As used herein, the term "polymer" refers to a material having repeating units and a weight average molecular weight (Mw) of 1,000 or more. Preferably, the weight average molecular weight (Mw) of the polymer used as a transparent matrix material is in the range of 1,000 to 300,000, more preferably in the range of 10,000 to 250,000.

[0241] Also, preferably, the glass transition temperature (Tg) of the transparent polymer is 70°C or higher and 250°C or lower. Tg can be measured based on the change in thermal capacity observed in differential scanning colorimetry, as described at http: / / pslc.ws / macrog / dsc.htm.

[0242] A suitable electron transport material (or hole blocking material, or hole injection material) is an electron transport material of an electronic device, preferably any material used in the prior art in an electron transport layer (or hole blocking layer or electron injection layer). Aluminum complexes, e.g., Alq3; zirconium complexes, e.g., Zrq4; lithium complexes, e.g., Liq; benzimidazole derivatives; triazine derivatives; pyrimidine derivatives; pyridine derivatives; pyrazine derivatives; quinoxaline derivatives; quinoline derivatives; oxadiazole derivatives; aromatic ketones; lactams; boranes; diazphosphol derivatives; and phosphine oxide derivatives are particularly preferred. Additional suitable materials are derivatives of the above-mentioned compounds as disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975 and WO 2010 / 072300.

[0243] A suitable hole transport material (or electron blocking material, or hole injection material) is a hole transport material of an electronic device, and preferably, it may be any material used in the prior art in a hole transport layer (or electron blocking layer or hole injection layer). Preferred examples of hole transport materials are indenofluorenamines and derivatives (e.g., according to WO 06 / 122630 or WO 06 / 100896), amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g., according to WO 01 / 049806), amine derivatives having a condensed aromatic group (e.g., according to U.S. Patent 5,061,569), amine derivatives disclosed in WO 95 / 09147, monobenzoindeno-fluorenamine (e.g., according to WO 08 / 006449), or dibenzoindenofluorenamine (e.g., according to WO 07 / 140847). Suitable hole transport and hole injection materials are also derivatives of the compounds described above, as disclosed in JP 2001 / 226331, EP 676461, EP 650955, WO 01 / 049806, U.S. Patent 4,780,536, WO 98 / 30071, EP 891121, EP 1661888, JP 2006 / 253445, EP 650955, WO 06 / 073054 and U.S. Patent 5,061,569.

[0244] The n-dopant used according to the present invention is preferably such an organic electron donor compound capable of reducing one or more other compounds in a mixture. Preferred examples of n-dopants include W(hpp)4 according to WO 2005 / 086251 A2 and additional electron-rich metal complexes, P=N compounds (e.g., WO 2012 / 175535 A1, WO 2012 / 175219 A1), naphthylenecarbodiimide (e.g., WO 2012 / 168358 A1), fluorene (e.g., WO 2012 / 031735 A1), radicals and biradics (e.g., EP 1837926 A1, WO 2007 / 107306 A1), pyridines (e.g., EP 2452946 A1, EP 2463927 A1), N-heterocyclic compounds (e.g., WO 2009 / 000237 A1), and acridines and phenazines (e.g., US 2007 / 145355 A1) or other materials used according to prior art.

[0245] The p-dopant used according to the present invention is preferably such an organic electron acceptor compound capable of oxidizing one or more other compounds in the mixture. Preferred examples of p-dopants include F4-TCNQ, F6-TNAP, NDP-2 (Novaled), NDP-9 (Novaled), quinones (e.g., EP 1538684 A1, WO 2006 / 081780 A1, WO 2009 / 003455 A1, WO 2010 / 097433 A1), radialenes (e.g., EP 1988587 A1, US 2010 / 102709 A1, EP 2180029 A1, WO 2011 / 131185 A1, WO 2011134458 A1, US 2012 / 223296 A1), and sulfur-containing transition metal complexes (e.g., WO 2007 / 134873 A1, WO 2008 / 061517 A2, WO 2008 / 061518 A2, DE 102008051737 A1, WO 2009 / 089821 A1, US 2010 / 096600 A1), bisimidazole (e.g., WO 2008 / 138580 A1), phthalocyanine (e.g., WO 2008 / 058525 A2), purple-tetrazapentylene (e.g., WO 2007 / 115540 A1), fullerene (e.g., DE 102010046040 A1) and main group halides (e.g., WO 2008 / 128519 A2) or other materials used according to the prior art.

[0246] According to another preferred embodiment of the present invention, the composition may include at least one first semiconductor nanoparticle and at least one second semiconductor nanoparticle of the present invention as described above.

[0247] At least one second semiconductor nanoparticle may be added to at least one first semiconductor nanoparticle alone or in addition to at least one additional organic functional material defined above to form a composition.

[0248] Accordingly, according to a further preferred embodiment of the present invention, the composition may comprise at least one first semiconductor nanoparticle of the present invention as described above, at least one second semiconductor nanoparticle, and at least one additional organic functional material as defined above.

[0249] Preferably, at least one second semiconductor nanoparticle is selected from the semiconductor nanoparticles according to the present invention as described above. More preferably, at least one second semiconductor nanoparticle and the first semiconductor nanoparticle are different from each other. That is, for example, each of the first and second semiconductor nanoparticles may have a different ligand selected from the compounds according to the present invention as described above attached to its outermost surface.

[0250] Where the composition comprises—alone or in addition to at least one additional organic functional material as defined above—at least one second semiconductor nanoparticle different from at least one first semiconductor nanoparticle, according to one embodiment of the composition, the at least one first semiconductor nanoparticle comprises at least one ligand attached to its outermost surface comprising a delay fluorescence group, and the at least one second semiconductor nanoparticle comprises at least one ligand attached to its outermost surface comprising a hole transport group or an electron transport group. Here, the charge carriers may recombine to form an excited state in the delay fluorescence group, and subsequently the excited state energy is energy transferred (e.g., F It can be transferred to semiconductor nanoparticles (commonly referred to as "hyperfluorescence") through rster resonance energy transfer.

[0251] According to another preferred embodiment of a composition comprising first and second semiconductor nanoparticles that are different from each other as described above, at least one first semiconductor nanoparticle comprises at least one ligand attached to an outermost surface comprising a phosphorescent group, and at least one second semiconductor nanoparticle comprises at least one ligand attached to an outermost surface comprising a hole transporter or an electron transporter. Here, the charge carriers may recombine to form an excited state in the phosphorescent group, and subsequently the excited state energy is energy transferred (e.g., F It can be transferred to semiconductor nanoparticles (commonly referred to as "hyperphosphorescence") through pyroelectric energy transfer.

[0252] Both the superfluorescence and superphosphorescence described earlier can lead to an increase in quantum efficiency.

[0253] According to a further preferred embodiment of a composition comprising first and second semiconductor nanoparticles that are different from each other as described above, at least one first semiconductor nanoparticle comprises at least one ligand attached to an outermost surface comprising an electron transport group, and at least one second semiconductor nanoparticle comprises at least one ligand attached to an outermost surface comprising a hole transport group, which enables exciplex formation as described above.

[0254] In each embodiment of the composition disclosed above, the ligands attached to the surfaces of the first and second semiconductor nanoparticles, respectively, are selected from compounds according to the present invention. Accordingly, the preferred hole transporters and electron transporters included in the ligands as described above are selected from the hole transporter HT and electron transporter ET defined herein in relation to the present invention. Likewise, the preferred phosphorescent and delayed fluorescent groups mentioned above are selected from the phosphorescent and delayed fluorescent groups defined above.

[0255] Formula

[0256] For example, to process the compound, semiconductor particle, or composition of the present invention from a liquid phase by spin coating or by a printing method, a formulation comprising the compound, semiconductor particle, or composition of the present invention is required. Such a formulation may be, for example, a solution, a dispersion, or an emulsion. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-, or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, particularly 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, It is decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetol, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or a mixture of these solvents.

[0257] Accordingly, the present invention also provides a solution, dispersion, or emulsion comprising a compound selected from the compounds of the present invention as described above, or semiconductor nanoparticles according to the present invention as described above, or a composition according to the present invention as described above, and at least one solvent, preferably an organic solvent. Methods for preparing such a solution are known to those skilled in the art and are described, for example, in WO 2002 / 072714, WO 2003 / 019694 and the literature cited therein.

[0258] method

[0259] The problem addressed by the present invention is also solved by a method for manufacturing semiconductor nanoparticles according to the present invention, wherein the method comprises the step of providing a compound according to the present invention acting as a ligand, and semiconductor nanoparticles comprising a core and one or more shell layers, to a solvent to obtain a mixture.

[0260] Preferably, the method is performed under inert conditions such as an N2 or argon atmosphere. More preferably, the compound acting as a ligand and the semiconductor nanoparticles in the method are stirred for at least 1 second, more preferably at least 30 seconds. Even more preferably, the stirring time in the method is in the range of 1 minute to 100 hours, preferably 10 minutes to 1 hour.

[0261] More preferably, the method is performed at a temperature in the range of 0°C to 100°C, more preferably at room temperature.

[0262] As a solvent, for example, toluene, hexane, chloroform, ethyl acetate, benzene, xylene, ether, tetrahydrofuran, dichloromethane and heptane and mixtures thereof may be used, but are not limited thereto.

[0263] The semiconductor nanoparticles obtained in this way may also be purified by a subsequent precipitation and / or re-suspending step.

[0264] The synthesis steps and conditions for the preparation and purification of semiconductor nanoparticles according to the present invention are well known to those skilled in the art and are described in the literature (e.g., R. Gomes et al., J. Phys. Chem. Lett . 2011, 2 , 145-152; JS Owen J. Chem. Soc. 2008, 130 It is listed in , 12279-12281).

[0265] The present invention also relates to semiconductor nanoparticles obtainable from or obtained from a method.

[0266] electronic devices

[0267] The semiconductor nanoparticles and compositions of the present invention are suitable for use in electronic devices, particularly organic electroluminescent devices, such as OLEDs, particularly in the emission layer.

[0268] Accordingly, the present invention further provides an electronic device comprising at least one semiconductor nanoparticle according to the present invention as described above, or a composition according to the present invention as described above.

[0269] The electronic device is preferably selected from the group consisting of organic integrated circuits (OIC), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, and more preferably, organic electroluminescent devices (EL devices). Preferred EL devices are organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs), of which OLEDs are most preferred.

[0270] Also preferably, the electronic device is an organic electroluminescent device comprising semiconductor nanoparticles or a composition of the present invention in the emission layer.

[0271] Particularly preferably, the electronic device is an organic electroluminescent device comprising an anode, a cathode, and one organic layer, and at least one organic layer (which is particularly preferably an emission layer) comprises at least one semiconductor nanoparticle or composition according to the present invention as described above.

[0272] In the present invention, the term "organic layer" is understood to mean any layer of an electronic device comprising one or more organic compounds as a functional material.

[0273] In addition to the cathode, anode, and emission layer, the organic electroluminescent device may also include additional layers. These include, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge generation layers (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer It is selected from ), and / or organic or inorganic p / n junctions.

[0274] Within the context of the present invention, the order of the layers of an organic electroluminescent device is preferably as follows: anode-hole injection layer-hole transport layer-optional additional hole transport layer(s)-optional electron blocking layer-emission layer-optional hole blocking layer-electron transport layer-electron injection layer-cathode. Additional layers may be present in the organic electroluminescent device.

[0275] The hole transport layer according to the present application is a layer having a hole transport function between an anode and an emission layer. The electron transport layer according to the present application is a layer having an electron transport function between an anode and an emission layer.

[0276] The hole injection layer and the electron blocking layer are understood to be specific embodiments of the hole transport layer in the context of this application. The hole injection layer is a hole transport layer that is immediately adjacent to the anode or separated from it only by a single coating of the anode, in the case where there are multiple hole transport layers between the anode and the emission layer. The electron blocking layer is a hole transport layer that is immediately adjacent to the emission layer on the anode side, in the case where there are multiple hole transport layers between the anode and the emission layer. Accordingly, the same applies to the electron injection layer and the hole blocking layer that are understood to be specific embodiments of the electron transport layer in the context of this application. A hole transport material (or electron blocking material, or hole injection material) suitable for use in the hole transport layer, the hole injection layer, or the electron blocking layer may be selected from such organic functional materials as described above in relation to the composition of the present invention. A hole transport material (or hole blocking material, or electron injection material) suitable for use in the electron transport layer, the electron injection layer, or the hole blocking layer may be selected from such organic functional materials as described above in relation to the composition of the present invention.

[0277] The organic light-emitting diode of the present invention may comprise two or more emission layers. More preferably, in this case, the emission layers have various emission peaks generally ranging from 380 nm to 750 nm so that the overall result is white emission; that is, they may emit fluorescence or phosphorescence, and various emission compounds emitting blue, green, yellow, orange, or red light may be used in the emission layers alone or in combination, or in combination with the semiconducting light-emitting nanoparticles of the present invention. Particularly preferred is a three-layer system, i.e., a system having three emission layers, wherein the three layers exhibit blue, green, and orange or red emission (for basic structures, refer, for example, to WO 2005 / 011013). The semiconducting light-emitting nanoparticles according to the present invention may be present in one or more (if present) emission layers. Preferably, the semiconductor nanoparticles or compositions according to the present invention are present in at least one emission layer, more preferably in all present emission layers.

[0278] Suitable phosphorescent or fluorescent emitting compounds that may be used in the emission layer in combination with the semiconducting luminescent nanoparticles of the present invention may be selected from such organic functional materials as described above in relation to the composition of the present invention. Likewise, a matrix or host material suitable for use in the emission layer may be selected from such organic functional materials as described above in relation to the composition of the present invention.

[0279] The emission layer of an organic electroluminescent device may also comprise a system comprising a plurality of matrix materials (a mixed matrix system). The mixed-matrix system preferably comprises two or three different matrix materials, particularly preferably two different matrix materials. Preferably, one of the two materials represents a material having hole transport properties, and the other material represents a material having electron transport properties. A particularly suitable matrix material that can be used in combination with the semiconductor nanoparticles according to the present invention as a matrix component of the mixed matrix system may be selected from such organic functional materials as described above in relation to the composition of the present invention.

[0280] A desirable cathode for an electronic device is a metal alloy or multilayer structure composed of a metal having a low work function, various metals, e.g., alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Additionally, an alloy composed of an alkali metal or alkaline earth metal and silver, e.g., an alloy composed of magnesium and silver, is suitable. In the case of a multilayer structure, in addition to the metals mentioned, it is also possible to use additional metals having a relatively high work function, e.g., Ag or Al, in which case combinations of metals such as Ca / Ag, Mg / Ag, or Ba / Ag are generally used. Furthermore, it may be desirable to introduce a thin intermediate layer of a material having a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials useful for this purpose are alkali metal or alkaline earth metal fluorides, as well as corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). It is also possible to use lithium quinolinate (LiQ) for this purpose. The thickness of such a layer is preferably 0.5 to 5 nm.

[0281] A desirable anode is a material having a high work function. Preferably, the anode has a work function greater than 4.5 eV with respect to vacuum. First, metals with high redox potentials, such as Ag, Pt, or Au, are suitable for this purpose. Second, metal / metal oxide electrodes (e.g., Al / Ni / NiO x , Al / PtO xThis may also be desirable. For some applications, at least one of the electrodes must be transparent or partially transparent to enable irradiation of the organic material (organic solar cell) or emission of light (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. ITO (indium tin oxide) or IZO (indium zinc oxide) are particularly preferred. Additionally, conductive doped organic materials, particularly conductive doped polymers, are preferred. Furthermore, the anode may also consist of two or more layers, for example, an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0282] To exclude the effects of damage caused by water and air, the device is appropriately structured (depending on the application), contact-connected, and finally sealed.

[0283] In a preferred embodiment, the electronic device is characterized by having one or more layers coated by a sublimation process. In this case, the material is 10 -5 Less than mbar, preferably 10 -6 It is applied by deposition in a vacuum sublimation system at an initial pressure of less than mbar. However, in this case, the initial pressure is much lower, for example, 10 -7 It may be less than mbar.

[0284] Likewise, an electronic device is preferred in which one or more layers are coated by an OVPD (Organic Vapor Deposition) method or with the help of carrier gas sublimation. In this case, the material is 10 -5It is applied at pressures between mbar and 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, where the material is applied directly by a nozzle and structured accordingly (e.g., MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0285] Additionally, an electronic device is preferred in which one or more layers are formed from a solution, for example by spin-coating, or by any printing method, for example, screen printing, flexographic printing, nozzle printing, or offset printing, but more preferably by LITI (photo-induced thermal imaging, thermal transfer printing) or inkjet printing. The solubility of the compound may be improved by appropriate substitution of the compound as known to those skilled in the art, for example, by substitution with a group that increases solubility in an organic solvent, such as an aromatic group (e.g., terphenyl group) or an alkyl group.

[0286] In addition, it is preferable that the electronic device of the present invention be manufactured by applying one or more layers from a solution and one or more layers by a sublimation method.

[0287] An electronic device according to the present invention comprising at least one semiconductor nanoparticle or composition of the present invention as described above is advantageous in terms of operating voltage and external quantum efficiency, as shown below.

[0288] Accordingly, an electronic device comprising at least one semiconductor nanoparticle or composition of the present invention can be used as a light source in displays, in lighting applications, and as a light source in medical and / or cosmetic applications (e.g., phototherapy).

[0289] The present invention is described in more detail below with the help of embodiments that are not considered to limit the scope of the invention. Specific details for implementing the invention

[0290] yes

[0291] Work Example 1 - Preparation of Compound (1):

[0292]

[0293] 1. Biphenyl-4-ylmethylphosphonic acid diethyl ester

[0294] 2.3 g of 4-phenylbenzyl chloride (98%, Sigma-Aldrich) is dissolved in 48.52 g of triethylphosphite (98%, Sigma-Aldrich) in a 100 mL, three-necked round-bottom flask connected to a condenser under an argon atmosphere. The system is heated to 160 °C for 26 hours. The formed product is separated by column chromatography using silica as an adsorbent and ethyl acetate and heptane as eluents.

[0295] 2. Biphenyl-4-ylmethylphosphonic acid (compound (1))

[0296] 2.0 g of the product obtained above, biphenyl-4-ylmethylphosphonic acid diethyl ester (96%, determined by gas chromatography-mass spectrometry (GCMS) on commercially available equipment (HP 6890 series, 5973 detector)), was mixed with 3.05 g of bromotrimethylsilane in 20 mL of dichloromethane in a 100 mL, three-necked round-bottom flask connected to a condenser under an argon atmosphere. The mixture was stirred at room temperature for 16 hours. Then, the solvent was evaporated using a rotary evaporator. The dried residue was dissolved in methanol (10% water, Sigma Aldrich) and mixed under argon at room temperature for 16 hours. The suspension was filtered through a paper filter and washed twice with methanol to obtain the product (yield: 62%).

[0297] Work Example 2 - Preparation of Compound (2):

[0298]

[0299] 1. Bis-biphenyl-4-yl-[4-(3-chloro-propyl)-phenyl]-amine

[0300] 6.48 mL of a 1.7 M solution of tert-butyllithium (t-BuLi) in pentane (Sigma-Aldrich) is placed in a dropping funnel in a glove box. 2.5 g of bis-biphenyl-4-yl-(4-bromo-phenyl)-amine (Merck) is dissolved in dry tetrahydrofuran (THF) in a 100 mL three-necked flask, and then cooled to -78°C using a dry ice bath (Aceton). The dropping funnel containing t-BuLi is removed from the glove box and connected to the flask. t-BuLi is slowly added dropwise directly to the solution. Afterward, the funnel is carefully rinsed with dry THF. The solution is stirred at -78°C for 1 hour.

[0301] Then, 0.62 mL of 1-bromo-3-chloropropane is slowly added to the reaction using an argon-flushed syringe. The solution is allowed to be heated back to room temperature and stirred further overnight under argon. Afterward, the mixture is cooled back to 0°C in an ice bath and 10 mL of H2O is slowly added using a syringe. Then, 5 mL of 1M HCl is slowly added. After the solution turns green, an additional 5 mL of 1M HCl is added. The ice bath is removed and the mixture is stirred until it reaches room temperature (RT). The reaction product has two phases. The organic phase is separated, the aqueous phase is extracted with dichloromethane (3 x 15 mL), and dried with MgSO4.

[0302] 2. 3-[4-(bis-biphenyl-4-yl-amino)-phenyl]-propyl}-phosphonic acid diethyl ester

[0303] 1.34 g of bis-biphenyl-4-yl-[4-(3-chloro-propyl)-phenyl]-amine (97%) is mixed with 50 mL of TEP in a neck flask and stirred at 160°C for 72 hours under argon.

[0304] 3. {3-[4-(bis-biphenyl-4-yl-amino)-phenyl]-propyl}-phosphonic acid (compound (2))

[0305] 0.77 g of 3-[4-(bis-biphenyl-4-yl-amino)-phenyl]-propyl}-phosphonic acid diethyl ester was dissolved in 20 mL of dichloromethane and mixed with 0.63 g (0.55 mL) of bromotrimethyl silane (3 equivalents) under argon and stirred at room temperature for 12 hours.

[0306] When methanol (10% H2O) was added directly to the solution, it turned whitish. The mixture was stirred overnight at room temperature under argon. Afterward, the mixture evaporated, and a yellowish gel formed. The gel was recrystallized in 5 mL of acetonitrile to obtain a slightly yellowish-white wax and a yellowish supernatant. The supernatant was removed, and the wax was washed twice with a small amount of acetonitrile. The wax was recrystallized in 3 mL of ethanol. White wax was obtained. 5 mL of heptane was added, and the wax was resuspended at room temperature, filtered (washed twice with heptane), and dried in a vacuum chamber. A slightly greenish-white solid was obtained (yield: 38%).

[0307] The synthesis of additional compounds (3), (4), (6) and (7)—as shown in Table 2 below—is carried out in a similar manner:

[0308]

[0309]

[0310] Work Example 3 - Preparation of Semiconductor Nanoparticles

[0311] InP / ZnS core / shell nanoparticles Hussain et al. ChemPhysChem , 2009 It was synthesized in a manner similar to that described in , 10, 1466-1470.

[0312] 5 mL of a solution containing InP / ZnS core / shell nanoparticles (PL emission peak 625 nm) (50 mg / mL in toluene) was mixed with 0.25 g of an alternative surface ligand (i.e., compound (2) of Working Example 2) and stirred overnight at 50°C under an argon atmosphere. Next, the mixture was transferred to a centrifugation vial and 5 mL of dry methanol was added. Afterward, the mixture was centrifuged at 4000 rpm for 5 minutes under argon. Subsequently, the colorless supernatant was removed and the red precipitate was suspended in 5 mL of dried toluene.

[0313] A similar procedure may be used for other ligands according to the present invention. The amount of added ligand is calculated based on molar amount.

[0314] Work Example 4 - Fabrication of Solution-Processed OLED (Device E1)

[0315] The fabrication of solution-based OLEDs has already been described numerous times in the literature, e.g., WO 2004 / 037887 and WO 2010 / 097155. The process is adapted to the conditions (layer-thickness variation, material) described below.

[0316] The material combination of the present invention is used in the following layer order:

[0317] - Substrate,

[0318] - ITO (50 nm),

[0319] - buffer (20 nm),

[0320] - Hole transport layer (20 nm),

[0321] - Emission layer (EML) (30 nm),

[0322] - Electron transport layer (ETL) (50 nm),

[0323] - Electron injection layer (EIL) (3 nm),

[0324] - Cathode (Al) (100nm).

[0325] A glass plate coated with structured ITO (indium tin oxide) to a thickness of 50 nm serves as the substrate. This is coated with a buffer (PEDOT) Clevios P ​​VP AI 4083 (Heraeus Clevios GmbH, Leverkusen) by spin coating. Spin coating of the buffer is performed in air and water. Subsequently, the layer is dried by heating at 180°C for 10 minutes. A hole transport layer and an emission layer are applied to the glass plate coated in this manner.

[0326] For the hole transport layer, a polymer of the structure shown in Table 3, synthesized according to WO 2010 / 097155, is used. The polymer is dissolved in toluene so that the solid content of the solution is approximately 5 g / L to prepare a layer 20 nm thick. The layer is applied by spin coating in an argon atmosphere and dried by heating at 220°C for 30 minutes.

[0327] For the emission layer, red light-emitting InP / ZnS nanoparticles according to the present invention, i.e., quantum dots attached to surface ligands according to the present invention, are dissolved in toluene and used. The solid content of this solution is approximately 15 mg / mL to prepare a layer with a thickness of 30 nm. The layer is applied by spin coating in an argon atmosphere and dried by heating at 120°C for 10 minutes.

[0328]

[0329] Likewise, materials for the electron transport layer and electron injection layer are applied by thermal deposition in a vacuum chamber and are shown in Table 4. The electron transport layer consists of the material ETL, and the electron injection layer consists of EIL. The cathode is formed by thermal deposition of an aluminum layer with a thickness of 100 nm.

[0330]

[0331] Comparative Example 1 - Fabrication of Solution-Processed OLED (Device V1)

[0332] A solution-based OLED was prepared in the same manner as described in Work Example 4 above, using the same compound / material except that the latest red light-emitting semiconductor nanoparticles, namely QDs covered with a common alkyl ligand, were used in the preparation of the emission layer.

[0333] Task Example 5 - Device Characterization

[0334] The OLED is characterized by standard methods. For this purpose, the electroluminescence spectrum and external quantum efficiency (EQE, measured in %) are determined from the current / voltage / luminance characteristic line (IUL characteristic line) by assuming a Lambertian emission profile. The electroluminescence (EL) spectrum is recorded at a luminous density of 100 cd / m², and then the CIE 1931 x and y coordinates are calculated from the EL spectrum. The device data of the OLEDs prepared according to Working Example 4 and Comparative Example 1 are summarized in Table 5. In the following sections, examples are described in more detail to demonstrate the advantages of the OLED of the present invention.

[0335] Use of InP / ZnS nanoparticles according to the present invention as an emission material in OLEDs

[0336] The InP / ZnS nanoparticles according to the present invention are particularly suitable as emission materials in OLED devices. The characteristics of the fabricated OLEDs are summarized in Table 5. Example E1 shows the characteristics of an OLED containing the material of the present invention.

[0337]

[0338] As can be seen from the data shown in Table 5, in the structure (35) of this embodiment, the OLED using semiconductor nanoparticles (E1) according to the present invention, that is, quantum dots attached to surface ligands according to the present invention in the emission layer is the latest technology (V1, i.e., Hussain et. al. ChemPhysChem , 2009It provides a significant improvement in lower operating voltage and increased EQE compared to QDs covered with common carboxyl and thiol alkyl ligands as described in , 10, 1466-1470.

Claims

Claim 1 A compound comprising, in a given order, an anchor group AG capable of binding to the surface of a semiconductor nanoparticle, a conjugated hindering linker group L that is electronically inactive, and an organic functional group FG, wherein the compound has a molecular weight of 1000 g / mol or less, and wherein the organic functional group FG is an electron transporter selected from triazine, pyrimidine, pyridine, pyrazine, pyrazole, pyridazine, quinoline, isoquinoline, quinoxaline, quinazolin, thiazole, benzothiazole, oxazole, benzoxazole, benzimidazole, oxadiazole, phenoxazine, lactam, phenanthroline, and dibenzofuran, or a hole transporter selected from carbazole, biscarbazole, indenocarbazole, indolocarbazole, amine, triarylamine, fluorenamine, and spirobifluorenamine. Claim 2 A compound according to claim 1, characterized in that the anchor group AG is selected from the group consisting of thiol or its salt, phosphonic acid or its salt, carboxylic acid or its salt, selenol or its salt, sulfinic acid or its salt, mercaptoester or its salt, carbodithioic acid or its salt, boronic acid or its salt, amine, and phosphine. Claim 3 A compound according to claim 1, wherein the linker group L is selected from the group consisting of a straight-chain alkylene group having 1 to 20 carbon atoms or a cyclic or branched alkylene group having 3 to 20 carbon atoms, wherein one or more non-contiguous methylene groups can be replaced with -O-, -S-, -C(=O)O-, -C(=S)S-, an aromatic ring, or a heteroaromatic ring. Claim 4 In claim 1, the compound has the following general formula (1). The following applies to the symbols and exponents in the formula. In the formula, X is the anchor group AG, and X is -SH, -C(=O)OH, -NH2, -P(=O)(OH)(OH), -SeH, -P(R'R''), -S - Y + , -S(=O)OH, -S(=O)O - Y + , -C(=O)O - Y + , -OC(=O)R'''SH, -OC(=O)R'''S - Y + , -P(=O)(OH)(O - Y + ), -Se - Y + , -C(=S)SH, -C(=S)S - Y + , -B(OH)2, -B(OH)O - Y + , -B(O - Y + )2, -B(O - )2Z 2+ ,-P(=O)(O - Y + )(O - Y + ) or -P(=O)(O - )(O - )Z 2+ Selected from;Y + is Na + , K + , Li + , ½ Cd 2+ , ½ Zn 2+ , ½ Mg 2+ , ½ Ca 2+ , ½ Sr 2+ , ⅓ In 3+ , ⅓ Ga 3+ Selected from;Z 2+ is Cd 2+ , Zn 2+ , Mg 2+ , Ca 2+ , Sr 2+ A compound characterized in that; R', R'' are selected from H, a linear or branched alkyl group having 1 to 20 carbon atoms, either identically or differently; R''' is selected from a linear or branched alkyl group having 1 to 10 carbon atoms; and n is an integer from 0 to 20. Claim 5 A compound according to claim 1, characterized in that the organic functional group FG is an electron transport group. Claim 6 In claim 1, the organic functional group FG is an electron transport group selected from the following groups. In the equation, the dotted line indicates the bonding position for the linker group; Q' is the same or different in each case, CR 1 Selected from and N; Q'' is NR 1 Selected from , O and S; R 1 In each case, H, D, F, Cl, Br, I, N(R) are identical or different 2 )2, CN, NO2, Si(R 2 )3, B(OR 2 )2, C(〓O)R 2 , P(〓O)(R 2 )2, S(〓O)R 2 , S(〓O)2R 2 , OSO2R 2 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy, or thioalkoxy group having 3 to 40 carbon atoms (each of these having one or more R 2 It can be substituted by radicals, and one or more non-adjacent CH2 groups are R 2 C〓CR 2 , C≡C, Si(R 2 )2, Ge(R 2 )2, Sn(R 2 )2, C〓O, C〓S, C〓Se, C〓NR 2 , P(〓O)(R 2 ), SO, SO2, NR 2 , O, S or CONR 2 It can be replaced with and one or more hydrogen atoms can be replaced with D, F, Cl, Br, I, CN, or NO2), or having 5 to 60 aromatic ring atoms and in each case one or more R 2 An aromatic or heteroaromatic ring system capable of being substituted with radicals, or having 5 to 60 aromatic ring atoms and one or more R 2 An aryloxy, arylalkyl, or heteroaryloxy group capable of being substituted with a radical, or a combination of two or more of these groups or a crosslinkable Q group; wherein, two or more adjacent R 1 Radicals can together form a monocyclic or polycyclic, aliphatic or aromatic ring system, preferably two or more adjacent R 1 Radicals do not form monocyclic or polycyclic, aliphatic or aromatic ring systems together; R 2 are the same or different in each case, and H, D, F, Cl, Br, I, N(R 3 )2, CN, NO2, Si(R 3 )3, B(OR 3 )2, C(〓O)R 3 , P(〓O)(R 3 )2, S(〓O)R 3 , S(〓O)2R 3 , OSO2R 3 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy, or thioalkoxy group having 3 to 40 carbon atoms (each of these having one or more R 3 It can be substituted by radicals, and one or more non-adjacent CH2 groups are R 3 C〓CR 3 , C≡C, Si(R 3 )2, Ge(R 3 )2, Sn(R 3 )2, C〓O, C〓S, C〓Se, C〓NR 3 , P(〓O)(R 3 ), SO, SO2, NR 3 , O, S or CONR 3 It can be replaced with and one or more hydrogen atoms can be replaced with D, F, Cl, Br, I, CN, or NO2), or having 5 to 60 aromatic ring atoms and in each case one or more R 3 An aromatic or heteroaromatic ring system capable of being substituted with radicals, or having 5 to 60 aromatic ring atoms and one or more R 3 An aryloxy, arylalkyl, or heteroaryloxy group that can be substituted with a radical, or a combination of two or more of these groups; wherein two or more adjacent R 2 Radicals can together form monocyclic or polycyclic, aliphatic or aromatic ring systems; R 3 are, in each case, the same or different, an aliphatic, aromatic, and / or heteroaromatic hydrocarbyl radical having H, D, F, or 1 to 20 carbon atoms, wherein one or more hydrogen atoms may also be replaced by F; and also two or more R 3 A compound characterized in that the substituents can together form a monocyclic or polycyclic, aliphatic or aromatic ring system; and at least one Q' is N. Claim 7 A compound according to claim 1, characterized in that the organic functional group FG is a hole transporter. Claim 8 In claim 7, the above-mentioned hole transport device is the following device. ,foodAr L In each case, one or more radicals R, identically or differently 4 An aromatic ring system having 6 to 40 aromatic ring atoms that may be substituted with, and one or more radicals R 4 Selected from a heteroaromatic ring system having 5 to 40 aromatic ring atoms that may be substituted with; Ar 1 In each case, one or more radicals R, identically or differently 4 An aromatic ring system having 6 to 40 aromatic ring atoms that may be substituted with, and one or more radicals R 4 Selected from a heteroaromatic ring system having 5 to 40 aromatic ring atoms that may be substituted with; E is a single bond or -C(R 4 )2-, -N(R 4 2 selected from )-, -O-, and -S- are 0 or 1, identically or differently in each case; and if k=0, ar is 0 L ... does not exist and the nitrogen atom and the linker group are directly connected; m is 0 or 1, identically or differently in each case, and when m=0, group E does not exist and group Ar 1 is not connected;R 4 In each case, identically or differently, H, D, F, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 , selected from a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more radicals R 4 They may be connected to each other to form a ring; and the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems each have one or more radicals R in each case 5 It may also be substituted by, and one or more CH2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are -R in each case. 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), can be replaced by -O-, -S-, SO or SO2;R 5 In each case, identically or differently, H, D, F, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , selected from a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more radicals R 5 They may be connected to each other to form a ring; and the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems each have one or more radicals R in each case 6 It may also be substituted by, and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups are -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), may be replaced by -O-, -S-, SO or SO2;R 6 ...is selected, in each case identically or differently, from H, D, F, CN, alkyl groups having 1 to 20 carbon atoms, aromatic ring systems having 6 to 40 carbon atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more radicals R 6 A compound characterized in that the groups may be connected to each other to form a ring; and the alkyl group, aromatic ring system and heteroaromatic ring system may be substituted by F and CN. Claim 9 A semiconductor nanoparticle comprising a core, one or more shell layers, and at least one ligand attached to the outermost surface of the one or more shell layers, wherein the at least one ligand is selected from a compound according to any one of claims 1 to 8. Claim 10 A semiconductor nanoparticle according to claim 9, wherein the semiconductor nanoparticle comprises at least two different ligands, or exactly two different ligands, and the ligands are selected from the compounds. Claim 11 A semiconductor nanoparticle according to claim 10, wherein the semiconductor nanoparticle comprises a first ligand and a second ligand, wherein the first ligand comprises an organic functional group selected from electron transporters and the second ligand comprises an organic functional group selected from hole transporters. Claim 12 A composition comprising at least one first semiconductor nanoparticle and at least one second semiconductor nanoparticle according to claim 9, or comprising at least one first semiconductor nanoparticle according to claim 9 and at least one additional organic functional material, wherein the at least one additional organic functional material is selected from electron injection materials, electron transport materials, hole blocking materials, n-dopants, host materials, matrix materials, wide band gap materials, fluorescence emitter materials, delayed fluorescence materials, phosphorescence emitter materials, electron blocking materials, hole transport materials, hole injection materials, and p-dopants. Claim 13 ◈Claim 13 was abandoned upon payment of the registration fee.◈ A composition comprising at least one first semiconductor nanoparticle according to claim 9, at least one second semiconductor nanoparticle, and at least one additional organic functional material, wherein the at least one additional organic functional material is selected from electron injection materials, electron transport materials, hole blocking materials, n-dopants, host materials, matrix materials, wide band gap materials, fluorescence emitter materials, delayed fluorescence materials, phosphorescence emitter materials, electron blocking materials, hole transport materials, hole injection materials, and p-dopants. Claim 14 A composition comprising at least one first semiconductor nanoparticle and at least one second semiconductor nanoparticle according to claim 9, or comprising at least one first semiconductor nanoparticle according to claim 9 and at least one additional organic functional material, wherein the at least one additional organic functional material is selected from electron injection materials, electron transport materials, hole blocking materials, n-dopants, host materials, matrix materials, wide band gap materials, fluorescence emitter materials, delayed fluorescence materials, phosphorescence emitter materials, electron blocking materials, hole transport materials, hole injection materials, and p-dopants, wherein the at least one second semiconductor nanoparticle is selected from claim 9, and the at least one second semiconductor nanoparticle and the at least one first semiconductor nanoparticle are different from each other. Claim 15 ◈Claim 15 was abandoned upon payment of registration fee.◈ A composition comprising at least one first semiconductor nanoparticle according to Claim 9, at least one second semiconductor nanoparticle, and at least one additional organic functional material, wherein the at least one additional organic functional material is selected from electron injection materials, electron transport materials, hole blocking materials, n-dopants, host materials, matrix materials, wide band gap materials, fluorescence emitter materials, delayed fluorescence materials, phosphorescence emitter materials, electron blocking materials, hole transport materials, hole injection materials, and p-dopants, wherein the at least one second semiconductor nanoparticle is selected from Claim 9, and the at least one second semiconductor nanoparticle and the at least one first semiconductor nanoparticle are different from each other. Claim 16 A composition according to claim 14, wherein the at least one first semiconductor nanoparticle comprises at least one ligand attached to the outermost surface comprising a delay fluorescence group, and the at least one second semiconductor nanoparticle comprises at least one ligand attached to the outermost surface comprising a hole transporter or an electron transporter. Claim 17 A composition according to claim 14, wherein the at least one first semiconductor nanoparticle comprises at least one ligand attached to the outermost surface comprising a phosphorescent group, and the at least one second semiconductor nanoparticle comprises at least one ligand attached to the outermost surface comprising a hole transporter or an electron transporter. Claim 18 A formulation comprising a semiconductor nanoparticle and at least one solvent, wherein the semiconductor nanoparticle comprises a compound or core according to any one of claims 1 to 8, one or more shell layers, and at least one ligand attached to the outermost surface of said one or more shell layers, wherein said at least one ligand is selected from the compound according to any one of claims 1 to 8. Claim 19 A method for manufacturing semiconductor nanoparticles as described in claim 9, characterized in that semiconductor nanoparticles comprising a core and one or more shell layers are provided in a solvent together with said compound to obtain a mixture. Claim 20 ◈Claim 20 was abandoned upon payment of the registration fee.◈ Semiconductor nanoparticles obtained from the method according to Claim 19. Claim 21 An electronic device comprising a composition including at least one semiconductor nanoparticle according to claim 9, or at least one first semiconductor nanoparticle and at least one second semiconductor nanoparticle according to claim 9, or at least one first semiconductor nanoparticle according to claim 9 and at least one additional organic functional material, wherein the at least one additional organic functional material is selected from electron injection materials, electron transport materials, hole blocking materials, n-dopants, host materials, matrix materials, wide band gap materials, fluorescence emitter materials, delayed fluorescence materials, phosphorescence emitter materials, electron blocking materials, hole transport materials, hole injection materials, and p-dopants. Claim 22 An electronic device according to claim 21, characterized in that the device is an electroluminescent device. Claim 23 An electronic device according to claim 21, characterized in that the device is an electroluminescent device comprising the semiconductor nanoparticles or the composition in the emission layer. Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete

Images