阅读说明：本技术 用于纳米尺寸材料的配体 (Ligands for nanosized materials ) 是由 I·利伯曼 M·汉布格尔 C·马图舍克 T·埃贝勒 B·布克哈特 S·迈尔 于 2020-03-02 设计创作，主要内容包括：本发明涉及一种适用于结合到半导体纳米颗粒表面的配体的化合物,所述化合物包括锚定基团、连接基团和有机官能团；半导体纳米颗粒具有连接到最外部颗粒表面的所述配体；组合物、制剂和用于制备所述半导体纳米颗粒的方法；以及电子器件。(The present invention relates to a compound suitable for binding to a ligand on the surface of a semiconductor nanoparticle, said compound comprising an anchoring group, a linking group and an organic functional group; the semiconductor nanoparticles having the ligands attached to the outermost particle surface; compositions, formulations, and methods for making the semiconductor nanoparticles; and an electronic device.)

1. A compound comprising, in the given order, an anchoring group AG capable of binding to the surface of a semiconductor nanoparticle, followed by an electronically inert and conjugated interrupting linking group L, followed by an organic functional group FG, and wherein the compound has a molecular weight of 1000g/mol or less.

2. The compound according to claim 1, characterized in that the anchoring group AG is selected from the group consisting of thiols or salts thereof, phosphonic acids or salts thereof, carboxylic acids or salts thereof, selenols or salts thereof, sulfinic acids or salts thereof, mercapto esters or salts thereof, dithiocarboxylic acids or salts thereof, boronic acids or salts thereof, amines and phosphines.

3. A compound according to claim 1 or 2, wherein the linking group L is selected from a linear alkylene group having 1 to 20C atoms, or a cyclic or branched alkylene group having 3 to 20C atoms, wherein one or more non-adjacent methylene groups may be replaced by-O-, -S-, -C (═ O) O-, -C (═ S) S-, an aromatic ring or a heteroaromatic ring.

4. A compound according to one or more of claims 1 to 3, characterized in that the organic functional group FG is selected from 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 may optionally be further substituted.

5. Compound according to one or more of claims 1 to 4, characterized in that the organic functional group FG is selected from the group consisting of electron-injecting groups, electron-transporting groups, hole-blocking groups, n-dopant groups, host groups, matrix groups, wide-bandgap groups, fluorescence emitter groups, delayed fluorescence groups, phosphorescence groups, electron-blocking groups, hole-transporting groups, hole-injecting groups or p-dopant groups.

6. Compound according to one or more of claims 1 to 5, characterized in that it has general formula (1)

Wherein the following applies to symbols and indices

Wherein X is an anchoring group AG, and wherein

X is selected from-SH, -C (═ O) OH and-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^-)₂Z²⁺,-P(＝O)(O^-Y⁺)(O^-Y⁺) or-P (═ O) (O)^-)(O^-)Z²⁺；

Y⁺Selected from Na⁺、K⁺、Li⁺、¹/₂Cd²⁺、¹/₂Zn²⁺、¹/₂Mg²⁺、¹/₂Ca²⁺、¹/₂Sr²⁺、¹/₃In³⁺、¹/₃Ga³⁺；

Z²⁺Is Cd²⁺、Zn²⁺、Mg²⁺、Ca²⁺、Sr²⁺；

R ', R' are selected, identically or differently, from H, linear or branched alkyl having 1 to 20C atoms;

r' "is selected from linear or branched alkyl groups having 1 to 10C atoms;

n is an integer of 0 to 20.

7. A compound according to one or more of claims 1 to 6, characterised in that the group FG is an electron-transporting group.

8. The compound according to one or more of claims 1 to 7, characterized in that the group FG is an electron transport group selected from triazine, pyrimidine, pyridine, pyrazine, pyrazole, pyridazine, quinoline, isoquinoline, quinoxaline, quinazoline, triazole, benzothiazole, oxazole, benzoxazole, benzimidazole, oxadiazole, phenoxazine, lactam, phenanthroline and dibenzofuran.

9. Compound according to one or more of claims 1 to 8, characterized in that the group FG is an electron-transporting group selected from the following groups

Wherein the dotted line represents the binding site to the linking group;

q' is selected, identically or differently on each occurrence, from CR¹And N;

q' is selected from NR¹O and S;

R¹selected from H, D, F, Cl, Br, I, N (R), the same or different at each occurrence²)₂、CN、NO₂、Si(R²)₃、B(OR²)₂、C(═O)R²、P(═O)(R²)₂、S(═O)R²、S(═O)₂R²、OSO₂R²A 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 which may be substituted with one or more R²Radical substitution of one or more non-adjacent CH₂The group can be represented by R²C═CR²、C≡C、Si(R²)₂、Ge(R²)₂、Sn(R²)₂、C═O、C═S、C═Se、C═NR²、P(═O)(R²)、SO、SO₂、NR²O, S or CONR²And wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Alternatively, or with 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R²Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 60 aromatic ring atoms and which may be substituted by one or more R²A group-substituted aryloxy, aralkyl or heteroaryloxy group, or a combination of two or more of these groups or a crosslinkable Q group; wherein two or more adjacent R¹The radicals may together form a mono-or polycyclic, aliphatic or aromatic ring system, where preferably two or more adjacent R¹The radicals together do not form a mono-or polycyclic, aliphatic or aromatic ring system;

R²in each case identical or different and are H, D, F, Cl, Br, I, N (R)³)₂、CN、NO₂、Si(R³)₃、B(OR³)₂、C(═O)R³、P(═O)(R³)₂、S(═O)R³、S(═O)₂R³、OSO₂R³A 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 which may be substituted with one or more R³Radical substitution of one or more non-adjacent CH₂The group can be represented by R³C═CR³、C≡C、Si(R³)₂、Ge(R³)₂、Sn(R³)₂、C═O、C═S、C═Se、C═NR³、P(═O)(R³)、SO、SO₂、NR³O, S or CONR³And wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Alternatively, or with 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R³An aromatic or heteroaromatic ring system substituted by radicals, or having 5 to 60 aromatic ring atoms and which may be substituted by one or more R³A group-substituted aryloxy, aralkyl, or heteroaryloxy group, or a combination of two or more of these groups; wherein two or more adjacent R²The radicals may together form a mono-or polycyclic, aliphatic or aromatic ring system;

R³identical or different on each occurrence and is H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having from 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; wherein two or more R³The substituents together may also form a mono-or polycyclic, aliphatic or aromatic ring system.

And wherein at least one Q' is N.

10. A compound as claimed in one or more of claims 1 to 6, characterized in that the group FG is a hole-transporting group.

11. A compound according to claim 10, wherein the group FG is a hole transporting group selected from carbazole, biscarbazole, indenocarbazole, indolocarbazole, amines, triarylamines, fluoremines and spirobifluorinamines.

12. A compound according to claim 10 or 11, characterised in that the hole-transporting group is a group

Wherein

Ar^LSelected, identically or differently on each occurrence, from aromatic ring systems having 6 to 40 aromatic ring atoms, which may be substituted by one or more radicals R⁴Substituted, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R⁴Substitution;

Ar¹selected, identically or differently on each occurrence, from aromatic ring systems having 6 to 40 aromatic ring atoms, which may be substituted by one or more radicals R⁴Substituted, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R⁴Substitution;

e is a single bond or is selected from-C (R)⁴)₂-、-N(R⁴) A divalent group of-O-and-S-; and

k, on each occurrence, is, identically or differently, 0 or 1; wherein in the case where k is 0, there is no group Ar^LAnd the nitrogen atom and the linking group are directly linked;

m is, identically or differently, at each occurrence 0 or 1, where, in the case where m ═ 0, there is no group E and the group Ar is¹Is not connected;

R⁴selected from H, D, F, C (═ O) R, the same or different at each occurrence⁵、CN、Si(R⁵)₃、N(R⁵)₂、P(＝O)(R⁵)₂、OR⁵、S(＝O)R⁵、S(＝O)₂R⁵A straight chain alkyl or alkoxy group having 1 to 20C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20C atoms, an alkenyl or alkynyl group having 2 to 20C 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 R⁴May be linked to each other to form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R⁵And wherein one or more CH of said alkyl, alkoxy, alkenyl and alkynyl groups₂The radicals may in each case be represented by-R⁵C＝CR⁵-、-C≡C-、Si(R⁵)₂、C＝O、C＝NR⁵、-C(＝O)O-、-C(＝O)NR⁵-、NR⁵、P(＝O)(R⁵) -O-, -S-, SO or SO₂Replacement;

R⁵selected from H, D, F, C (═ O) R, the same or different at each occurrence⁶、CN、Si(R⁶)₃、N(R⁶)₂、P(＝O)(R⁶)₂、OR⁶、S(＝O)R⁶、S(＝O)₂R⁶A straight chain alkyl or alkoxy group having 1 to 20C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20C atoms, an alkenyl or alkynyl group having 2 to 20C atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; it is composed ofIn which two or more radicals R⁵May be linked to each other to form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R⁶And wherein one or more CH of said alkyl, alkoxy, alkenyl and alkynyl groups₂The radicals may in each case be represented by-R⁶C＝CR⁶-、-C≡C-、Si(R⁶)₂、C＝O、C＝NR⁶、-C(＝O)O-、-C(＝O)NR⁶-、NR⁶、P(＝O)(R⁶) -O-, -S-, SO or SO₂Replacement; and

R⁶selected, identically or differently at each occurrence, from H, D, F, CN, an alkyl group having 1 to 20C atoms, an aromatic ring system having 6 to 40C atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more radicals R⁶May be linked to each other to form a ring; and wherein the alkyl, aromatic ring system and heteroaromatic ring system may be substituted by F and CN.

13. 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, characterized in that the at least one ligand is selected from the compounds according to one or more of claims 1 to 12.

14. The semiconductor nanoparticle according to claim 13, comprising at least two different ligands, preferably exactly two different ligands, wherein the ligands are selected from the compounds according to one or more of claims 1 to 12.

15. The semiconductor nanoparticle of claim 14, wherein the semiconductor nanoparticle comprises a first ligand and a second ligand, and wherein the first ligand comprises an organofunctional group selected from an electron transporting group, and wherein the second ligand comprises an organofunctional group selected from a hole transporting group.

16. Composition comprising at least one first semiconducting nanoparticle and at least one second semiconducting nanoparticle according to one or more of claims 13 to 15, or comprising at least one first semiconducting nanoparticle according to one or more of claims 13 to 15 and at least one further organofunctional material selected from: electron injecting materials, electron transporting materials, hole blocking materials, n-dopants, host materials, wide band gap materials, fluorescent emitter materials, delayed fluorescence materials, phosphorescent emitter materials, electron blocking materials, hole transporting materials, hole injecting materials, and p-dopants.

17. Composition comprising at least one first semiconducting nanoparticle, at least one second semiconducting nanoparticle and at least one further organofunctional material selected from the group consisting of: electron injecting materials, electron transporting materials, hole blocking materials, n-dopants, host materials, wide band gap materials, fluorescent emitter materials, delayed fluorescence materials, phosphorescent emitter materials, electron blocking materials, hole transporting materials, hole injecting materials, and p-dopants.

18. The composition according to claim 16 or 17, wherein the at least one second semiconductor nanoparticle is selected from one or more of claims 13 to 15, and wherein the at least one second semiconductor nanoparticle and the at least one first semiconductor nanoparticle are different from each other.

19. The composition of claim 18, wherein the at least one first semiconductor nanoparticle comprises at least one ligand attached to an outermost surface thereof, the ligand comprising a delayed fluorescent group, and wherein the at least one second semiconductor nanoparticle comprises at least one ligand attached to an outermost surface thereof, the ligand comprising a hole-transporting group or an electron-transporting group.

20. The composition of claim 18, wherein the at least one first semiconducting nanoparticle comprises at least one ligand attached to its outermost surface, the ligand comprising a phosphorescent group, and wherein the at least one second semiconducting nanoparticle comprises at least one ligand attached to its outermost surface, the ligand comprising a hole transporting group or an electron transporting group.

21. Formulation comprising a compound according to one or more of claims 1 to 12 or a semiconducting nanoparticle according to one or more of claims 13 to 15 or a composition according to one or more of claims 16 to 20 and at least one solvent.

22. Method for preparing semiconductor nanoparticles according to one or more of claims 13 to 15, characterized in that semiconductor nanoparticles comprising a core and one or more shell layers are provided together with a compound according to one or more of claims 1 to 12 into a solvent to obtain a mixture.

23. Semiconductor nanoparticles obtained by the method according to claim 22.

24. Electronic device comprising at least one semiconductor nanoparticle according to one or more of claims 13 to 15 or a composition according to one or more of claims 16 to 20.

25. An electronic device according to claim 24, characterized in that the device is an electroluminescent device.

26. An electronic device according to claim 24 or 25, wherein the device is an electroluminescent device comprising the semiconductor nanoparticles or the composition in an emissive layer.

Examples

Working example 1 preparation of Compound (1)

1. Biphenyl-4-ylmethyl phosphonic acid diethyl ester

In a 100mL 3-neck round-bottom flask connected to a condenser, 2.3g of 4-chloromethylbiphenyl (98%, Sigma-Aldrich) was dissolved in 48.52g of triethyl phosphite (98%, Sigma-Aldrich) under an argon atmosphere. The system was heated to 160 ℃ for 26 hours. The product formed was then separated by column chromatography using silica as adsorbent and ethyl acetate and heptane as eluents.

2. Biphenyl-4-ylmethyl phosphonic acid (Compound (1))

2.0 g of the product obtained above, diethyl biphenyl-4-ylmethylphosphonate (96%, determined by gas chromatography-mass spectrometry (GCMS) on a commercial apparatus (HP6890 series, 5973 detector)) was mixed with 3.05g of bromomethylsilane (in 20mL of dichloromethane) under an argon atmosphere in a 100mL 3-necked round-bottomed flask connected to a condenser. The mixture was mixed at room temperature for 16 hours. The solvent was then evaporated using a rotary evaporator. The dried residue was dissolved in methanol (10% water, Sigma Aldrich) at room temperature under argon and mixed for 16 hours. The suspension was filtered on a paper filter and washed twice with methanol to obtain the product (yield: 62%).

Working example 2 preparation of Compound (2)

1. Bis-biphenyl-4-yl- [4- (3-chloropropyl) -phenyl ] -amine

In a glove box, 6.48mL of t-butyllithium (t-BuLi), 1.7M solution in pentane (Sigma-Aldrich) was placed into the dropping funnel. 2.5g of bisbiphenyl-4-yl- (4-bromo-phenyl) -amine (Merck) were dissolved in dry Tetrahydrofuran (THF) in a 100ml 3-neck flask and then cooled to-78 ℃ using a dry ice bath (acetone). The dropping funnel with t-BuLi was taken out from the glove box and connected to the flask. t-BuLi was slowly added dropwise directly to the solution. After that, the funnel was carefully rinsed with anhydrous THF. The solution was stirred at-78 ℃ for 1 hour.

Then, 0.62mL of 1-bromo-3-chloropropane was slowly added to the reaction using an argon-flushed syringe. The solution was allowed to warm back to room temperature and then stirred further overnight (under argon). The mixture was then cooled again in an ice bathTo 0 ℃ and slowly add 10mL of H with syringe₂And O. Then 5ml of 1M HCl was slowly added. After the solution became green, an additional 5ml of 1M HCl was added. The ice bath was removed and the mixture was stirred until it reached Room Temperature (RT). The reaction product has two phases. The organic phase was separated, the aqueous phase was extracted with dichloromethane (3 × 15mL) and MgSO₄And (5) drying.

3- [4- (Biphenyl-4-yl-amino) -phenyl ] -propyl } -phosphonic acid diethyl ester 1.34g of bis-biphenyl-4-yl- [4- (3-chloropropyl) -phenyl ] -amine (97%) were mixed with 50mL of TEP in a one-necked flask under argon at 160 ℃ and stirred for 72 h.

{3- [4- (Biphenyl-4-yl-amino) -phenyl ] -propyl } -phosphonic acid (Compound (2))

0.77g of 3- [4- (bis-biphenyl-4-yl-amino) -phenyl ] is reacted under argon]Diethyl-propyl } -phosphonate was dissolved in 20mL of dichloromethane and mixed with 0.63g (0.55mL) bromotrimethylsilane (3 equiv.) and stirred at room temperature for 12 h. Methanol (10% H)₂O) was added directly to the solution, which became white. The mixture was stirred at room temperature under argon overnight. The mixture was then evaporated and a pale yellow gel formed. The gel was recrystallized in 5mL of acetonitrile to obtain white yellowish wax and a yellow supernatant. The supernatant was removed and the wax was washed twice with a small amount of acetonitrile. The wax was recrystallized in 3ml ethanol. A white wax is received. 5ml of heptane were added and the wax was resuspended at room temperature, filtered (2 washes with heptane) and dried in a vacuum chamber. A white slightly green solid was received (yield: 38%).

The syntheses of the other compounds (3), (4), (6) and (7) as shown in table 2 below were carried out analogously;

TABLE 2

Working example 3 preparation of semiconductor nanoparticles

InP/ZnS core/shell nanoparticles were synthesized in a manner similar to that described in Hussain et al, ChemPhysChem,2009,10, 1466-1470. 5mL of a solution (50mg/mL in toluene) containing InP/ZnS core/shell nanoparticles (PL emission peak 625nm) was mixed with 0.25 g of an alternative surface ligand (i.e., Compound (2) of working example 2) and stirred under an argon atmosphere at 50 ℃ overnight. The mixture was then transferred to a centrifuge vial and 5ml of dry methanol was added. After that, the mixture was centrifuged at 4000rpm for 5 minutes under argon. After this time, the colorless supernatant was removed and the red precipitate was suspended in 5mL of dry toluene.

Similar procedures can be used for other ligands according to the invention. The amount of ligand added was calculated on a molar basis.

Working example 4-manufacture of a solution-treated OLED (device E1)

The preparation of solution-based OLEDs has been described many times in the literature, for example in WO2004/037887 and WO 2010/097155. This method is applicable to the following cases (layer thickness variation, material).

The material combination of the invention is used in the following layer sequence:

-a substrate,

-ITO(50nm)，

-a buffer layer (buffer) (20nm),

a hole transport layer (20nm),

-an emission layer (EML) (30nm),

-an Electron Transport Layer (ETL) (50nm),

an Electron Injection Layer (EIL) (3nm),

cathode (Al) (100 nm).

A glass plate coated with structured ITO (indium tin oxide) at a thickness of 50nm was used as substrate. These were coated by spin coating with buffer layer (PEDOT) Clevios P VP AI 4083(Heraeus Clevios GmbH, Leverkusen). The spin coating of the buffer layer was performed with water in air. The layer was then dried by heating at 180 ℃ for 10 minutes. A hole-transporting layer and an emission layer are applied to the glass plate coated in this way.

For the hole transport layer, polymers of the structure shown in table 3 were used, which were synthesized according to WO 2010/097155. The polymer was dissolved in toluene so that the solution had a solid content of about 5g/L, in order to prepare a 20nm thick layer. The layers were applied by spin coating in an argon atmosphere and dried by heating at 220 ℃ for 30 minutes.

For the emission layer, red-emitting InP/ZnS nanoparticles according to the present invention, i.e. quantum dots attached to their surface ligands according to the present invention, dissolved in toluene, were used. The solids content of this solution was about 15mg/mL to prepare a 30nm thick layer. The layers were applied by spin coating in an argon atmosphere and dried by heating at 120 ℃ for 10 minutes.

Table 3: structural formula of additional material for solution processed layer in OLED

The materials of the electron transport layer and the electron injection layer were also applied by thermal vapor 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 evaporation of a layer of aluminum having a thickness of 100 nm.

Comparative example 1-manufacture of a solution-treated OLED (device V1)

A solution-based OLED was prepared in the same way as described in working example 4 above, using the same compounds/materials, except that the emission layer was prepared with the prior art red light emitting semiconductor nanoparticles, i.e. QDs covered with common alkyl ligands.

Working example 5 device characterization

OLEDs are characterized by standard methods. For this purpose, a Lambertian emission curve (profile) is taken, from which the electroluminescence spectrum and the external quantum efficiency (EQE, measured in%) are determined from the current/voltage/brightness characteristic line (IUL characteristic line). The Electroluminescence (EL) spectrum was recorded at a luminous density of 100cd/m2, and CIE 1931 x and y coordinates were calculated from the EL spectrum. Device data for OLEDs prepared according to working example 4 and comparative example 1 are summarized in table 5. In the following sections, embodiments are described in more detail to show the advantages of the OLED of the invention.

Use of InP/ZnS nanoparticles according to the invention as an emitting material in OLEDs

The InP/ZnS nanoparticles according to the invention are particularly suitable as emissive material in OLED devices. The properties of the prepared OLEDs are summarized in table 5. Example E1 shows the properties of an OLED comprising the material of the invention.

As can be seen from the data shown in table 5, the OLED using semiconductor nanoparticles (E1) according to the invention in the emissive layer, i.e. quantum dots attached to their surface ligands according to the invention, in this example the structure (35) provides a significant improvement compared to the prior art (V1, i.e. QD covered with conventional carboxylic acid and thioalkyl ligands, as described in Hussain et al ChemPhysChem,2009,10, 1466-.