CN117730639A

CN117730639A - Organic electronic device comprising a compound of formula (I), display device comprising said organic electronic device, and compound of formula (I)

Info

Publication number: CN117730639A
Application number: CN202280038457.4A
Authority: CN
Inventors: 弗拉迪米尔·乌瓦罗夫; 乌尔里希·赫格曼; 斯特芬·维尔曼; 皮尔马里亚·平特; 茂真朴
Original assignee: NovaLED GmbH
Current assignee: NovaLED GmbH
Priority date: 2021-06-18
Filing date: 2022-06-15
Publication date: 2024-03-19

Abstract

The present invention relates to a benzodiphenylfluorene compound represented by formula (I):

Description

Organic electronic device comprising a compound of formula (I), display device comprising said organic electronic device, and compound of formula (I)

Technical Field

The present invention relates to organic electronic devices comprising compounds of formula (I) and display devices comprising said organic electronic devices. The invention also relates to novel compounds of formula (I) which can be used in organic electronic devices.

Background

An organic electronic device such as an organic light emitting diode OLED as a self-light emitting device has a wide viewing angle, excellent contrast, quick response, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED includes an anode, a hole transport layer HTL, an emission layer EML, an electron transport layer ETL, and a cathode, which are sequentially stacked on a substrate. In this regard, HTL, EML, and ETL are thin films formed of organic compounds.

When a voltage is applied to the anode and the cathode, holes injected from the anode move to the EML through the HTL, and electrons injected from the cathode move to the EML through the ETL. Holes and electrons recombine in the EML to generate excitons. When the exciton falls from an excited state to a ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that the OLED having the above-described structure has excellent efficiency and/or long lifetime.

The performance of the organic light emitting diode may be affected by the characteristics of the semiconductor layer, wherein it may be affected by the characteristics of the compound of formula (I) contained in the semiconductor layer.

There remains a need to improve the performance of organic semiconductor materials, semiconductor layers and organic electronic devices thereof, in particular to achieve improved operating voltage stability over time by improving the characteristics of the compounds contained therein.

Disclosure of Invention

One aspect of the present invention provides a benzodiphenylfluorene compound represented by formula (I):

wherein Ar is ⁴ Represented by formula (Ia) or (Ib),

wherein the asterisks indicate the binding position of (Ia) and (Ib), an

Wherein the method comprises the steps of

Ar＝Ar ¹ And Ar is Ar ¹ Selected from substituted or unsubstituted C ₆ To C ₂₄ Aryl or substituted or unsubstituted C ₃ To C ₂₅ A heteroaryl group, which is a group,

Ar ¹ at least one substituent on the ring is selected from C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl, C ₃ To C ₁₂ Heteroaryl;

R ^a 、R ^b 、R ^c and R is ^d Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl, and R ^a 、R ^b 、R ^c Or R is ^d One of them represents a single bond to N of formula (I), selected from R ^a 、R ^b 、R ^c And R is ^d Optionally two adjacent substituents of (a) form a substituted or unsubstituted condensed ring system, wherein

The condensationAt least one substituent on the ring system is independently selected from C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl or C ₂ To C ₁₂ Heteroaryl;

R ^e 、R ^f 、R ^g and R is ^h Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl;

X ¹ selected from O, S, NAr ^1a ；

Ar ^1a Selected from C ₆ To C ₁₂ An aryl group;

or (b)

Ar＝Ar ² And Ar is ² Selected from C ₆ To C ₁₂ Aryl or C ₂ To C ₂₅ Heteroaryl;

R ^a2 、R ^b2 、R ^c2 and R is ^d2 Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl, and R ^a2 、R ^b2 、R ^c2 Or R is ^d2 One of them represents a single bond to N of formula (I), selected from R ^a2 、R ^b2 、R ^c2 And R is ^d2 Optionally two adjacent substituents of (a) form a substituted or unsubstituted condensed ring system, wherein

At least one substituent on the condensed ring system is independently selected from C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl or C ₂ To C ₁₂ Heteroaryl;

R ^e2 、R ^f2 、R ^g2 and R is ^h2 Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl;

X ² selected from O, S, NAr ^2b 、CR ^1b R ^2b 、SiR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

R ^1b And R is ^2b Independently selected from C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl or C ₂ To C ₁₂ Heteroaryl groups.

It should be noted that throughout the application and claims, unless otherwise indicated, any Ar, ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ 、R ^a 、R ^b 、R ^c 、R ^d 、R ^e 、R ^f 、R ^g 、R ^h 、X ¹ 、X ² _、 X ^1b 、Ar ^1a 、Ar ^2b 、R ^1b 、R ^2b 、R ^a2 、R ^b2 、R ^c2 、R ^d2 、R ^e2 、R ^f2 、R ^g2 、R ^h2 Etc. refer to the same parts throughout.

In the present specification, "substituted" means substituted with the following groups when no definition is otherwise provided: h or deuterium; or C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl, C ₅ To C ₁₂ Heteroaryl; or C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl or C ₂ To C ₁₂ Heteroaryl; or H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl groups.

However, in this specification, "aryl substituted" means substituted with one or more aryl groups, which may themselves be substituted with one or more aryl and/or heteroaryl groups.

Accordingly, in this specification, "heteroaryl substituted" means substituted with one or more heteroaryl groups, which may themselves be substituted with one or more aryl and/or heteroaryl groups.

In the present specification, when not otherwise defined, "alkyl group" means a saturated aliphatic hydrocarbon group. The alkyl group may be C ₁ To C ₁₂ An alkyl group. More specifically, the alkyl group may be C ₁ To C ₁₀ Alkyl groups or C ₁ To C ₆ An alkyl group. For example, C ₁ To C ₄ The alkyl group contains 1 to 4 carbons in the alkyl chain and may be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Specific examples of the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group.

The term "cycloalkyl" refers to a saturated hydrocarbyl group derived from a cycloalkane by formally subtracting one hydrogen atom from the ring atom contained in the corresponding cycloalkane. Examples of cycloalkyl groups may be cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, methylcyclohexyl groups, adamantyl groups, and the like.

The term "hetero" is understood to mean the way in which at least one carbon atom is replaced by another multivalent atom in the structure that may be formed by covalently bonded carbon atoms. Preferably, the heteroatom is selected from B, si, N, P, O, S; more preferably from N, P, O, S.

In the present specification, an "aryl group" refers to a hydrocarbon group generated by formally subtracting one hydrogen atom from an aromatic ring in a corresponding aromatic hydrocarbon. Aromatic hydrocarbons refer to hydrocarbons containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system refers to a planar ring or ring system covalently bonded to a carbon atom, wherein the planar ring or ring system comprises a conjugated system of delocalized electrons meeting the huckel rule. Examples of aryl groups include: monocyclic groups such as phenyl or tolyl; polycyclic groups comprising multiple aromatic rings linked by single bonds, such as biphenyl; and polycyclic groups containing fused rings such as naphthyl or fluoren-2-yl.

Similarly, heteroaryl is particularly suitable to be understood as meaning a radical obtained by formally subtracting one ring hydrogen from the heterocyclic aromatic ring in a compound comprising at least one heterocyclic aromatic ring.

Heterocycloalkyl is particularly suitable to be understood as meaning a radical obtained by formally subtracting one ring hydrogen from the saturated cycloalkyl ring in a compound comprising at least one saturated cycloalkyl ring.

The term "fused aryl ring" or "condensed aryl ring" is understood to mean when two aryl rings share at least two common sp ² They are considered to be a means of fusion or condensation when hybridising carbon atoms.

The term "cyano moiety" refers to a CN substituent.

In the present specification, a single bond means a direct bond.

The term "n-type charge generating layer" is sometimes also referred to in the art as an n-CGL or electron generating layer and is intended to encompass both.

The term "p-type charge generating layer" is sometimes also referred to in the art as a p-CGL or hole generating layer and is intended to encompass both.

According to one embodiment of the invention, the p-type and/or n-type charge generating layer and/or the compound of formula (I) is non-luminescent.

The terms "free", "not containing" do not exclude impurities that may be present in the compound prior to deposition. The impurities have no technical influence on the object achieved by the invention.

The term "contact sandwich" refers to a three layer arrangement in which an intermediate layer is in direct contact with two adjacent layers.

The terms "light absorbing layer" and "light absorbing layer" are used synonymously.

The terms "light emitting layer", "light emitting layer" and "emissive layer" are used synonymously.

The terms "OLED", "organic light emitting diode" and "organic light emitting device" are synonymously used.

The terms "anode", "anode layer" and "anode electrode" are used synonymously.

The terms "cathode", "cathode layer" and "cathode electrode" are used synonymously.

The term "top-emitting device" is understood to mean an organic electronic device in which light is emitted through the cathode layer.

The term "bottom emission device" is understood to mean an organic electronic device in which light is emitted through a substrate.

The operating voltage U is measured in volts.

In the context of the present specification, the term "essentially non-luminescent" or "non-luminescent" refers to compounds of formula I, ia, ib, ic, id, ie, if, ig, ih, ik, organic electron transporting compounds, organic hole transporting compounds, matrix compounds of formula (VI) or formula (VII), metal complexes and/or layers, p-type charge generating layers and n-type charge generating layers having a contribution to the visible light emission spectrum derived from an organic electronic device, such as an OLED or display device, of less than 10%, preferably less than 5%, relative to the visible light emission spectrum. The visible light emission spectrum is an emission spectrum having a wavelength of about 380nm to about 780 nm.

In this specification, the hole characteristics refer to the ability to provide one electron to form a hole when an electric field is applied and allow the hole formed in the anode to be easily injected into and transported in the light emitting layer due to the conductive characteristics according to the Highest Occupied Molecular Orbital (HOMO) level.

Further, the electron characteristics refer to the ability to accept electrons when an electric field is applied and allow electrons formed in a cathode to be easily injected into and transported in a light emitting layer due to the conductive characteristics according to the Lowest Unoccupied Molecular Orbital (LUMO) level.

The term "HOMO level" is understood to mean the highest occupied molecular orbital and is determined in eV (electron volt).

The term "HOMO level far from the vacuum level" is understood to mean that the absolute value of the HOMO level is higher than that of the reference compound. For example, the term "the HOMO energy level of 8 ' -tetramine is further from the vacuum energy level than N2, N2, N2', N2', N7, N7', N7' -octa (4-methoxyphenyl) -9,9' -spirodi [ fluorene ] -2,2', 7' -tetramine" is understood to mean that the absolute value of the HOMO energy level of the organic matrix of the p-type charge generating layer is higher than N2, HOMO levels of N2, N2', N7' -octa (4-methoxyphenyl) -9,9' -spirodi [ fluorene ] -2,2', 7' -tetramine.

The term "absolute value" is understood to mean a value without the "-" symbol. According to one embodiment of the present invention, the HOMO level of the organic matrix of the p-type charge generating layer may be calculated by quantum mechanical methods.

The work function of the first metal is measured in eV (electron volts). List values of work functions can be found in handbook of chemistry and physics CRC (CRC Handbook of Chemistry and Physics) 2008 edition pages 12-114. Furthermore, list values of Work functions can be found in, for example, https:// en.wikipedia.org/wiki/work_function#ci_note-12.

Advantageous effects

Surprisingly, it has been found that the organic electronic device according to the invention solves the underlying problems of the invention, in particular in terms of operating voltage during the lifetime, by making the device superior in various respects to organic electroluminescent devices known in the art.

Description of the embodiments

According to one embodiment, the benzodiphenylfluorene compound is represented by formula (I):

wherein Ar is ⁴ Represented by formula (Ia) or (Ib),

wherein the asterisks indicate the binding position of (Ia) and (Ib), an

Wherein the method comprises the steps of

Ar＝Ar ¹ And Ar is Ar ¹ Selected from substituted or unsubstituted C ₆ To C ₂₄ Aryl groupOr substituted or unsubstituted C ₅ To C ₂₅ A heteroaryl group, which is a group,

Ar ¹ at least one substituent on the ring is selected from C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl, C ₅ To C ₁₂ Heteroaryl;

X ¹ selected from O, S, NAr ^1a ；

Ar ^1a Selected from C ₆ To C ₁₂ An aryl group;

or (b)

Ar＝Ar ² And Ar is ² Selected from C ₆ To C ₁₂ Aryl or C ₅ To C ₂₅ Heteroaryl or biphenyl;

R ^a2 、R ^b2 、R ^c2 and R is ^d2 Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl, and R ^a2 、R ^b2 、R ^c2 Or R is ^d2 One of them represents a single bond to N of formula (I), selected from R ^a2 、R ^b2 、R ^c2 And R is ^d2 Optionally in (3)Two adjacent substituents form a substituted or unsubstituted condensed ring system in which

X ² selected from O, S, NAr ^2b 、CR ^1b R ^2b 、SiR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

According to one embodiment, wherein the benzodiphenylfluorene compound is represented by formula (I):

wherein Ar is ⁴ Represented by formula (Ia) or (Ib),

wherein the asterisks indicate the binding position of (Ia) and (Ib), an

Wherein the method comprises the steps of

Ar＝Ar ¹ And Ar is Ar ¹ Selected from unsubstituted C ₆ To C ₂₄ Aryl or unsubstituted C ₅ To C ₂₅ Heteroaryl;

R ^a 、R ^b 、R ^c and R is ^d Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl, and R ^a 、R ^b 、R ^c Or R is ^d One of them represents a single bond to N of formula (I), selected from R ^a 、R ^b 、R ^c And R is ^d Optionally two adjacent substituents of (a) form an unsubstituted condensed ring system;

X ¹ selected from O, S, NAr ^1a ；

Ar ^1a Selected from C ₆ To C ₁₂ An aryl group;

or (b)

Ar＝Ar ² And Ar is ² Selected from C ₆ To C ₁₂ Aryl, C ₅ To C ₂₅ Heteroaryl or biphenyl;

R ^a2 、R ^b2 、R ^c2 and R is ^d2 Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl, and R ^a2 、R ^b2 、R ^c2 Or R is ^d2 One of them represents a single bond to N of formula (I), selected from R ^a2 、R ^b2 、R ^c2 And R is ^d2 Optionally two adjacent substituents of (a) form an unsubstituted condensed ring system;

X ² selected from O, S, NAr ^2b 、CR ^1b R ^2b 、SiR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

wherein Ar is ⁴ Represented by formula (Ia) or (Ib),

wherein the asterisks indicate the binding position of (Ia) and (Ib), an

Wherein the method comprises the steps of

Ar＝Ar ¹ And Ar is Ar ¹ Selected from substituted or unsubstituted C ₆ To C ₂₄ Aryl or substituted or unsubstituted C ₅ To C ₂₅ Heteroaryl;

X ¹ selected from O, S, NAr ^1a ；

Ar ^1a Selected from C ₆ To C ₁₂ An aryl group;

or (b)

X ² selected from O, S, NAr ^2b 、CR ^1b R ^2b 、SiR ^1b R ^2b ；

Ar ^2b Selected from biphenyl groups; and is also provided with

According to one embodiment, wherein the compound of formula (I) is represented by a compound of formula (Ic), (Id) or (Ie), wherein

The formula (Ic) is:

wherein the method comprises the steps of

Ar ¹ Selected from substituted or unsubstituted C ₆ To C ₂₄ Aryl or substituted or unsubstituted C ₅ To C ₂₅ A heteroaryl group, which is a group,

X ¹ selected from O, S, NAr ^1a ；

Ar ^1a Selected from C ₆ To C ₁₂ An aryl group;

or (b)

The formula (Id) is:

wherein the method comprises the steps of

Ar ² Selected from C ₆ To C ₁₂ Aryl or C ₅ To C ₂₅ Heteroaryl;

X ² selected from O, S, NAr ^2b 、CR ^1b R ^2b 、SiR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

R ^1b And R is ^2b Independently selected from C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl or C ₂ To C ₁₂ Heteroaryl;

or (b)

The formula (Ie) is:

wherein the method comprises the steps of

Ar ³ Is selected from the group consisting of biphenyl groups,

X ³ selected from O, S, NAr ^2b 、CR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

The formula (Ic) is:

wherein the method comprises the steps of

Ar ¹ Selected from unsubstituted C ₆ To C ₂₄ Aryl or unsubstituted C ₅ To C ₂₅ Heteroaryl;

X ¹ selected from O, S, NAr ^1a ；

Ar ^1a Selected from C ₆ To C ₁₂ An aryl group;

or (b)

The formula (Id) is:

wherein the method comprises the steps of

Ar ² Selected from C ₆ To C ₁₂ Aryl or C ₅ To C ₂₅ Heteroaryl;

R ^a2 、R ^b2 、R ^c2 and R is ^d2 Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl, and R ^a2 、R ^b2 、R ^c2 Or R is ^d2 One of them represents a single bond to N of formula (Ib) selected from R ^a2 、R ^b2 、R ^c2 And R is ^d2 Optionally two adjacent substituents of (a) form an unsubstituted condensed ring system;

X ² selected from O, S, NAr ^2b 、CR ^1b R ^2b 、SiR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

or (b)

The formula (Ie) is:

wherein the method comprises the steps of

Ar ³ Is selected from the group consisting of biphenyl groups,

X ³ selected from O, S, NAr ^2b 、CR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

Ar ¹

According to one embodiment, ar ¹ Can be selected identically or independently from one another from C ₆ To C ₂₄ Aryl, C ₆ To C ₂₂ Aryl, C ₆ To C ₂₀ Aryl, C ₆ To C ₁₈ Aryl, C ₆ To C ₁₆ Aryl, C ₆ To C ₁₄ Aryl or C ₆ To C ₁₃ Aryl groups. According to one embodiment, ar ¹ Can be selected identically or independently from one another from C ₅ To C ₂₅ Heteroaryl, C ₅ To C ₂₃ Heteroaryl, C ₅ To C ₂₁ Heteroaryl, C ₅ To C ₁₉ Heteroaryl, C ₅ To C ₁₇ Heteroaryl, C ₅ To C ₁₅ Heteroaryl, C ₅ To C ₁₃ Heteroaryl or C ₅ To C ₁₂ Heteroaryl groups. According to one embodiment, ar ¹ May be selected from substituted or unsubstituted C ₆ To C ₁₃ Aryl and substituted or unsubstituted C ₁₂ Heteroaryl groups. According to one embodiment, ar ¹ Selected from substituted C ₆ To C ₁₃ Aryl and substituted or unsubstituted C ₁₂ Heteroaryl groups. According to one embodiment, ar ¹ Selected from substituted C ₆ To C ₁₃ Aryl and substituted C ₁₂ Heteroaryl groups. According to one embodiment, ar ¹ Selected from substituted C ₆ To C ₁₃ Aryl groups. According to another embodiment, ar ¹ The substituents on the radicals can be identical or independently of one another selected from C ₁ To C ₆ Alkyl, C ₁ To C ₅ Alkyl, preferably C ₁ To C ₄ Alkyl, more preferably C ₁ To C ₃ Alkyl, still more preferably C ₁ To C ₂ Alkyl or most preferably C ₁ An alkyl group. According to one embodiment, ar ¹ At least one substituent on the two groups being able to be identical or independently of one another selected from C ₆ To C ₁₂ Aryl, C ₆ To C ₁₀ Aryl or C ₆ Aryl groups. According to one embodiment, ar ¹ At least one substituent on the two groups being able to be identical or independently of one another selected from C ₅ To C ₁₂ Heteroaryl, C ₅ To C ₁₁ Heteroaryl, C ₅ To C ₁₀ Heteroaryl or C ₅ To C ₉ Heteroaryl groups. According to one embodiment, ar ¹ At least one substituent on the ring is selected from C ₁ To C ₆ An alkyl group.

Ar ²

According to one embodiment, wherein Ar ² Can be selected from C ₅ To C ₂₅ Heteroaryl, C ₅ To C ₂₃ Heteroaryl, C ₅ To C ₂₁ Heteroaryl, C ₅ To C ₁₉ Heteroaryl, C ₅ To C ₁₇ Heteroaryl, C ₅ To C ₁₅ Heteroaryl, C ₅ To C ₁₃ Heteroaryl or C ₅ To C ₁₂ Heteroaryl groups.

According to one embodiment, wherein Ar ² Can be selected from C ₆ To C ₁₂ Aryl, C ₁₀ To C ₁₂ Aryl and more preferably C ₁₂ Aryl groups. According to one embodiment, ar ² Selected from C ₆ To C ₁₀ Aryl groups. According to one embodiment, ar ² Selected from C ₆ Aryl groups. According to one embodiment, ar ² Can be selected from biphenyl and naphthyl. According to one embodiment, ar ² Can be selected from biphenyl groups.

Ar ^2b

According to one embodiment, ar ^2b Selected from C ₆ To C ₁₀ Aryl groups. According to one embodiment, ar ^2b Selected from C ₆ Aryl groups.

X

According to one embodiment, X is selected from O, S, NAr ² 。

X ¹

According to one embodiment, wherein X is selected from O, S, NAr ^1b . According to one embodiment, wherein X is selected from O or NAr ^1b . According to one embodiment, wherein X is selected from O.

According to one embodiment, wherein X is selected from O, S, NAr ^2b 、CR ^1b R ^2b And SiR ^1b R ^2b . According to one embodiment, wherein X is selected from O, S, NAr ² . According to one embodiment, wherein X is selected from O or NAr ² . According to one embodiment, wherein X is selected from O.

X ²

According to one embodiment, wherein X ² Selected from O, NAr ^2b 、CR ^1b R ^2b And SiR ^1b R ^2b . According to one embodiment, wherein X ² Selected from O, NAr ^2b And CR (CR) ^1b R ^2b . According to one embodiment, wherein X ² Selected from O and CR ^1b R ^2b . According to one embodiment, wherein X ² Selected from CR ^1b R ^2b 。

X ³

According to one embodiment, wherein X ³ Selected from O, S, NAr ^2b 、CR ^1b R ^2b . According to one embodiment, wherein X ³ Selected from O and CR ^1b R ^2b . According to one embodiment, wherein X ³ Selected from CR ^1b R ^2b 。

X ^1b

R ^1b And R is ^2b

According to one embodiment, R ^1b And R is ^2b Can be selected identically or independently from one another from C ₁ To C ₆ Alkyl, C ₁ To C ₅ Alkyl, preferably C ₁ To C ₄ Alkyl, more preferably C ₁ To C ₃ Alkyl groupStill more preferably C ₁ To C ₂ Alkyl or most preferably C ₁ An alkyl group. According to one embodiment, R ^1b And R is ^2b Can be selected identically or independently from one another from C ₆ To C ₁₂ Aryl, C ₆ To C ₁₀ Aryl, and preferably C ₆ An alkyl group. According to one embodiment, R ^1b And R is ^2b Can be selected identically or independently from one another from C ₂ To C ₁₂ Heteroaryl, C ₃ To C ₁₂ Heteroaryl, C ₄ To C ₁₂ Heteroaryl, C ₅ To C ₁₂ Heteroaryl, C ₅ To C ₁₁ Heteroaryl, C ₅ To C ₁₀ Heteroaryl or C ₅ To C ₉ Heteroaryl groups. According to one embodiment, R ^1b And R is ^2b Independently selected from C ₁ To C ₆ Alkyl, preferably C ₁ To C ₅ Alkyl, more preferably C ₁ To C ₄ Alkyl, more preferably C ₁ To C ₃ Alkyl, still more preferably C ₁ To C ₂ Alkyl or most preferably C ₁ An alkyl group.

R ^a 、R ^b 、R ^c And R is ^d

According to one embodiment, R ^a 、R ^b 、R ^c And R is ^d Can be selected identically or independently from one another from C ₁ To C ₆ Alkyl, C ₁ To C ₅ Alkyl, C ₁ To C ₄ Alkyl, C ₁ To C ₃ Alkyl, C ₁ To C ₂ Alkyl or C ₁ An alkyl group. According to one embodiment, R ^a 、R ^b 、R ^c And R is ^d Can be selected identically or independently from one another from C ₆ To C ₁₈ Aryl, C ₆ To C ₁₆ Aryl, C ₆ To C ₁₄ Aryl, C ₆ To C ₁₂ Aryl, C ₆ To C ₁₀ Aryl or C ₆ Aryl groups. According to one embodiment, R ^a 、R ^b 、R ^c And R is ^d Can be selected identically or independently from one another from C ₂ To C ₁₈ Heteroaryl, C ₃ To C ₁₈ Heteroaryl, C ₄ To C ₁₈ Heteroaryl, C ₅ To C ₁₈ Heteroaryl, C ₅ To C ₁₇ Heteroaryl, C ₅ To C ₁₆ Heteroaryl, C ₅ To C ₁₅ Heteroaryl, C ₅ To C ₁₄ Heteroaryl, C ₅ To C ₁₃ Heteroaryl, C ₅ To C ₁₂ Heteroaryl, C ₅ To C ₁₁ Heteroaryl, C ₅ To C ₁₀ Heteroaryl or C ₅ To C ₁₉ Heteroaryl groups. According to one embodiment, R ^a 、R ^b 、R ^c And R is ^d Can be the same or independently selected from H, C ₁ To C ₆ Alkyl and C ₆ To C ₁₈ Aryl groups.

R ^e 、R ^f 、R ^g And R is ^h

According to one embodiment, R ^e 、R ^f 、R ^g And R is ^h Can be selected identically or independently from one another from C ₁ To C ₆ Alkyl, C ₁ To C ₅ Alkyl, C ₁ To C ₄ Alkyl, C ₁ To C ₃ Alkyl, C ₁ To C ₂ Alkyl or C ₁ An alkyl group. According to one embodiment, R ^e 、R ^f 、R ^g And R is ^h C of (2) ₆ To C ₁₈ Aryl groups can be the same or independently of one another selected from C ₆ To C ₁₆ Aryl, C ₆ To C ₁₄ Aryl, C ₆ To C ₁₂ Aryl, C ₆ To C ₁₀ Aryl or C ₆ Aryl groups. According to one embodiment, R ^e 、R ^f 、R ^g And R is ^h Can be selected identically or independently from one another from C ₂ To C ₁₈ Heteroaryl, C ₃ To C ₁₈ Heteroaryl, C ₄ To C ₁₈ Heteroaryl, C ₅ To C ₁₈ Heteroaryl, C ₅ To C ₁₇ Heteroaryl, C ₅ To C ₁₆ Heteroaryl, C ₅ To C ₁₅ Heteroaryl, C ₅ To C ₁₄ Heteroaryl, C ₅ To C ₁₃ Heteroaryl, C ₅ To C ₁₂ Heteroaryl, C ₅ To C ₁₁ Heteroaryl, C ₅ To C ₁₀ Heteroaryl or C ₅ To C ₁₉ Heteroaryl groups. According to one embodiment, R ^e 、R ^f 、R ^g And R is ^h Independently selected from H, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl groups. According to one embodiment, R ^e 、R ^f 、R ^g And R is ^h Independently selected from H and C ₆ To C ₁₈ Aryl groups. According to one embodiment, R ^e 、R ^f 、R ^g And R is ^h Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl groups.

R ^a2 、R ^b2 、R ^c2 And R is ^d2

According to one embodiment, R ^a2 、R ^b2 、R ^c2 And R is ^d2 Can be selected identically or independently from one another from C ₁ To C ₆ Alkyl, C ₁ To C ₅ Alkyl, C ₁ To C ₄ Alkyl, C ₁ To C ₃ Alkyl, C ₁ To C ₂ Alkyl or C ₁ An alkyl group. According to one embodiment, R ^a2 、R ^b2 、R ^c2 And R is ^d2 Can be selected identically or independently from one another from C ₆ To C ₁₈ Aryl, C ₆ To C ₁₆ Aryl, C ₆ To C ₁₄ Aryl, C ₆ To C ₁₂ Aryl, C ₆ To C ₁₀ Aryl or C ₆ Aryl groups. According to one embodiment, R ^a2 、R ^b2 、R ^c2 And R is ^d2 Can be selected identically or independently from one another from C ₂ To C ₁₈ Heteroaryl, C ₃ To C ₁₈ Heteroaryl, C ₄ To C ₁₈ Heteroaryl, C ₅ To C ₁₈ Heteroaryl, C ₅ To C ₁₇ Heteroaryl, C ₅ To C ₁₆ Heteroaryl, C ₅ To C ₁₅ Heteroaryl, C ₅ To C ₁₄ Heteroaryl, C ₅ To C ₁₃ Heteroaryl, C ₅ To C ₁₂ Heteroaryl, C ₅ To C ₁₁ Heteroaryl, C ₅ To C ₁₀ Heteroaryl or C ₅ To C ₁₉ Heteroaryl groups. According to one embodiment, R ^a 、R ^b 、R ^c And R is ^d Independently selected from H, C ₁ To C ₆ Alkyl and C ₆ To C ₁₈ Aryl groups.

R ^e2 、R ^f2 、R ^g2 And R is ^h2

According to one embodiment, R ^e2 、R ^f2 、R ^g2 And R is ^h2 Can be selected identically or independently from one another from C ₁ To C ₆ Alkyl, C ₁ To C ₅ Alkyl, C ₁ To C ₄ Alkyl, C ₁ To C ₃ Alkyl, C ₁ To C ₂ Alkyl or C ₁ An alkyl group. According to one embodiment, R ^e2 、R ^f2 、R ^g2 And R is ^h2 Can be selected identically or independently from one another from C ₆ To C ₁₈ Aryl, C ₆ To C ₁₆ Aryl, C ₆ To C ₁₄ Aryl, C ₆ To C ₁₂ Aryl, C ₆ To C ₁₀ Aryl or C ₆ Aryl groups. According to one embodiment, R ^e2 、R ^f2 、R ^g2 And R is ^h2 Can be selected identically or independently from one another from C ₂ To C ₁₈ Heteroaryl, C ₃ To C ₁₈ Heteroaryl, C ₄ To C ₁₈ Heteroaryl, C ₅ To C ₁₈ Heteroaryl, C ₅ To C ₁₇ Heteroaryl, C ₅ To C ₁₆ Heteroaryl, C ₅ To C ₁₅ Heteroaryl, C ₅ To C ₁₄ Heteroaryl, C ₅ To C ₁₃ Heteroaryl, C ₅ To C ₁₂ Heteroaryl, C ₅ To C ₁₁ Heteroaryl, C ₅ To C ₁₀ Heteroaryl or C ₅ To C ₁₉ Heteroaryl groups. According to one embodiment, R ^e2 、R ^f2 、R ^g2 And R is ^h2 Independently selected from H, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl groups. According to one embodiment, R ^e2 、R ^f2 、R ^g2 And R is ^h2 Independently selected from H and C ₆ To C ₁₈ Aryl groups.

Substituents on condensed ring systems

According to one embodiment, in the case of formulae (Ia), (Ib), (Ic), (Id), (If), (Ig), (Ih) and (Ik), at least one substituent on the condensed ring system can be chosen independently of one another from C ₁ To C ₆ Alkyl, C ₁ To C ₅ Alkyl, preferably C ₁ To C ₄ Alkyl, more preferably C ₁ To C ₃ Alkyl, still more preferably C ₁ To C ₂ Alkyl and most preferably C ₁ An alkyl group. According to one embodiment, at least one substituent on the condensed ring system is selected from C ₁ To C ₆ An alkyl group.

Formulas (Ic), (Id), (Ie)

According to one embodiment of the benzodiphenylfluorene compound, wherein for formula (Ic), X ¹ Selected from O or NAr ² O is preferred.

According to one embodiment of the benzodiphenylfluorene compounds, wherein for formula (Id), X ² Selected from O, NAr ^2b 、CR ^1b R ^2b And SiR ^1b R ^2b Preferably selected from O and CR ^1b R ^2b And is also preferably selected from CR ^1b R ^2b 。

According to one embodiment of the benzodiphenylfluorene compound, wherein for formula (Ie), X ³ Selected from O, S and SiR ^1b R ^2b Preferably selected from O and S, and also preferably selected from O.

According to one embodiment of the benzodiphenylfluorene compounds, wherein for formula (Ic), X ¹ Selected from O or NAr ² Preferably O; for formula (Id), X ² Selected from O, NAr ^2b 、CR ^1b R ^2b And SiR ^1b R ^2b Preferably selected from O and CR ^1b R ^2b Also preferably selected from CR ^1b R ^2b The method comprises the steps of carrying out a first treatment on the surface of the And for formula (Ie), X ³ Selected from O, S and SiR ^1b R ^2b Preferably selected from O and S, and also preferably selected from O.

According to one embodiment of the benzodiphenylfluorene compoundIn which for formula (Ic), ar ¹ Selected from substituted or unsubstituted C ₆ To C ₁₃ Aryl and substituted or unsubstituted C ₁₂ Heteroaryl, preferably Ar ¹ Selected from substituted C ₆ To C ₁₃ Aryl groups.

According to one embodiment of the benzodiphenylfluorene compounds, wherein Ar for formula (Id) ² Selected from C ₆ To C ₁₀ Aryl, and preferably Ar ² Selected from C ₆ Aryl groups.

According to one embodiment of the benzodiphenylfluorene compounds, wherein Ar for formula (Ic) ¹ Selected from substituted or unsubstituted C ₆ To C ₁₃ Aryl and substituted or unsubstituted C ₁₂ Heteroaryl, preferably Ar ¹ Selected from substituted C ₆ To C ₁₃ An aryl group; and for formula (Id), ar ² Selected from C ₆ To C ₁₀ Aryl, and preferably Ar ² Selected from C ₆ Aryl groups.

Ar、Ar ¹ And/or Ar ²

According to one embodiment of the benzodiphenylfluorene compound, wherein Ar, ar ¹ And/or Ar ² A group selected from B1 to B13:

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wherein asterisks indicate Ar, ar ¹ And/or Ar ² Is a combination of the binding sites of the above.

According to one embodiment of the benzodiphenylfluorene compound, wherein Ar ¹ Selected from B1 to B12, preferably from B1, B2, B3, B4, B5, B6, and also preferably from B1, B2, B3.

According to one embodiment of the benzodiphenylfluorene compound, wherein

Ar ² Selected from B1 to B12, preferably from B1, B2, B3, B4, B5, B6, and also preferably from B1, B2, B3.

According to one embodiment of the benzodiphenylfluorene compound, wherein

Ar ¹ Selected from B1 to B12, preferably from B1, B2, B3, B4, B5, B6, further preferably from B1, B2, B3; and/or

Ar ⁴

According to one embodiment of the benzodiphenylfluorene compound, wherein Ar ⁴ A group selected from D1 to D7:

wherein asterisks indicate Ar ⁴ Is a combination of the binding sites of the above.

If (If)

According to one embodiment, the benzodiphenylfluorene compound of formula I is represented by formula If:

wherein the method comprises the steps of

R ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl, C ₅ To C ₁₂ Heteroaryl;

R ^j 、R ^k 、R ^l and R is ^m Independently represents a single bond, provided that N of formula (If) is bonded to R ^j 、R ^k 、R ^l And R is ^m ；

R ^a 、R ^b 、R ^c And R is ^d Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ A heteroaryl group, which is a group,

R ^a 、R ^b 、R ^c and R is ^d Independently represents a single bond, provided that N of formula (If) is bonded to R ^a 、R ^b 、R ^c And R is ^d ；

Wherein the method comprises the steps of

When R is ^a 、R ^b 、R ^c And R is ^d When two of them are adjacent to each other, R ^a 、R ^b 、R ^c And R is ^d Can form a substituted or unsubstituted condensed ring system;

x is selected from O, S, NAr ² ；

Ar ² Selected from C ₆ To C ₁₂ An aryl group;

X ² selected from O, S, NAr ³ 、CR ³ R ⁴ And SiR ³ R ⁴ ；

R ³ And R is ⁴ Independently selected from C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl or C ₂ To C ₁₂ Heteroaryl; and is also provided with

Ar ³ Selected from C ₆ To C ₁₂ Aryl groups.

R of formula (If) ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q

According to one embodiment, R ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q C of (2) ₁ To C ₆ The alkyl group being capable of being C ₁ To C ₅ Alkyl, C ₁ To C ₄ Alkyl, C ₁ To C ₃ Alkyl, C ₁ To C ₂ Alkyl or C ₁ An alkyl group.

According to one embodiment, R ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q C of (2) ₆ To C ₁₈ Aryl can be C ₆ To C ₁₆ Aryl, C ₆ To C ₁₄ Aryl, C ₆ To C ₁₂ Aryl, C ₆ To C ₁₀ Aryl or C ₆ Aryl groups.

According to one embodiment, R ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q C of (2) ₂ To C ₁₈ Heteroaryl can be C ₃ To C ₁₈ Heteroaryl, C ₄ To C ₁₈ Heteroaryl, C ₅ To C ₁₈ Heteroaryl, C ₅ To C ₁₇ Heteroaryl, C ₅ To C ₁₆ Heteroaryl, C ₅ To C ₁₅ Heteroaryl, C ₅ To C ₁₄ Heteroaryl, C ₅ To C ₁₃ Heteroaryl, C ₅ To C ₁₂ Heteroaryl, C ₅ To C ₁₁ Heteroaryl, C ₅ To C ₁₀ Heteroaryl or C ₅ To C ₁₉ Heteroaryl groups.

According to one embodiment, R ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q Independently selected from H, C ₁ To C ₆ Alkyl and C ₆ To C ₁₈ Aryl groups.

X of formula (If)

According to one embodiment, wherein X is selected from O, S, NAr ² 。

X of formula (If) ²

According to one embodiment, wherein X ² Selected from O, NAr ³ 、CR ³ R ⁴ And SiR ³ R ⁴ . According to one embodiment, wherein X ² Selected from O, CR ³ R ⁴ And SiR ³ R ⁴ . According to one embodiment, wherein X ² Selected from CR ³ R ⁴ And SiR ³ R ⁴ . According to one embodiment, wherein X ² Selected from CR ³ R ⁴ 。

R of formula (If) ³ And R is ⁴

According to one embodiment, R ³ And R is ⁴ C of (2) ₁ To C ₆ The alkyl group being capable of being C ₁ To C ₅ Alkyl, preferably C ₁ To C ₄ Alkyl, more preferably C ₁ To C ₃ Alkyl, still more preferably C ₁ To C ₂ Alkyl or most preferably C ₁ An alkyl group. According to one embodiment, R ³ And R is ⁴ C of (2) ₆ To C ₁₂ Aryl can be C ₆ To C ₁₀ Aryl, and preferably C ₆ An alkyl group. According to one embodiment, R ³ And R is ⁴ C of (2) ₂ To C ₁₂ Heteroaryl can be C ₃ To C ₁₂ Heteroaryl, C ₄ To C ₁₂ Heteroaryl, C ₅ To C ₁₂ Heteroaryl, C ₅ To C ₁₁ Heteroaryl, C ₅ To C ₁₀ Heteroaryl or C ₅ To C ₉ Heteroaryl groups. According to one embodiment, R ³ And R is ⁴ Independently selected from C ₁ To C ₆ Alkyl, preferably C ₁ To C ₅ Alkyl, more preferably C ₁ To C ₄ Alkyl, more preferably C ₁ To C ₃ Alkyl, still more preferably C ₁ To C ₂ Alkyl or most preferably C ₁ An alkyl group.

Ar of formula (If) ³

According to one embodiment, ar ³ Selected from C ₆ To C ₁₀ Aryl groups. According to one embodiment, ar ³ Selected from C ₆ Aryl groups.

(Ig)

According to one embodiment, the compound of formula I is represented by formula Ig:

wherein the method comprises the steps of

R ^j 、R ^k 、R ^l and R is ^m Independently represents a single bond, provided that N of formula (Ig) is bonded to R ^j 、R ^k 、R ^l And R is ^m ；

R ^a 、R ^b 、R ^c and R is ^d Independently represents a single bond, provided that N of formula (Ig) is bonded to R ^a 、R ^b 、R ^c And R is ^d ；

x is selected from O, S, NAr ² ；

Ar ² Selected from C ₆ To C ₁₂ An aryl group;

X ² selected from O, S, NAr ³ 、CR ³ R ⁴ And SiR ³ R ⁴ ；

Ar ³ Selected from C ₆ To C ₁₂ Aryl groups.

R of formula (Ig) ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q

According to one embodiment, R ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q C of (2) ₆ To C ₁₂ Aryl can be C ₆ To C ₁₀ Aryl, C ₆ To C ₈ Aryl or C ₆ Aryl groups.

According to one embodiment, R ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q C of (2) ₅ To C ₁₂ Heteroaryl can be C ₅ To C ₁₆ Heteroaryl, C ₅ To C ₁₄ Heteroaryl, C ₅ To C ₁₂ Heteroaryl, C ₅ To C ₁₀ Heteroaryl, C ₅ To C ₈ Heteroaryl or C ₅ Heteroaryl groups.

According to one embodiment, R ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl or C ₅ To C ₁₂ Heteroaryl groups.

X of formula (Ig)

According to one embodiment, wherein X is selected from O, S, NAr ² 。

X of formula (Ig) ²

R of formula (Ig) ³ And R is ⁴

Ar of formula (Ig) ³

Ih (Ih)

According to one embodiment, the compound of formula I is represented by formula Ih:

wherein the method comprises the steps of

R ^j 、R ^k 、R ^l and R is ^m Independently represents a single bond, provided that N of formula (Ih) is bonded to R ^j 、R ^k 、R ^l And R is ^m ；

R ^a 、R ^b 、R ^c and R is ^d Independently represents a single bond, provided that N in formula (Ih) is bonded to R ^a 、R ^b 、R ^c And R is ^d ；

at least one of the condensed ring systemsThe substituents are independently selected from C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl or C ₂ To C ₁₂ Heteroaryl;

x is selected from O, S, NAr ² The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with

Ar ² Selected from C ₆ To C ₁₂ Aryl groups.

According to another embodiment, the compound of formula I is represented by formula (Ih),

wherein the method comprises the steps of

wherein R is ^a 、R ^b 、R ^c And R is ^d Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ A heteroaryl group, which is a group,

at least one substituent on the condensed ring system is independently selected from C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl or C ₂ To C ₁₂ Heteroaryl groupA base;

Ar ² Selected from C ₆ To C ₁₂ Aryl groups.

R of formula (Ih) ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q

According to one embodiment, R ^j 、R ^k 、R ^l 、R ^m 、R ⁿ 、R ^o 、R ^p And R is ^q Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl, C ₅ To C ₁₂ Heteroaryl groups.

X of formula (Ih)

According to one embodiment, wherein X is selected from O, S, NAr ² 。

Ar of formula (Ih) ³

According to one embodiment, ar ³ Selected from C ₆ To C ₁₂ Aryl or C ₆ To C ₁₀ Aryl groups. According to one embodiment, ar ³ Selected from C ₆ Aryl groups.

(Ik)

According to one embodiment, the compound of formula I is represented by formula Ik:

wherein the method comprises the steps of

Ar ^1b Selected from C ₆ To C ₁₂ Aryl or C ₅ To C ₂₅ Heteroaryl;

R ^a2 、R ^b2 、R ^c2 and R is ^d2 Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ A heteroaryl group, which is a group,

R ^a2 、R ^b2 、R ^c2 and R is ^d2 Independently represents a single bond, provided that N of formula (Ik) is bonded to R ^a2 、R ^b2 、R ^c2 And R is ^d2 ；

When R is ^a2 、R ^b2 、R ^c2 And R is ^d2 When two of them are adjacent to each other, R ^a2 、R ^b2 、R ^c2 And R is ^d2 Can form a substituted or unsubstituted condensed ring system;

X ^1b selected from O, S, NAr ^2b 、CR ^1b R ^2b 、SiR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

wherein the method comprises the steps of

Ar ^1b Selected from C ₆ To C ₁₂ Aryl or C ₅ To C ₂₅ Heteroaryl;

X ^1b selected from O, S, NAr ^2b And CR (CR) ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

wherein the method comprises the steps of

Ar ^1b Selected from biphenyl groups;

X ^1b selected from O, S, NAr ^2b 、CR ^1b R ^2b And SiR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

wherein the method comprises the steps of

Ar ^1b Selected from biphenyl groups;

X ^1b selected from O, S, NAr ^2b And CR (CR) ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik comprises from 50 to 80 carbon atoms.

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik comprises from 50 to 75 carbon atoms.

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik comprises from 50 to 70 carbon atoms.

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik comprises from 55 to 65 carbon atoms.

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik comprises from 55 to 61 carbon atoms.

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik comprises from 10 to 13 rings.

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik comprises 10 to 12 rings.

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik comprises 11 to 12 rings.

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik has a glass transition temperature with a Tg of ≡130 ℃.

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik has a glass transition temperature of Tg > 135 ℃.

According to one embodiment, the compound of formula I, ia, ib, ic, id, ie, if, ig, ih, ik has a glass transition temperature of Tg. Gtoreq.140 ℃.

Compounds of formula I

According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A1 to a37:

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according to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A1 to a16 and a34 and a35 and a36 or A1 to a16 and a34 and a35 and a36 and a37. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A1 to a14, a34, a35 and/or a36. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from a17 to a33. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from a17 to a36. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A1 to A4 and a10 and a16. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A1 to a14 and a35 and a36. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A1 to a14. According to one embodiment of the benzodiphenylfluorene compounds of formula I wherein the compounds of formula I are selected from A1 to A8 and a11 to a14 and a35 and a36. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A1 to A8 and a11 to a14. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A1 to A8 and a11 to a14. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A3 to A8 and a14. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A3 to A8. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A1, A2, A9, a11, a14 and a34. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compound of formula I is selected from A1, A2, A9, a11, a14. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compounds of formula I are selected from A1, A2, a14 and a34 and a35 and a36. According to one embodiment of the benzodiphenylfluorene compounds of formula I, wherein the compound of formula I is selected from A1, A2 and a14.

Semiconductor layer

According to another embodiment, the semiconductor layer, preferably the organic semiconductor layer, comprises at least one benzodiphenylfluorene compound selected from the group consisting of: a formula I; or at least one benzodiphenylfluorene compound selected from the formula Ia, ib, ic, id, ie, if, ig, ih, ik according to the present invention.

According to another embodiment, wherein the organic semiconductor layer is a hole injection layer and/or a hole transport layer. According to another embodiment, wherein the organic semiconductor layer is a hole injection layer. According to another embodiment, wherein the organic semiconductor layer is a hole transport layer.

According to another embodiment, wherein the organic semiconductor layer further comprises an organic p-type dopant. According to another embodiment, wherein the organic semiconductor layer is a hole injection layer and/or a hole transport layer and further comprises an organic p-type dopant. According to another embodiment, wherein the organic semiconductor layer is a hole injection layer and further comprises an organic p-type dopant. According to another embodiment, wherein the organic semiconductor layer is a hole transport layer and further comprises an organic p-type dopant.

According to one embodiment, the organic semiconductor layer is arranged between the photoactive layer and the anode.

According to one embodiment, the organic semiconductor layer is selected from a hole transport layer and a hole injection layer.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, and wherein the organic semiconductor layer comprises an organic p-type dopant.

According to one embodiment, the organic semiconductor layer is arranged between the photoactive layer and the anode, and the organic semiconductor layer is selected from a hole transport layer and a hole injection layer.

According to one embodiment, the thickness of the organic semiconductor layer may be in the range of about 1nm to about 200nm, such as in the range of about 2nm to about 175nm or about 2nm to about 150 nm.

According to one embodiment, the organic semiconductor layer may include:

-at least about 0.5% to about 30% by weight, preferably about 0.5% to about 20% by weight and more preferably about 1% to about 15% by weight of a compound of formula (II); and

-at least about ≡70% to about +.99.5% by weight, preferably about +.80% to about +.99.5% by weight and more preferably about +.85% to about +.99% by weight of a compound of formula (I), (Ic), (Id), (Ie), (If), (Ig), (Ih) or (Ik); preferably, the weight% of the compound of formula (II) is lower than the weight% of the compound of formula (I), (Ic), (Id), (Ie), (If), (Ig), (Ih) or (Ik); wherein the weight% of the components is based on the total weight of the organic semiconductor layer.

According to one embodiment, the organic semiconductor layer is a hole injection layer having a thickness in the range of about 1nm to about 100nm, for example about 1nm to about 25 nm. When the thickness of the HIL is within this range, the HIL may have excellent hole injection characteristics without causing substantial damage to the driving voltage.

According to one embodiment, the organic semiconductor layer is a hole transport layer having a thickness in the range of about 5nm to about 250nm, preferably about 10nm to about 200nm, further about 20nm to about 190nm, further about 40nm to about 180nm, further about 60nm to about 170nm, further about 80nm to about 160nm, further about 100nm to about 160nm, further about 120nm to about 140 nm. One preferred thickness of the HTL may be 170nm to 200nm.

Organic electronic device

According to one embodiment, the organic electronic device is an Organic Light Emitting Diode (OLED), a light emitting device, a thin film transistor, a battery, a display device, an organic photovoltaic cell (OPV), a solar cell, preferably a perovskite solar cell, a photoconductor, a photodiode or a photodetector.

According to one embodiment, the organic electronic device is an electroluminescent device, a solar cell, preferably a perovskite solar cell, an organic photovoltaic cell, a photoconductor, a photodiode or a photodetector.

According to one embodiment, the organic electronic device is an Organic Light Emitting Diode (OLED), a light emitting device, a thin film transistor, a battery, a display device, an organic photovoltaic cell (OPV).

According to one embodiment, the organic electronic device is an electroluminescent device, a solar cell, preferably a perovskite solar cell, a photoconductor, a photodiode or a photodetector.

According to one embodiment, the organic electronic device is an electroluminescent device, a solar cell, preferably a perovskite solar cell, a photodiode or a photodetector.

According to one embodiment, the electronic device is an electroluminescent device, a solar cell, preferably a perovskite solar cell or a photodetector.

According to one embodiment, the organic electronic device comprises an organic p-type dopant.

Axis olefine compound

According to another embodiment, wherein the organic p-type dopant is a pivotable compound.

According to one embodiment, wherein the organic p-type dopant is a decenyl compound, wherein the decenyl compound is represented by formula (II):

wherein in formula (II)

A ¹ Independently selected from the group (1)

Ar ¹ Independently selected from substituted or unsubstituted C ₆ To C ₃₆ Aryl and substituted or unsubstituted C ₂ To C ₃₆ Heteroaryl;

if Ar is ¹ Is substituted, then one or more substituents are independently selected from electron withdrawing groups, F, CN, partially perfluorinated or perfluorinated alkyl, -NO ₂ ；

A ² And A ³ Independently selected from the group (2)

Ar ² And Ar is a group ³ Independently selected from substituted or unsubstituted C ₆ To C ₃₆ Aryl and substituted or unsubstituted C ₂ To C ₃₆ Heteroaryl; and

if Ar is ² And Ar is a group ³ Is substituted, then one or more substituents are independently selected from electron withdrawing groups, F, CN, partially perfluorinated or perfluorinated alkyl, -NO ₂ ；

Each R' is independently selected from electron withdrawing groups.

According to one embodiment, ar ¹ C of (2) ₆ To C ₃₆ The aryl groups can be selected from C ₆ To C ₃₆ Aryl, C ₆ To C ₃₀ Aryl, C ₆ To C ₂₆ Aryl, C ₆ To C ₃₄ Aryl, C ₆ To C ₂₂ Aryl, C ₆ To C ₂₀ Aryl, C ₆ To C ₁₈ Aryl, C ₆ To C ₁₆ Aryl, C ₆ To C ₁₄ Aryl, C ₆ To C ₁₂ Aryl or C ₆ To C ₁₀ Aryl groups.

According to one embodiment, ar ¹ C of (2) ₆ To C ₃₆ The aryl groups can be selected from C ₆ To C ₃₆ Heteroaryl, C ₆ To C ₃₀ Heteroaryl, C ₆ To C ₂₆ Heteroaryl, C ₆ To C ₃₄ Heteroaryl, C ₆ To C ₂₂ Heteroaryl, C ₆ To C ₂₀ Heteroaryl, C ₆ To C ₁₈ Heteroaryl, C ₆ To C ₁₆ Heteroaryl, C ₆ To C ₁₄ Heteroaryl, C ₆ To C ₁₂ Heteroaryl or C ₆ To C ₁₀ Heteroaryl groups.

According to one embodiment, ar ¹ Independently selected from substituted or unsubstituted C ₆ To C ₂₄ Aryl and substituted or unsubstituted C ₂ To C ₂₄ Heteroaryl groups.

According to one embodiment, ar ¹ Independently selected from substituted or unsubstituted C ₆ To C ₁₈ Aryl and substituted or unsubstituted C ₂ To C ₁₈ Heteroaryl groups.

According to one embodiment, ar ¹ Independently selected from substituted or unsubstituted C ₆ To C ₁₂ Aryl and substituted or unsubstituted C ₂ To C ₁₂ Heteroaryl groups.

According to one embodiment, ar ¹ Can be selected from F, CN, partially perfluorinated or perfluorinated alkyl or-NO ₂ 。

According to one embodiment, ar ¹ Can be selected from F, CN or partially perfluorinated or perfluorinated alkyl groups.

According to one embodiment, ar ¹ Can be selected from F, CN or CF ₃ 。

According to one embodiment, ar ² C of (2) ₆ To C ₃₆ The aryl groups can be independently selected from C ₆ To C ₃₆ Aryl, C ₆ To C ₃₀ Aryl, C ₆ To C ₂₆ Aryl group,C ₆ To C ₃₄ Aryl, C ₆ To C ₂₂ Aryl, C ₆ To C ₂₀ Aryl, C ₆ To C ₁₈ Aryl, C ₆ To C ₁₆ Aryl, C ₆ To C ₁₄ Aryl, C ₆ To C ₁₂ Aryl or C ₆ To C ₁₀ Aryl groups.

According to one embodiment, ar ² C of (2) ₆ To C ₃₆ The aryl groups can be independently selected from C ₆ To C ₃₆ Heteroaryl, C ₆ To C ₃₀ Heteroaryl, C ₆ To C ₂₆ Heteroaryl, C ₆ To C ₃₄ Heteroaryl, C ₆ To C ₂₂ Heteroaryl, C ₆ To C ₂₀ Heteroaryl, C ₆ To C ₁₈ Heteroaryl, C ₆ To C ₁₆ Heteroaryl, C ₆ To C ₁₄ Heteroaryl, C ₆ To C ₁₂ Heteroaryl or C ₆ To C ₁₀ Heteroaryl groups.

According to one embodiment, ar ² Independently selected from substituted or unsubstituted C ₆ To C ₂₄ Aryl and substituted or unsubstituted C ₂ To C ₂₄ Heteroaryl groups.

According to one embodiment, ar ² Independently selected from substituted or unsubstituted C ₆ To C ₁₈ Aryl and substituted or unsubstituted C ₂ To C ₁₈ Heteroaryl groups.

According to one embodiment, ar ² Independently selected from substituted or unsubstituted C ₆ To C ₁₂ Aryl and substituted or unsubstituted C ₂ To C ₁₂ Heteroaryl groups.

According to one embodiment, ar ² Can be independently selected from F, CN, partially perfluorinated or perfluorinated alkyl or-NO ₂ 。

According to one embodiment, ar ² Can be independently selected from F, CN or partially perfluorinated or perfluorinated alkyl.

According to one embodiment, ar ² Can be independently selected from F,CN or CF ₃ 。

According to one embodiment, the electron withdrawing group of R' can be selected from CN, partially fluorinated or perfluorinated C ₁ To C ₆ Alkyl groups, preferably selected from CF ₃ 、NO ₂ Or F.

According to one embodiment, the electron withdrawing group of R' can be selected from CF ₃ F or CN.

According to one embodiment, the electron withdrawing group of R' can be selected from CF ₃ Or CN.

According to one embodiment, the electron withdrawing group of R' can be selected from CN.

According to one embodiment, the compound of formula (III) is selected from the group consisting of compounds of formula (III)

Wherein B is ¹ Selected from Ar ¹

Wherein B is ³ And B ⁵ Independently selected from Ar ² 。

According to one embodiment of the invention, B ³ And B ⁵ Ar is selected from the group consisting of substituted and unsubstituted C ₆ To C ₁₂ Aryl and substituted or unsubstituted C ₃ To C ₁₂ Heteroaryl, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C ₁ To C ₄ Alkyl, halogen, F; preferably Ar is selected from substituted phenyl, pyridyl, pyrimidinyl or triazinyl, wherein the substituents on Ar are independently selected from CN, CF ₃ Or F.

According to one embodiment of the invention, B ² 、B ⁴ And B ⁶ R' is selected from CN, partially or perfluorinated C ₁ To C ₄ Alkyl, -NO ₂ C, partially or perfluorinated ₁ To C ₄ Alkoxy, substituted or unsubstituted C ₆ To C ₁₂ Aryl or C ₃ To C ₁₂ Heteroaryl, wherein the substituents are selected from halogen, F, cl, CN, partially or fully fluorinated C ₁ To C ₄ Alkyl, partially or fully fluorinatedChemical C ₁ To C ₄ An alkoxy group; more preferably R ³ Selected from CN, CF ₃ 、OCF ₃ Or F, most preferably CN.

According to one embodiment, the organic semiconductor layer comprises a composition comprising a compound of formula (V) and at least one compound of formulas (Va) to (Vd)

/>

According to one embodiment, the compound of formula (III) comprises less than nine cyano moieties.

According to one embodiment, the compound of formula (III) comprises 3 to 8 cyano moieties.

According to one embodiment, the compound of formula (III) comprises 6 to 8 cyano moieties.

According to one embodiment of the invention, ar ¹ Selected from (IVa)

Wherein in formula (IVa)

X ¹ Selected from CR ¹ Or N;

X ² selected from CR ² Or N;

X ³ selected from CR ³ Or N;

X ⁴ selected from CR ⁴ Or N;

X ⁵ selected from CR ⁵ Or N;

R ¹ 、R ² 、R ³ 、R ⁴ and R is ⁵ Independently selected from electron withdrawing groups, CN, partially fluorinated C, if present ₁ To C ₈ Alkyl, perfluorinated C ₁ To C ₈ Alkyl, -NO ₂ Halogen, cl, F, D or H, where R is ¹ 、R ² 、R ³ 、R ⁴ And R is ⁵ When any one of them is present, then the corresponding X ¹ 、X ² 、X ³ 、X ⁴ And X ⁵ Is not N;

wherein asterisks indicate binding sites.

According to one embodiment of the invention, ar ² And Ar is a group ³ Independently selected from formula (IVb)

Wherein in formula (IVb)

X ¹ ' selected from CR ¹ ' or N;

X ² ' selected from CR ² ' or N;

X ³ ' selected from CR ³ ' or N;

X ⁴ ' selected from CR ⁴ ' or N;

X ⁵ ' selected from CR ⁵ ' or N;

R ¹ '、R ² '、R ³ '、R ⁴ ' and R ⁵ ' (if present) is independently selected from electron withdrawing groups, CN, partially fluorinated C ₁ To C ₈ Alkyl, perfluorinated C ₁ To C ₈ Alkyl, -NO ₂ Halogen, cl, F, D or H, where R is ¹ '、R ² '、R ³ '、R ⁴ ' and R ⁵ When any of' is present, then the corresponding X ¹ '、X ² '、X ³ '、X ⁴ ' and X ⁵ ' is not N;

wherein asterisks indicate binding sites.

According to one embodiment, ar ¹ Selected from the group consisting of

/>

Wherein asterisks indicate binding sites.

According to one embodiment, ar ¹ 、Ar ² And Ar is a group ³ Independently selected from G1 to G55.

According to one embodiment, the organic semiconductor layer, the stack of organic layers, and/or the organic electronic device does not comprise bipyrazino [2,3-f:2',3' -h ] quinoxaline-2, 3,6,7,10, 11-Hexanitrile (HATCN), or the like. According to one embodiment, the organic semiconductor layer, the stack of organic layers and/or the organic electronic device does not comprise bipyrazino [2,3-f:2',3' -h ] quinoxaline-2, 3,6,7,10, 11-Hexanitrile (HATCN).

According to one embodiment, the organic semiconductor layer, the stack of organic layers and/or the organic electronic device does not comprise a bipyrazino [2,3-F:2',3' -h ] quinoxaline-2, 3,6,7,10, 11-Hexanitrile (HATCN) or a similar 2,2'- (2, 5-cyclohexadiene-1, 4-diyl) bipropiodinitrile (TCNQ) or 2,2' - (perfluorocyclohexa-2, 5-diene-1, 4-diyl) dipropylene dinitrile (F4-TCNQ). According to one embodiment, the organic semiconductor layer, the stack of organic layers and/or the organic electronic device does not comprise a bipyrazino [2,3-F:2',3' -h ] quinoxaline-2, 3,6,7,10, 11-Hexanitrile (HATCN), 2'- (2, 5-cyclohexadiene-1, 4-diyl) bipropiodinitrile (TCNQ) or 2,2' - (perfluorocyclohexa-2, 5-diene-1, 4-diyl) dipropylene dinitrile (F4-TCNQ).

According to one embodiment, the organic semiconductor layer, the stack of organic layers and/or the organic electronic device does not comprise a bipyrazino [2,3-F:2',3' -h ] quinoxaline-2, 3,6,7,10, 11-Hexanitrile (HATCN) or a similar 2,2' - (2, 5-cyclohexadiene-1, 4-diyl) bipropiodinitrile (TCNQ), 2' - (perfluorocyclohexa-2, 5-diene-1, 4-diyl) dipropylene dinitrile (F4-TCNQ) or 2,2' - (1, 3,4,5,7, 8-hexafluoro-2, 6-naphthalenediyl) bis [ malononitrile ] (F6-TCNNQ). According to one embodiment, the organic semiconductor layer, the stack of organic layers and/or the organic electronic device does not comprise a bipyrazino [2,3-F:2',3' -h ] quinoxaline-2, 3,6,7,10, 11-Hexanitrile (HATCN), 2' - (2, 5-cyclohexadiene-1, 4-diyl) dipropylene dinitrile (TCNQ), 2' - (perfluorocyclohexane-2, 5-diene-1, 4-diyl) dipropylene dinitrile (F4-TCNQ) or 2,2' - (1, 3,4,5,7, 8-hexafluoro-2, 6-naphthalenediyl) bis [ malononitrile ] (F6-TCNQ).

Any of the specifications of formula (I) described above in the context of an organic electronic device apply mutatis mutandis.

Organic semiconductor layer

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, and wherein the organic electronic device comprises a further organic semiconductor layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, and wherein the organic electronic device further comprises a hole injection layer, preferably comprising an organic p-type dopant, and more preferably comprising an organic p-type dopant and a host compound.

According to one embodiment, the organic semiconductor layer is a hole transport layer and the organic electronic device comprises a further organic semiconductor layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound.

According to one embodiment, the organic semiconductor layer is a hole transport layer, and the organic electronic device further comprises a hole injection layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, wherein the organic semiconductor layer is a hole transport layer, and wherein the organic electronic device comprises a further organic semiconductor layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, wherein the organic semiconductor layer is a hole transport layer, and wherein the organic electronic device further comprises a hole injection layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, wherein the organic electronic device further comprises a hole injection layer, preferably comprising an organic p-type dopant, and wherein the hole injection layer adjoins the anode.

According to one embodiment, wherein the organic semiconductor layer is a hole transport layer, wherein the organic electronic device further comprises a hole injection layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound, and wherein the hole injection layer adjoins the anode.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, wherein the organic semiconductor layer is a hole transport layer, and wherein the organic electronic device comprises a further organic semiconductor layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound, wherein the hole injection layer adjoins the anode.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, wherein the organic semiconductor layer is a hole transport layer, and wherein the organic electronic device further comprises a hole injection layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound, wherein the hole injection layer adjoins the anode.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, wherein the organic electronic device further comprises a hole injection layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound, and wherein the hole injection layer is in direct contact with the anode.

According to one embodiment, wherein the organic semiconductor layer is a hole transport layer, wherein the organic electronic device further comprises a hole injection layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound, and wherein the hole injection layer is in direct contact with the anode.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, wherein the organic semiconductor layer is a hole transport layer, and wherein the organic electronic device further comprises a hole injection layer, preferably comprising an organic p-type dopant and more preferably comprising an organic p-type dopant and a host compound, wherein the hole injection layer is in direct contact with the anode.

Preferably, the host compound is a hole transporting material.

According to one embodiment, the organic electronic device comprises a hole injection layer, wherein the hole injection layer comprises a compound of formula (I) or (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih) and (Ik).

According to one embodiment, the organic electronic device further comprises a hole injection layer, wherein the hole injection layer comprises a compound of formula (I) or (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih) and (Ik) and an organic p-type dopant.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, wherein the organic semiconductor layer is a hole injection layer, and wherein the organic semiconductor layer comprises an organic p-type dopant.

The Hole Injection Layer (HIL) may be formed on the anode layer by vacuum deposition, spin coating, printing, casting, slot die coating, langmuir-Blodgett (LB) deposition, or the like. When using vacuum deposition to form HIL, the deposition conditions may be dependent on the compound used to form the HIL and the desired structural and thermal properties of the HILAnd (3) a change. However, in general, the conditions of vacuum deposition may include a deposition temperature of 100 to 500 ℃, 10 ° ^-8 To 10 ^-3 A pressure of torr (1 torr equals 133.322 Pa) and a deposition rate of 0.1 to 10 nm/sec.

When spin coating or printing is used to form the HIL, the coating conditions may vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, the coating conditions may include a coating speed of about 2000rpm to about 5000rpm and a heat treatment temperature of about 80 ℃ to about 200 ℃. After the coating, a heat treatment is performed to remove the solvent.

The HIL may be formed from any compound commonly used to form HIL. Examples of compounds that may be used to form the HIL include phthalocyanine compounds such as copper phthalocyanine (CuPc), 4' -tris (3-methylphenyl phenylamino) triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), and polyaniline/poly (4-styrenesulfonate (PANI/PSS).

The HIL may comprise or consist of p-type dopants and the p-type dopants may be selected from: tetrafluoro-tetracyanoquinodimethane (F4 TCNQ), 2'- (perfluoronaphthalene-2, 6-diyl) dipropylenedinitrile, or 2,2',2"- (cyclopropane-1, 2, 3-diyl) tris (2- (p-cyanotetrafluorophenyl) acetonitrile), but is not limited thereto. The HIL may be selected from hole transporting host compounds doped with p-type dopants. Typical examples of known doped hole transport materials are: copper phthalocyanine (CuPc) doped with tetrafluoro-tetracyanoquinodimethane (F4 TCNQ), the HOMO level of the copper phthalocyanine (CuPc) being about-5.2 eV and the LUMO level of the tetrafluoro-tetracyanoquinodimethane (F4 TCNQ) being about-5.2 eV; zinc phthalocyanine doped with F4TCNQ (ZnPc) (homo= -5.2 eV); α -NPD doped with F4TCNQ (N, N '-bis (naphthalen-1-yl) -N, N' -bis (phenyl) -benzidine); alpha-NPD doped with 2,2' - (perfluoronaphthalene-2, 6-diyl) dipropyldinitrile. The concentration of the p-type dopant can be selected from 1 to 20 wt%, more preferably from 3 to 10 wt%.

The thickness of the HIL may be in the range of about 1nm to about 100nm, and for example in the range of about 1nm to about 25 nm. When the thickness of the HIL is within this range, the HIL may have excellent hole injection characteristics without causing substantial damage to the driving voltage.

Basic covalent matrix compounds

The organic semiconductor layer or the organic electronic device may further comprise a covalent matrix compound, also referred to as a "basic covalent matrix compound". Preferably, the covalent matrix compound is a hole transporting compound preferably used in the hole injection layer and/or the hole transporting layer.

According to one embodiment, the substantially covalent matrix compound may be selected from at least one organic compound. The substantially covalent matrix may consist essentially of covalently bound C, H, O, N, S, which optionally additionally comprises covalently bound B, P, as and/or Se.

According to one embodiment of the organic electronic device, the organic semiconductor layer further comprises a basic covalent matrix compound, wherein the basic covalent matrix compound may be selected from organic compounds consisting essentially of covalently bound C, H, O, N, S, optionally additionally comprising covalently bound B, P, as and/or Se.

Organometallic compounds comprising a covalent bond carbon-metal, metal complexes comprising an organic ligand, and metal salts of organic acids are also examples of organic compounds that can be used as the basic covalent matrix compound of the hole injection layer.

In one embodiment, the substantially covalent matrix compound lacks metal atoms and a substantial portion of its backbone atoms may be selected from C, O, S, N. Alternatively, the substantially covalent matrix compound lacks metal atoms and a substantial portion of its backbone atoms may be selected from C and N.

According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of 400 and 2000g/mol or more, preferably 450 and 1500g/mol or less, more preferably 500 and 1000g/mol or less, more preferably 550 and 900g/mol or more, more preferably 600 and 800g/mol or less.

Preferably, the substantially covalent matrix compound comprises at least one aryl amine moiety or diarylamine moiety or triarylamine moiety.

Preferably, the substantially covalent matrix compound is free of metal and/or ionic bonds.

Compounds of formula (VI) or (VII)

According to another aspect of the invention, the at least one matrix compound, also referred to as "substantially covalent matrix compound", may comprise at least one arylamine compound, diarylamine compound, triarylamine compound, compound of formula (VI), or compound of formula (VII):

Wherein:

T ¹ 、T ² 、T ³ 、T ⁴ and T ⁵ Independently selected from a single bond, a benzene subunit, a biphenyl subunit, a terphenyl subunit or a naphthalene subunit, preferably a single bond or a benzene subunit;

T ⁶ is benzene subunit, biphenyl subunit, terphenyl subunit or naphthalene subunit;

Ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ and Ar is a group ⁵ Independently selected from: substituted or unsubstituted C ₆ To C ₂₀ Aryl or substituted or unsubstituted C ₃ To C ₂₀ Heteroaryl subunit, substituted or unsubstituted biphenyl subunit, substituted or unsubstituted fluorene, substituted 9-fluorene, substituted 9, 9-fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted benzidine, substituted or unsubstituted tetracene, substituted or unsubstituted benzo (a) anthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo [ b, f]]Azepine, substituted or unsubstituted 9,9' -spirobis [ fluorene ]]Substituted or unsubstituted spiro [ fluorene-9, 9' -xanthenes]The method comprises the steps of carrying out a first treatment on the surface of the Or substituted or unsubstituted aromaticA fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group consisting of substituted or unsubstituted non-heterocyclic, substituted or unsubstituted hetero 5-membered, substituted or unsubstituted 6-membered and/or substituted or unsubstituted 7-membered rings, substituted or unsubstituted fluorenes; or a fused ring system comprising 2 to 6 substituted or unsubstituted 5 to 7 membered rings, and said rings are selected from: (i) an unsaturated 5-to 7-membered ring of a heterocycle; (ii) a 5 to 6 membered ring of an aromatic heterocycle; (iii) a non-heterocyclic unsaturated 5-to 7-membered ring; (iv) an aromatic non-heterocyclic 6-membered ring;

Wherein the method comprises the steps of

Ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ And Ar is a group ⁵ The substituents of (a) are identically or differently selected from: H. d, F, C (-O) R ² 、CN、Si(R ² ) ₃ 、P(-O)(R ² ) ₂ 、OR ² 、S(-O)R ² 、S(-O) ₂ R ² A substituted or unsubstituted straight chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl or alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic ring system having 6 to 40 aromatic ring atoms and a substituted or unsubstituted heteroaromatic ring system having 5 to 40 aromatic ring atoms, unsubstituted C ₆ To C ₁₈ Aryl, unsubstituted C ₃ To C ₁₈ Heteroaryl, fused ring systems comprising 2 to 6 unsubstituted 5 to 7 membered rings and said rings are selected from: unsaturated 5-to 7-membered rings of heterocycles, 5-to 6-membered rings of aromatic heterocycles, unsaturated 5-to 7-membered rings of non-heterocycles and 6-membered rings of aromatic non-heterocycles,

wherein R is ² Can be selected from H, D, straight-chain alkyl having 1 to 6 carbon atoms, branched-chain alkyl having 1 to 6 carbon atoms, cyclic alkyl having 3 to 6 carbon atoms, alkenyl or alkynyl having 2 to 6 carbon atoms, C ₆ To C ₁₈ Aryl or C ₃ To C ₁₈ Heteroaryl groups.

According to one embodiment, wherein T ¹ 、T ² 、T ³ 、T ⁴ And T ⁵ May be independently selected from a single bond, a benzene subunit, a biphenyl subunit, or a terphenyl subunit. According to one embodiment, wherein T ¹ 、T ² 、T ³ 、T ⁴ And T ⁵ May be independently selected from the group consisting of a benzene subunit, a biphenyl subunit or a terphenyl subunit and T ¹ 、T ² 、T ³ 、T ⁴ And T ⁵ One of which is a single bond. According to one embodiment, wherein T ¹ 、T ² 、T ³ 、T ⁴ And T ⁵ May be independently selected from benzene or biphenyl subunits and T ¹ 、T ² 、T ³ 、T ⁴ And T ⁵ One of which is a single bond. According to one embodiment, wherein T ¹ 、T ² 、T ³ 、T ⁴ And T ⁵ May be independently selected from benzene or biphenyl subunits and T ¹ 、T ² 、T ³ 、T ⁴ And T ⁵ Is a single bond.

According to one embodiment, wherein T ¹ 、T ² And T ³ May be independently selected from benzene subunits and T ¹ 、T ² And T ³ One of which is a single bond. According to one embodiment, wherein T ¹ 、T ² And T ³ May be independently selected from benzene subunits and T ¹ 、T ² And T ³ Is a single bond.

According to one embodiment, wherein T ⁶ May be benzene subunit, biphenyl subunit or terphenyl subunit. According to one embodiment, wherein T ⁶ May be a benzene subunit. According to one embodiment, wherein T ⁶ May be a biphenylene group. According to one embodiment, wherein T ⁶ May be a terphenylene group.

According to one embodiment, wherein Ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ And Ar is a group ⁵ May be independently selected from D1 to D16:

wherein asterisks indicate binding sites.

According to one embodiment, wherein Ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ And Ar is a group ⁵ May be independently selected from D1 to D15; or from D1 to D10 and D13 to D15.

According to one embodiment, wherein Ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ And Ar is a group ⁵ May be independently selected from D1, D2, D5, D7, D9, D10, D13 to D16.

When Ar is ¹ 、Ar ² 、Ar ³ 、Ar ⁴ And Ar is a group ⁵ When selected within this range, the standard starting temperature may be within a range that is particularly suitable for mass production.

The "matrix compound of formula (VI) or formula (VII)" may also be referred to as "hole transporting compound".

According to one embodiment, the basic covalent matrix compound comprises at least one naphthyl group, carbazole group, dibenzofuran group, dibenzothiophene group and/or substituted fluorenyl group, wherein the substituents are independently selected from methyl, phenyl or fluorenyl groups.

According to one embodiment of the electronic device, wherein the matrix compound of formula (VI) or formula (VII) is selected from F1 to F18:

/>

according to one embodiment, the electronic organic device is an electroluminescent device, preferably an organic light emitting diode.

According to a preferred embodiment, the organic electronic device is an electroluminescent device, preferably an organic light emitting diode, wherein light is emitted through the cathode layer.

The invention also relates to a display device comprising an organic electronic device according to the invention.

According to a preferred embodiment, the display device comprises an organic electronic device according to the invention, wherein the cathode layer is transparent.

Other layers

According to the invention, the organic electronic device may comprise further layers in addition to the layers already mentioned above. Exemplary embodiments of the various layers are described below:

substrate

The substrate may be any substrate commonly used in the manufacture of electronic devices such as organic light emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate may be either a transparent or an opaque material, such as a glass substrate, a plastic substrate, a metal substrate, a silicon substrate, or a back plate.

Electrode

In one embodiment, the first electrode is transparent. In another embodiment, the second electrode is transparent. In one other embodiment, the transparent electrode material is a Thin Conductive Oxide (TCO). In another embodiment, the transparent electrode material is selected from Indium Tin Oxide (ITO), fluorine doped thin oxide (FTO), aluminum Zinc Oxide (AZO), indium Gallium Zinc Oxide (IGZO), indium Zinc Oxide (IZO), molybdenum Zinc Oxide (MZO), and Indium Molybdenum Oxide (IMO).

In another embodiment, the transparent electrode material is selected from magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), silver (Ag), gold (Au), and the like.

According to one embodiment, wherein the second electrode comprises at least one metal, wherein the metal is selected from Al, ag, au, ti, pt, cr, zn, sn, sr, in, sc, hf or a mixture thereof.

According to one embodiment, the first electrode is an anode and the second electrode is a cathode. According to one embodiment, the first electrode is a cathode and the second electrode is an anode.

Anode layer

The anode layer may be formed by depositing or sputtering a material for forming the anode layer. The material used to form the anode layer may be a high work function material to facilitate hole injection. The anode material may also be selected from low work function materials (i.e., aluminum). The anode electrode may be a transparent or reflective electrode. Transparent conductive oxides such as Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) ₂ ) An aluminum zinc oxide (AlZO) and zinc oxide (ZnO) to form an anode electrode. The anode layer may also be formed using a metal, typically silver (Ag), gold (Au), or a metal alloy.

P-type charge generation layer

The p-type charge generation layer may be formed on the anode layer or the cathode layer by vacuum deposition, spin coating, printing, casting, slot die coating, langmuir-Blodgett (LB) deposition, or the like. When vacuum deposition is used to form the p-type charge generation layer, the deposition conditions may vary depending on the compound used to form the layer and the desired structural and thermal properties of the layer. However, in general, the conditions of vacuum deposition may include a deposition temperature of 100 to 350 ℃, 10 ° ^-8 To 10 ^-3 A pressure of torr (1 torr equals 133.322 Pa) and a deposition rate of 0.1 to 10 nm/sec.

When the p-type charge generation layer is formed using spin coating or printing, the coating conditions may vary depending on the compound used to form the layer and the desired structure and thermal properties of the organic semiconductor layer. For example, the coating conditions may include a coating speed of about 2000rpm to about 5000rpm and a heat treatment temperature of about 80 ℃ to about 200 ℃. After the coating, a heat treatment is performed to remove the solvent.

n-type charge generation layer

The organic electronic device may include an n-type charge generation layer.

According to one embodiment, the n-type charge generating layer may comprise an n-CGL matrix compound, preferably comprising at least one C ₂ To C ₂₄ N-heteroaryl or a p=x group, wherein X is O, P, se, with p=o being particularly preferred.

According to one embodiment, at least one C ₂ To C ₂₄ The N-heteroaryl group may be selected from compounds comprising at least one azine group, preferably at least two azine groups, and also preferably three azine groups.

According to one embodiment, the n-type charge generating layer may comprise an n-CGL host compound comprising at least one group selected from the group consisting of: pyridine, pyrimidine, triazine, imidazole, benzimidazole, benzoOxazole, quinone, benzoquinone, quinoxaline, benzoquinoxaline, acridine, phenanthroline, benzacridine, dibenzoacridine.

According to one embodiment, the n-type charge generating layer may comprise an n-CGL matrix compound comprising at least one phenanthroline group, preferably two phenanthroline groups.

According to one embodiment, the n-type charge generating layer may comprise a metal dopant, wherein the metal dopant may be a metal selected from Li, na, cs, mg, ca, sr, S or Yb, preferably a metal selected from Li or Yb.

Hole injection layer

According to one embodiment, wherein the organic electronic device further comprises a hole injection layer in direct contact with the anode, wherein the organic semiconductor layer is arranged between the hole injection layer and the light emitting layer.

According to one embodiment, wherein the organic electronic device further comprises a hole injection layer in direct contact with the anode, wherein the organic semiconductor layer is arranged between the hole injection layer and the light emitting layer, and wherein the hole transport layer is in direct contact with the hole injection layer.

The Hole Injection Layer (HIL) may be formed on the anode layer by vacuum deposition, spin coating, printing, casting, slot die coating, langmuir-Blodgett (LB) deposition, or the like. When using vacuum deposition to form the HIL, the deposition conditions may vary depending on the compound used to form the HIL and the desired structural and thermal properties of the HIL. However, in general, the conditions of vacuum deposition may include a deposition temperature of 100 to 500 ℃, 10 ° ^-8 To 10 ^-3 A pressure of torr (1 torr equals 133.322 Pa) and a deposition rate of 0.1 to 10 nm/sec.

When spin coating or printing is used to form the HIL, the coating conditions may vary depending on the compound used to form the HIL and the desired structural and thermal properties of the HIL. For example, the coating conditions may include a coating speed of about 2000rpm to about 5000rpm and a heat treatment temperature of about 80 ℃ to about 200 ℃. After the coating, a heat treatment is performed to remove the solvent.

The HIL may be formed from any compound commonly used to form HIL. Examples of compounds that may be used to form the HIL include phthalocyanine compounds such as copper phthalocyanine (CuPc), 4' -tris (3-methylphenyl phenylamino) triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), and polyaniline/poly (4-styrenesulfonate) (PANI/PSS).

The HIL may comprise or consist of p-type dopants and the p-type dopants may be selected from: tetrafluoro-tetracyanoquinodimethane (F4 TCNQ), 2'- (perfluoronaphthalene-2, 6-diyl) dipropylenedinitrile, or 2,2',2"- (cyclopropane-1, 2, 3-diyl) tris (2- (p-cyanotetrafluorophenyl) acetonitrile), but is not limited thereto.

Preferably, the p-type dopant is selected from the group consisting of axial compounds such as 2,2' - (cyclopropane-1, 2, 3-trimethylene) tris (2- (p-cyanotetrafluorophenyl) acetonitrile) (CC 3).

The HIL may comprise a substantially covalent host compound and a p-type dopant.

The p-type dopant concentration can be selected from 1 to 20 wt%, more preferably 3 to 10 wt%.

The p-type dopant concentration can be selected from 1 to 20% by volume, more preferably 3% to 10% by volume.

However, according to a preferred embodiment, the HIL comprises a compound of formula (I) or (IV) as described above.

According to a preferred embodiment, the HIL may comprise the same compounds of formula (I) and/or (IV) as in the p-type charge generating layer.

According to a preferred embodiment, the HIL may comprise a substantially covalent matrix compound as described above.

According to a preferred embodiment, the HIL may comprise a compound of formula (I) or (IV) as described above and a compound of formula (VI) or (VII) as described above.

According to a preferred embodiment, the p-type charge generating layer and the hole injection layer may comprise the same substantially covalent host compound.

Hole transport layer

According to one embodiment, wherein the semiconductor layer, preferably the organic semiconductor layer, is a hole transport layer, wherein the organic semiconductor layer comprises an organic p-type dopant.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, wherein the organic semiconductor layer is a hole transport layer, and wherein the organic semiconductor layer comprises an organic p-type dopant.

According to one embodiment, wherein the organic semiconductor layer is arranged between the photoactive layer and the anode, wherein the organic semiconductor layer is a hole transport layer, and wherein the organic electronic device comprises an organic p-type dopant.

The Hole Transport Layer (HTL) may be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, langmuir-Blodgett (LB) deposition, or the like. When the HTL is formed by vacuum deposition or spin coating, the conditions of deposition and coating may be similar to those of formation of the HIL. However, the conditions of vacuum or solution deposition may vary depending on the compound used to form the HTL.

The HTL may be formed of any compound commonly used to form HTLs. Compounds that can be suitably used are disclosed, for example, in Yasuhiko Shirota and Hiroshi Kageyama, chem. Rev.2007,107,953-1010, incorporated herein by reference. Examples of compounds that can be used to form the HTL are: carbazole derivatives such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives such as N, N ' -bis (3-methylphenyl) -N, N ' -diphenyl- [1, 1-biphenyl ] -4,4' -diamine (TPD) or N, N ' -bis (naphthalen-1-yl) -N, N ' -diphenyl benzidine (α -NPD); and triphenylamine compound 4,4' -tri (N-carbazolyl) triphenylamine (TCTA). Among these compounds, TCTA is capable of transporting holes and inhibiting excitons from diffusing into the EML.

According to one embodiment, the hole transport layer may comprise a substantially covalent matrix compound as described above.

According to a preferred embodiment, the hole injection layer and the hole transport layer may comprise the same basic covalent matrix compound as described above.

According to one embodiment, the hole transport layer may comprise a compound of formula (VI) or (VII) as described above.

According to a preferred embodiment, the hole injection layer and the hole transport layer may comprise the same compound of formula (VI) or (VII) as described above.

According to a preferred embodiment, the p-type charge generation layer, the hole injection layer and the hole transport layer may comprise the same basic covalent matrix compound.

According to a preferred embodiment, the p-type charge generation layer, the hole injection layer and the hole transport layer may comprise the same compound of formula (VI) or (VII) as described above.

According to a preferred embodiment, the hole injection layer, the hole transport layer and the p-type charge generation layer may comprise the same compounds of formula (I) or (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih) and (Ik) as described above.

According to one embodiment of the invention, the hole transport layer may comprise the same basic covalent matrix compound as the organic semiconductor layer.

The HTL may have a thickness in the range of about 5nm to about 250nm, preferably about 10nm to about 200nm, further about 20nm to about 190nm, further about 40nm to about 180nm, further about 60nm to about 170nm, further about 80nm to about 160nm, further about 100nm to about 160nm, further about 120nm to about 140 nm. One preferred thickness of the HTL may be 170nm to 200nm.

When the thickness of the HTL is within this range, the HTL may have excellent hole transport characteristics without causing substantial damage to the driving voltage.

Electron blocking layer

The Electron Blocking Layer (EBL) functions to prevent electrons from being transferred from the light emitting layer to the hole transporting layer, thereby confining electrons to the light emitting layer. Thereby, efficiency, operating voltage and/or lifetime are improved. Typically, the electron blocking layer comprises a triarylamine compound. The LUMO level of the triarylamine compound is closer to the vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level that is further from the vacuum level than the HOMO level of the hole transport layer. The thickness of the electron blocking layer may be selected between 2 and 20 nm.

The electron blocking layer may also be described as a triplet control layer if it has a high triplet level.

If phosphorescent green or blue light emitting layers are used, the function of the triplet control layer is to reduce quenching of the triplet state. Thereby, higher luminous efficiency derived from the phosphorescent light emitting layer can be achieved. The triplet control layer is selected from triarylamine compounds having a triplet energy level higher than the triplet energy level of the phosphorescent emitter in the adjacent light emitting layer. Suitable compounds for the triplet-control layer, in particular triarylamine compounds, are described in EP 2 722 A1.

Photoactive layer (PAL)

The photoactive layer converts a current into a photon or a photon into a current.

PAL may be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When PAL is formed by vacuum deposition or spin coating, the conditions of deposition and coating may be similar to those of formation of HIL. However, the conditions of deposition and coating may vary depending on the compound used to form PAL.

According to one embodiment, the organic electronic device may further comprise a photoactive layer, wherein the photoactive layer is disposed between the anode layer and the cathode layer.

According to one embodiment, the photoactive layer does not comprise a compound of formula (I).

The photoactive layer may be a light emitting layer or a light absorbing layer.

Luminous layer (EML)

According to one embodiment, the organic electronic device may further comprise a light emitting layer, wherein the light emitting layer is arranged between the anode layer and the cathode layer.

The EML may be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When EML is formed using vacuum deposition or spin coating, the conditions of deposition and coating may be similar to those of formation of HIL. However, the conditions of deposition and coating may vary depending on the compound used to form the EML.

According to one embodiment of the invention, the light-emitting layer does not comprise a compound of formula (I).

An emission layer (EML) may be formed from a combination of a host and an emitter dopant. Examples of hosts are Alq3, 4' -N, N ' -dicarbazole-biphenyl (CBP), poly (N-vinylcarbazole) (PVK), 9, 10-di (naphthalen-2-yl) Anthracene (ADN), 4' -tris (carbazol-9-yl) -triphenylamine (TCTA), 1,3, 5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBI), 3-tert-butyl-9, 10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA) and Bis (BI)(2- (2-hydroxyphenyl) benzothiazole) zinc (Zn (BTZ) ₂ )。

The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via a Thermally Activated Delayed Fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The luminophore may be a small molecule or a polymer.

Examples of red emitter dopants are PtOEP, ir (piq) ₃ And Btp ₂ Ir (acac), but is not limited thereto. These compounds are phosphorescent emitters, however, fluorescent red emitter dopants may also be used.

An example of a phosphorescent green emitter dopant is Ir (ppy) ₃ (ppy=phenylpyridine), ir (ppy) ₂ (acac)、Ir(mpyp) ₃ 。

Examples of phosphorescent blue emitter dopants are: f2Irpic, (F2 ppy) 2Ir (tmd) and Ir (dfppz) 3; and (3) a trifluorene. 4,4' -bis (4-diphenylaminostyryl) biphenyl (DPAVBi), 2,5,8, 11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue emitter dopants.

The amount of the emitter dopant may be in the range of about 0.01 to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the light emitting layer may be composed of a light emitting polymer. The EML may have a thickness of about 10nm to about 100nm, for example about 20nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent light emission without causing substantial damage to the driving voltage.

Hole Blocking Layer (HBL)

A Hole Blocking Layer (HBL) may be formed on the EML by using vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. to prevent holes from diffusing into the ETL. When the EML contains phosphorescent dopants, the HBL may also have a triplet exciton blocking function.

The HBL may also be named auxiliary ETL or a-ETL.

When HBL is formed using vacuum deposition or spin coating, the conditions of deposition and coating may be similar to those used to form HIL. However, the conditions of deposition and coating may vary with the compound used to form the HBL. Can use the methods commonly used for the formation of HBAny compound of L. Examples of the compound for forming HBL includeDiazole derivatives, triazole derivatives, phenanthroline derivatives and azine derivatives, preferably triazine or pyrimidine derivatives.

The thickness of the HBL may be in the range of about 5nm to about 100nm, for example about 10nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without causing substantial damage to the driving voltage.

Electron Transport Layer (ETL)

The organic electronic device according to the present invention may further comprise an Electron Transport Layer (ETL).

According to another embodiment, the electron transport layer may further comprise an azine compound, preferably a triazine compound or a pyrimidine compound.

In one embodiment, the electron transport layer may further comprise a dopant selected from alkali metal organic complexes, preferably LiQ.

The ETL thickness may be in the range of about 15nm to about 50nm, for example in the range of about 20nm to about 40 nm. When the thickness of the ETL is within this range, the ETL may have satisfactory electron injection characteristics without causing substantial damage to the driving voltage.

According to another embodiment of the present invention, the organic electronic device may further comprise a hole blocking layer and an electron transporting layer, wherein the hole blocking layer and the electron transporting layer comprise azine compounds. Preferably, the azine compound is a triazine compound.

Electron Injection Layer (EIL)

On the ETL, an optional EIL may be formed, preferably directly on the electron transport layer, which may facilitate electron injection from the cathode. Examples of EIL forming materials include lithium 8-hydroxyquinoline (LiQ), liF, naCl, csF, li, which are known in the art ₂ O, baO, ca, ba, yb, mg. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions may vary with the material used to form the EIL.

The thickness of the EIL may be in the range of about 0.1nm to about 10nm, for example in the range of about 0.5nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection properties without causing substantial damage to the driving voltage.

Cathode layer

A cathode layer is formed on the ETL or optional EIL. The cathode layer may be formed of a metal, an alloy, a conductive compound, or a mixture thereof. The cathode electrode may have a low work function. For example, the cathode layer may be formed of lithium (Li), magnesium (Mg), aluminum (Al) -lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg) -indium (In), magnesium (Mg) -silver (Ag), or the like. Alternatively, the cathode electrode may be formed of a transparent conductive oxide such as ITO or IZO.

The thickness of the cathode layer may be in the range of about 5nm to about 1000nm, for example in the range of about 10nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5nm to about 50nm, the cathode layer may be transparent or translucent even if formed of a metal or a metal alloy.

In a preferred embodiment, the cathode layer comprises a metal or metal alloy and is transparent.

It should be understood that the cathode layer is not part of the electron injection layer or electron transport layer.

Organic Light Emitting Diode (OLED)

The organic electronic device according to the present invention may be an organic light emitting device.

According to one aspect of the present invention, there is provided an Organic Light Emitting Diode (OLED) comprising: a substrate; an anode electrode formed on the substrate; an organic semiconductor layer comprising a compound of formula (I), a hole transporting layer, a light emitting layer, an electron transporting layer and a cathode electrode.

According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode electrode formed on the substrate; an organic semiconductor layer comprising a compound of formula (I), a hole transporting layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, and a cathode electrode.

According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode electrode formed on the substrate; an organic semiconductor layer comprising a compound of formula (I), a hole transporting layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, an electron injecting layer, and a cathode electrode.

According to various embodiments of the present invention, an OLED layer may be provided that is disposed between the above layers, on the substrate, or on the top electrode.

According to one aspect of the present invention, there is provided an Organic Light Emitting Diode (OLED) comprising: a substrate; an anode layer formed on the substrate; a hole injection layer that may comprise a compound of formula (I); a hole transport layer; a light emitting layer; an electron transport layer; an n-type charge generation layer; a p-type charge generation layer comprising a compound of formula (I); a hole transport layer; an optional electron injection layer; and a cathode layer.

According to one aspect, an OLED can comprise the following layer structure: the substrate is arranged adjacent to the anode electrode, the anode electrode is arranged adjacent to the first hole injection layer, the first hole injection layer is arranged adjacent to the first hole transport layer, the first electron blocking layer is arranged adjacent to the first light emitting layer, the first light emitting layer is arranged adjacent to the first electron transport layer, the first electron transport layer is arranged adjacent to the n-type charge generating layer, the n-type charge generating layer is arranged adjacent to the p-type charge generating layer, the p-type charge generating layer is arranged adjacent to the second hole transport layer, the second hole transport layer is arranged adjacent to the second electron blocking layer, the second electron blocking layer is arranged adjacent to the second light emitting layer, and the optional electron transport layer and/or the optional electron injection layer is arranged between the second light emitting layer and the cathode electrode.

The organic semiconductor layer according to the present invention may be the first hole injection layer and/or the hole transport layer.

Organic electronic device

According to one embodiment, the organic electronic device may comprise at least one semiconductor layer comprising a compound of formula I or formula Ia, ib, ic, id, ie, if, ig, ih, ik according to the invention.

The organic electronic device may comprise an anode layer, a cathode layer and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is arranged between the anode layer and the cathode layer, wherein the at least one semiconductor layer comprises a compound of formula I or formula Ia, ib, ic, id, ie, if, ig, ih, ik according to the invention.

The organic electronic device according to the present invention may be an Organic Light Emitting Diode (OLED), a light emitting device, a thin film transistor, a battery, a display device, or an organic photovoltaic cell (OPV).

According to another aspect of the present invention, there is provided a method of manufacturing an organic electronic device, the method using:

at least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

Suitable deposition methods include:

deposition by vacuum thermal evaporation;

deposition by solution treatment, preferably selected from spin coating, printing, casting; and/or

-slot die coating.

According to various embodiments of the present invention, there is provided a method of using a deposition source comprising:

-a first deposition source for releasing a compound of formula (I) according to the invention; and

-a second deposition source for releasing a substantially covalent matrix compound;

the method includes the steps of forming an organic semiconductor layer; wherein for an Organic Light Emitting Diode (OLED):

-forming an organic semiconductor layer by releasing a compound of formula (I) according to the invention from a first deposition source and a substantially covalent matrix compound from a second deposition source.

According to various embodiments of the present invention, the method may further include forming at least one layer selected from the group consisting of forming a hole transport layer and forming a hole blocking layer on the anode electrode, and a light emitting layer between the anode electrode and the first electron transport layer.

According to various embodiments of the present invention, the method may further comprise a step for forming an Organic Light Emitting Diode (OLED), wherein

-forming an anode electrode on a substrate;

-forming an organic semiconductor layer comprising a compound of formula (I) on an anode electrode;

-forming a hole transport layer on the organic semiconductor layer comprising the compound of formula (I);

-forming a light emitting layer on the hole transporting layer;

-forming an electron transport layer on the light emitting layer, optionally forming a hole blocking layer on the light emitting layer;

-and finally forming a cathode electrode;

-forming an optional hole blocking layer between the first anode electrode and the light emitting layer in said order;

-forming an optional electron injection layer between the electron transport layer and the cathode electrode.

-a third deposition source for releasing the n-CGL matrix compound;

-a fourth deposition source for releasing n-CGL dopants;

the method includes the steps of forming a p-type charge generation layer; wherein for an Organic Light Emitting Diode (OLED):

-forming a p-type charge generating layer by releasing a compound of formula (I) according to the invention from a first deposition source and a substantially covalent matrix compound from a second deposition source;

the method includes the steps of forming an n-type charge generation layer; wherein for an Organic Light Emitting Diode (OLED):

-forming an n-type charge generating layer by releasing the n-CGL host compound according to the invention from a third deposition source and releasing the n-CGL dopant from a fourth deposition source.

According to various embodiments of the present invention, the method may further include forming at least one layer selected from the group consisting of: a hole transport layer or hole blocking layer, a light emitting layer, and an n-type charge generating layer between the anode electrode and the cathode layer.

According to various embodiments, an OLED may have a layer structure in which the layers have the following order:

an anode, an organic semiconductor layer comprising a compound of formula (I) according to the invention, a first hole transporting layer, a second hole transporting layer, a light emitting layer, an optional hole blocking layer, an electron transporting layer, an optional electron injecting layer and a cathode.

According to another aspect of the present invention, there is provided an electronic device comprising at least one organic light emitting device according to any of the embodiments described throughout this application, preferably comprising an organic light emitting diode according to one of the embodiments described throughout this application. More preferably, the electronic device is a display device.

Hereinafter, embodiments will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. Reference will now be made in detail to exemplary aspects.

Drawings

The above-described components as well as the claimed components and the components used in the embodiments according to the invention are not limited in their size, shape, material selection and technical concept by any particular exception, so that selection criteria known in the relevant art can be applied without limitation.

Further details, features and advantages of the object of the invention are disclosed in the subclaims and the following description of the respective figures-which by way of example-show a preferred embodiment according to the invention. However, any embodiment does not necessarily represent the full scope of the invention, and reference is therefore made to the claims and herein for interpreting the scope of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed.

FIG. 1 shows a simplified schematic of a substrate-less organic electronic device according to the present invention;

FIG. 2 shows a simplified schematic of an organic electronic device having a substrate according to the present invention;

FIG. 3 shows a simplified schematic diagram of an organic electronic device having a substrate according to the present invention;

Fig. 4 shows a simplified schematic of an organic electronic device with a substrate according to the present invention.

Fig. 5 shows the power conversion efficiency after 0H at 23±2 ℃ and after 450H aging at 85 ℃ of a perovskite solar cell comprising the compound A3 (N- (9, 9-dimethyl-9H-fluoren-2-yl) -N- (11, 11-diphenyl-11H-benzo [ a ] fluoren-9-yl) dibenzo [ b, d ] furan-1-amine) of the present invention or N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine as a comparative compound.

Hereinafter, the drawings will be described in more detail with reference to embodiments. However, the present invention is not limited to the following drawings.

In this regard, when a first element is referred to as being formed on or disposed "on" or "over" a second element, the first element can be directly on the second element or one or more other elements can be disposed therebetween. When a first element is referred to as being "directly on" or "disposed on" a second element, there are no other elements disposed therebetween.

Fig. 1 shows a simplified schematic of a substrate-less organic electronic device according to the present invention. The organic electronic device 1 is a solar cell and comprises a first electrode 2. An organic semiconductor layer is applied on the first electrode 2. A second electrode 7 is deposited on top of the organic semiconductor layer 4.

Fig. 2 shows a simplified schematic of an organic electronic device with a substrate according to the present invention. The organic electronic device 1 is a solar cell and comprises a first electrode 2 arranged on a substrate 3. An organic semiconductor layer is applied on the first electrode 2. A second electrode 7 is deposited on top of the organic semiconductor layer 4.

Fig. 3 shows a simplified schematic diagram of an organic electronic device with a substrate according to the present invention. The organic electronic device 1 is a solar cell and comprises a first electrode 2. A Hole Transport Layer (HTL) 4 is deposited on the first electrode 2. A Hole Transport Layer (HTL) 4. A photoactive layer 5 is deposited on the Hole Transport Layer (HTL) 4. An electron transport layer 6 is deposited on the photoactive layer. An Electron Transport Layer (ETL) 6. A second electrode 7 is deposited on top of the electron transport layer 6.

Fig. 4 shows a simplified schematic of an organic electronic device with a substrate according to the present invention. The organic electronic device 1 is a solar cell and comprises a first electrode 2 arranged on a substrate 3. A Hole Transport Layer (HTL) 4 is deposited on the first electrode 2. A Hole Transport Layer (HTL) 4. A photoactive layer 5 is deposited on the Hole Transport Layer (HTL) 4. An electron transport layer 6 is deposited on the photoactive layer. An Electron Transport Layer (ETL) 6. A second electrode 7 is deposited on top of the electron transport layer 6.

Fig. 5 shows the percentage of power conversion efficiency over lifetime (aging time) after 0H at 23±2 ℃ and after 450H aging at 85 ℃ of a perovskite solar cell comprising the inventive compound A3 (N- (9, 9-dimethyl-9H-fluoren-2-yl) -N- (11, 11-diphenyl-11H-benzo [ a ] fluoren-9-yl) dibenzo [ b, d ] furan-1-amine) according to the invention or the comparative compound N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine according to table 8.

Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of one or more exemplary embodiments of the invention.

Experimental data/synthesis of compounds/synthesis of intermediates

Synthesis of methyl 5-chloro-2- (naphthalen-2-yl) benzoate

The flask was purged with nitrogen and 2-bromo-5-chlorobenzoic acid methyl ester (50 g,0.20 mol), naphthalene-2-ylboronic acid (34.4 g,0.20 mol), pd (PPh) ₃ ) ₄ (11.6g，0.01mol)、K ₂ CO ₃ (82.9 g,0.60 mol), 1000mL twoAlkane and 300mL distilled water and stirred at 120 ℃ for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent is filtered, the solvent in the organic phase is evaporated under vacuum and purified by column chromatography. To obtain 5-chloro-2- (naphthalene-2-yl) benzoic acid methyl ester. (47.5 g, yield 80%)

Synthesis of (5-chloro-2- (naphthalen-2-yl) phenyl) benzhydrol

The flask was flushed with nitrogen and 5-chloro-2- (naphthalen-2-yl) benzoate (50 g,0.17 mol) and 1000mL THF were added. After cooling at-78 ℃, 430mL (0.43 mol) of a 1M solution of phenylmagnesium bromide in THF was slowly added and stirred at the same temperature for 1 hour. Thereafter, the mixture was stirred at room temperature for 24 hours. After the reaction was terminated, 500mL of distilled water was used to stop the reaction. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent is filtered, the solvent in the organic phase is evaporated under vacuum and purified by column chromatography. To obtain (5-chloro-2- (naphthalene-2-yl) phenyl) diphenyl methanol.

(57.2 g, yield 80%)

Synthesis of 9-chloro-11, 11-diphenyl-11H-benzo [ a ] fluorene

The flask was flushed with nitrogen and charged with (5-chloro-2- (naphthalen-2-yl) phenyl) diphenylmethanol (50 g,0.12 mo)l), 5.2mL of concentrated HCl and 780mL of AcOH, and stirred at 110℃for 6 hours. After the reaction was completed, it was cooled to room temperature. After the reaction was terminated, 500mL of distilled water was used to stop the reaction. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent is filtered, the solvent in the organic phase is evaporated under vacuum and purified by column chromatography. To obtain 9-chloro-11, 11-diphenyl-11H-benzo [ a ]]Fluorene. (19.3 g, 40% yield)

Synthesis of N- ([ 1,1' -biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine

The flask was purged with nitrogen and charged with 2-bromo-1, 1' -biphenyl (11.7 g,1 equivalent, 50 mmol), 9-dimethyl-9H-fluoren-2-amine (12.6 g,1.2 equivalent, 60 mmol), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 80℃for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent is filtered, the solvent in the organic phase is evaporated under vacuum and purified by column chromatography. Obtaining N- ([ 1,1' -biphenyl)]-2-yl) -9, 9-dimethyl-9H-fluoren-2-amine; CAS 1198395-24-2. (14.5 g, yield 80%)

Synthesis of N- ([ 1,1' -biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-3-amine

The flask was purged with nitrogen and charged with 3-bromo-9, 9-dimethyl-9H-fluorene (13.7 g,1 equivalent, 50 mmol), [1,1' -biphenyl)]-2-amine (10.2 g,1.2 eq, 60 mmol), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 80℃for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying.The drying agent is filtered, the solvent in the organic phase is evaporated under vacuum and purified by column chromatography. Obtaining N- ([ 1,1' -biphenyl)]-2-yl) -9, 9-dimethyl-9H-fluoren-3-amine; CAS 1421789-39-0. (13.6 g, yield 75%)

Synthesis of N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ] furan-1-amine

The flask was purged with nitrogen and charged with 1-bromodibenzo [ b, d ]]Furan (12.4 g,1 equivalent, 50 mmol), 9-dimethyl-9H-fluoren-2-amine (12.6 g,1.2 equivalent, 60 mmol), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 80℃for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent is filtered, the solvent in the organic phase is evaporated under vacuum and purified by column chromatography. To obtain the N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ]]Furan-1-amine; CAS 2225845-23-6. (15.4 g, yield 82%)

Synthesis of N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ] furan-3-amine

The flask was purged with nitrogen and charged with 3-bromodibenzo [ b, d ]]Furan (12.4 g,1 equivalent, 50 mmol), 9-dimethyl-9H-fluoren-2-amine (12.6 g,1.2 equivalent, 60 mmol), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 80℃for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent is filtered, the solvent in the organic phase is evaporated under vacuum and purified by column chromatography. To obtain the N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ]]Furan-3-amine; CAS1427556-50-0. (16.0 g, yield 85%)

Synthesis of N, 9-diphenyl-9H-carbazole-2-amine

The flask was purged with nitrogen and charged with 2-bromo-9-phenyl-9H-carbazole (16.1 g,1 eq, 50 mmol), aniline (5.6 g,1.2 eq, 60 mmol), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 60℃for 3 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent is filtered, the solvent in the organic phase is evaporated under vacuum and purified by column chromatography. Obtaining N, 9-diphenyl-9H-carbazole-2-amine; CAS1427316-55-9. (11.7 g, yield 70%)

Synthesis of 7, 7-dimethyl-N-phenyl-7H-fluoreno [4,3-b ] benzofuran-5-amine

The flask was purged with nitrogen and charged with 5-bromo-7, 7-dimethyl-7H-fluoreno [4,3-b]Benzofuran (18.2 g,1 eq., 50 mmol), aniline (5.6 g,1.2 eq., 60 mmol), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 60℃for 3 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent is filtered, the solvent in the organic phase is evaporated under vacuum and purified by column chromatography. To obtain 7, 7-dimethyl-N-phenyl-7H-fluoreno [4,3-b]Benzofuran-5-amine. (13.5 g, yield 72%)

Synthesis of N- ([ 1,1' -biphenyl ] -2-yl) -N- (9, 9-dimethyl-9H-fluoren-2-yl) -11, 11-diphenyl-11H-benzo [ a ] fluoren-9-amine (A2)

The flask was purged with nitrogen and charged with 9-chloro-11, 11-diphenyl-11H-benzo [ a ]]Fluorene (20.15 g,1.0 eq, 50 mmol), N- ([ 1,1' -biphenyl) ]-2-yl) -9, 9-dimethyl-9H-fluoren-2-amine (18.07 g,1.0 equivalent, 50mmol; CAS 1198395-24-2), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (500 mL) and stirred at 110℃for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent was filtered and the solvent in the organic phase was evaporated under vacuum. The crude product was dissolved in toluene and the resulting solution was filtered over silica with toluene as eluent. The organic solution was evaporated under vacuum and acetone was added. The suspension was then stirred at room temperature until precipitation. The solid was filtered, rinsed with acetone and dried under vacuum at 60 ℃ overnight to give 18.78g of crude product. Purification was further carried out by gradient sublimation. (sublimation yield 91%, HPLC purity after sublimation 100%)

Synthesis of N- ([ 1,1' -biphenyl ] -2-yl) -N- (9, 9-dimethyl-9H-fluoren-3-yl) -11, 11-diphenyl-11H-benzo [ a ] fluoren-9-amine (A3)

The flask was purged with nitrogen and charged with 9-chloro-11, 11-diphenyl-11H-benzo [ a ]]Fluorene (20.65 g,1.025 eq, 51.25 mmol), N- ([ 1,1' -biphenyl)]-2-yl) -9, 9-dimethyl-9H-fluoren-3-amine (18.07 g,1.0 eq, 50mmol; CAS 1421789-39-0), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 110℃for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent is filtered and the solvent in the organic phase is evaporated under vacuum. The crude product was dissolved in toluene and the resulting solution was filtered over silica with toluene as eluent. The organic solution was evaporated under vacuum and acetone was added. The suspension was then stirred at room temperature until precipitation. The solid was filtered, rinsed with acetone and dried under vacuum at 60 ℃ overnight to give 22.70g of crude product. Purification was further carried out by gradient sublimation. (sublimation yield 90%, HPLC purity after sublimation 99.97%)

Synthesis of N- (9, 9-dimethyl-9H-fluoren-2-yl) -N- (11, 11-diphenyl-11H-benzo [ a ] fluoren-9-yl) dibenzo [ b, d ] furan-1-amine (A5)

The flask was purged with nitrogen and charged with 9-chloro-11, 11-diphenyl-11H-benzo [ a ]]Fluorene (20.15 g,1.0 eq, 50 mmol), N- (9, 9-dimethyl-9H-fluoren-2-yl) -1-dibenzofuran amine (18.77 g,1.0 eq, 50mmol; CAS 2225845-23-6), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 110℃for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent was filtered and the solvent in the organic phase was evaporated under vacuum. The crude product was dissolved in toluene and the resulting solution was filtered over silica with toluene as eluent. The organic solution was evaporated under vacuum and acetone was added. The suspension was then stirred at room temperature until precipitation. The solid was filtered, rinsed with acetone and dried under vacuum at 60 ℃ overnight to give 17.30g of crude product. Purification was further carried out by gradient sublimation. (sublimation yield 94%, HPLC purity after sublimation 100%)

Synthesis of N- (9, 9-dimethyl-9H-fluoren-2-yl) -N- (11, 11-diphenyl-11H-benzo [ a ] fluoren-9-yl) dibenzo [ b, d ] furan-3-amine (A6)

The flask was purged with nitrogen and charged with 9-chloro-11, 11-diphenyl-11H-benzo [ a ]]Fluorene (20.65 g,1.025 eq, 51.25 mmol), N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d)]Furan-3-amine (18.77 g,1.0 eq, 50mmol; CAS 1427556-50-0), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 110℃for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent was filtered and the solvent in the organic phase was evaporated under vacuum. The crude product was dissolved in toluene and the resulting solution was filtered over silica with toluene as eluent. The organic solution was evaporated under vacuum and acetone was added. The suspension was then stirred at room temperature until precipitation. The solid was filtered, rinsed with acetone and dried under vacuum at 60 ℃ overnight to give 26.87g of crude product. Purification was further carried out by gradient sublimation. (sublimation yield 96%, HPLC purity after sublimation 99.88%)

Synthesis of N- (11, 11-diphenyl-11H-benzo [ a ] fluoren-9-yl) -N, 9-diphenyl-9H-carbazol-2-amine (A12)

The flask was purged with nitrogen and charged with 9-chloro-11, 11-diphenyl-11H-benzo [ a ]]Fluorene (20.65 g,1.025 eq, 51.25 mmol), N, 9-diphenyl-9H-carbazol-2-amine (16.72 g,1.0 eq, 50mmol; CAS 1427316-55-9), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 110℃for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent was filtered and the solvent in the organic phase was evaporated under vacuum. The crude product was dissolved in toluene and the resulting solution was filtered over silica with toluene as eluent. The organic solution was evaporated under vacuum and acetone was added. Then stirred at room temperature Floating until precipitation. The solid was filtered, rinsed with acetone and dried under vacuum at 60 ℃ overnight to give 28.61g of crude product. Purification was further carried out by gradient sublimation. (sublimation yield 94%, HPLC purity after sublimation 99.96%)

Synthesis of N- (11, 11-diphenyl-11H-benzo [ a ] fluoren-9-yl) -7, 7-dimethyl-N-phenyl-7H-fluoreno [4,3-b ] benzofuran-5-amine (A16)

The flask was purged with nitrogen and charged with 9-chloro-11, 11-diphenyl-11H-benzo [ a ]]Fluorene (20.65 g,1.025 eq, 51.25 mmol), 7-dimethyl-N-phenyl-7H-fluoreno [4,3-b ]]Benzofuran-5-amine (18.77 g,1.0 eq, 50 mmol), pd ₂ (dba) ₃ (1.3 g,0.03 eq, 1.5 mmol), P (t-Bu) ₃ (1.01 g,0.1 eq, 5 mmol), naO (t-Bu) (14.42 g,3 eq, 150 mmol) and toluene (400 mL) and stirred at 110℃for 12 hours. After the reaction was completed, it was cooled to room temperature. The organic layer was decanted and dried over MgSO ₄ And (5) drying. The drying agent was filtered and the solvent in the organic phase was evaporated under vacuum. The crude product was dissolved in toluene and the resulting solution was filtered over silica with toluene as eluent. The organic solution was evaporated under vacuum and acetone was added. The suspension was then stirred at room temperature until precipitation. The solid was filtered, rinsed with acetone and dried under vacuum at 60 ℃ overnight to give 24.50g of crude product. Purification was further carried out by gradient sublimation. (sublimation yield 94%, HPLC purity after sublimation 99.73%)

Detailed Description

The invention is further illustrated by the following examples, which are merely illustrative and are not limiting.

HOMO and LUMO

HOMO and LUMO were calculated using the package turbo V6.5 (turbo GmbH, litzenhardtstrasse 19,76135karlsruhe, germany). The optimal geometry of the molecular structure and HOMO and LUMO energy levels are determined by applying the hybrid functional B3LYP and 6-31G set of groups in the gas phase. If more than one conformation is feasible, the conformation with the lowest total energy is selected.

Thermogravimetric analysis

The term "TGA5%" means the temperature at which a5% weight loss occurs during thermogravimetric analysis, measured in units of c.

The TGA5% value can be determined by heating 9-11 mg of sample in a thermogravimetric analyzer at a heating rate of 10K/min in an open 100 μl aluminum pan, with 20mL/min in the equilibration zone and 30mL/min nitrogen flow rate in the oven zone.

The TGA5% value may indirectly measure the volatility and/or decomposition temperature of a compound. In a first approximation, the higher the TGA5% value, the lower the volatility of the compound and/or the higher the decomposition temperature.

According to one embodiment, the TGA5% value of the compound of formula (I) is selected from the range of ≡270 ℃ and ≡450 ℃, preferably ≡280 ℃ and ≡440 ℃, still preferably ≡295 ℃ and ≡430 ℃.

Glass transition temperature

The glass transition temperature, also known as Tg, is measured in units of degrees celsius and is determined by Differential Scanning Calorimetry (DSC).

The glass transition temperature was measured in a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen and using a heating rate of 10K/min as described in DIN EN ISO 11357 published 3 in 2010.

General procedure for manufacturing OLED

15 Ω/cm with 90nm ITO ² The glass substrate (available from Corning co.) was cut into dimensions of 50mm×50mm×0.7mm, ultrasonically cleaned with isopropyl alcohol for 5 minutes, then ultrasonically cleaned with pure water for 5 minutes, and then cleaned with ultraviolet ozone for 30 minutes, thereby preparing an anode.

Then, N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine (F3) or a compound of formula (Ia) according to table 3 and 4,4',4"- ((1 e,1' e,1" e) -cyclopropane-1, 2, 3-trisilyltri (cyanomethyl subunit)) tris (2, 3,5, 6-tetrafluorobenzonitrile) were vacuum-co-deposited on the anode to form HIL having a thickness of 10 nm. The composition of HIL is shown in Table 3.

Then, a compound of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine or a compound of formula (I) according to table 3 was vacuum deposited on the HIL to form a first HTL having a thickness of 128 nm.

Then, N- (4- (dibenzo [ b, d ] furan-4-yl) phenyl) -N- (4- (9-phenyl-9H-fluoren-9-yl) phenyl) - [1,1' -biphenyl ] -4-amine (CAS 1824678-59-2) was vacuum deposited on the HTL to form an Electron Blocking Layer (EBL) having a thickness of 5 nm.

Then, 97% by volume of H09 (trade name H09, provided by Sun Fine Chemicals in korea) as an EML host and 3% by volume of BD200 (trade name BD200, provided by Sun Fine Chemicals in korea) as a fluorescent blue dopant were co-deposited on the EBL to form a first blue light emitting EML having a thickness of 20 nm.

Then, a Hole Blocking Layer (HBL) having a thickness of 5nm was formed by depositing 2- (3 '- (9, 9-dimethyl-9H-fluoren-2-yl) - [1,1' -biphenyl ] -3-yl) -4, 6-diphenyl-1, 3, 5-triazine on the light emitting layer.

Then, an Electron Transport Layer (ETL) having a thickness of 31nm was formed on the hole blocking layer by co-depositing 50 wt% of 4'- (4- (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) naphthalen-1-yl) - [1,1' -biphenyl ] -4-carbonitrile and 50 wt% of LiQ.

Then, by at 10 ^-7 At mbar of 0.01 toAl is deposited at a rate of 100nm thick cathode is formed on the ETL.

By encapsulating the device with a glass slide, the OLED stack is protected from environmental conditions. Thereby forming a cavity containing a getter material for further protection.

To evaluate the performance of the inventive examples relative to the prior art, the current efficiency was measured at 20 ℃. The Keithley 2635 source measurement unit was used to determine the current-voltage characteristics by providing a voltage U in V and measuring the current in mA flowing through the device under test. The voltage applied to the device is in the range of 0V to 10VThe inner is changed by 0.1V as step length. Likewise, the luminance vs. voltage characteristics and CIE coordinates were measured in cd/m for each voltage value by using a Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungs stelle (DAkkS)) ² Is determined for the brightness of the unit. By interpolating the luminance-voltage and current-voltage characteristics, respectively, a luminance of at 10mA/cm was determined ² Cd/a efficiency at that time.

In bottom-emitting devices, the luminescence is predominantly lambertian and is quantified in terms of percent of External Quantum Efficiency (EQE). To determine the efficiency EQE (in%) a calibrated photodiode was used at 10mA/cm ² The light output of the device is measured.

In top-emitting devices, the emission is forward, non-lambertian and also highly dependent on microcavities. Therefore, the external quantum efficiency EQE will be higher compared to the bottom-emitting device. To determine the efficiency EQE (in%) a calibrated photodiode was used at 10mA/cm ² The light output of the device is measured below.

At ambient conditions (20 ℃) and 30mA/cm using a Keithley 2400 source meter ² The lifetime LT of the device was measured and recorded in hours.

The brightness of the device was measured using calibrated photodiodes. The lifetime LT is defined as the time until the luminance of the device decreases to 97% of its initial value.

The increment deltau of the operating voltage is used as a measure of the operating voltage stability of the device. During LT measurement, this increment is determined by subtracting the operating voltage after 1 hour from the operating voltage after 100 hours from the device start to operate.

ΔU＝[U(100h)-U(1h)]

The smaller the Δu value, the better the operating voltage stability.

General procedure for manufacturing vacuum processed perovskite solar cells

The ITO coated glass substrate is patterned by photolithography to limit the active area of the solar cell and to allow easy contact to the top electrode.

The materials used are: p-type dopant 4,4',4"- ((1E, 1' E,1" E) -cyclopropane-1, 2,3Tris (cyanomethyl subunit)) tris (2, 3,5, 6-tetrafluorobenzonitrile), the hole transport materials shown in table 8, and N-type dopant N1, N4-bis (tri-p-tolylphosphino subunit) benzene-1, 4-diamine (PhIm). The electron transport material is fullerene (C) ₆₀ ). The precursor materials of the perovskite light absorption layer are PbI2 and CH ₃ NH ₃ I(MAI)。

With respect to characterization of one embodiment prepared, grazing incidence X-ray diffraction (GIXRD) patterns were collected on a Empyrean PANanalytical powder diffractometer using Cu kα1 radiation at room temperature. Typically, three consecutive measurements are collected and averaged into a single spectrum. The surface topography of the films was analyzed using an atomic force microscope (AFM, multimode SPM, veeco, USA). Scanning Electron Microscope (SEM) images were performed on a Hitachi S-4800 microscope operating on platinum metallized samples at an accelerating voltage of 2 kV. An absorption spectrum was acquired using an avants Avaspec2048 spectrometer based on optical fibers.

The characterization of the solar cell is as follows: external Quantum Efficiency (EQE) was estimated using cell responses at different wavelengths (measured using white light halogen lamps and bandpass filters), with a calibrated silicon reference cell (MiniSun simulator of ECN, netherlands) used to correct for solar spectral mismatch.

Using a Keithley 2400 source measurement device, the current density-voltage (J-V) characteristics were obtained under white light illumination and the short circuit current density was corrected taking into account the device EQE. The electrical characteristics were verified using a solar simulator of Abet Technologies (model 10500, using an am1.5g xenon lamp as a light source). Before each measurement, a calibrated Si reference diode equipped with an infrared cut-off filter (KG-3, schottky) was used to determine the exact light intensity. The J-V curve is recorded in steps of 0.01V between-0.2 and 1.2V, and the 20ms signal is integrated after a 10ms delay. This corresponds to about 0.3V s ^-1 Is a function of the speed of the machine.

For solar cells aged at 85 ℃, the samples were measured at 0h, then placed on a hot plate (Stuart SD 160) at 85 ℃ for 450h. Characterization was performed after the sample reached room temperature.

The device layout for solar cell construction is composed of fourEqual pixel constitution (area of 0.06cm ² Defined as the overlap between the patterned ITO and the top metal contact), by having 0.01cm ² Shadow mask measurements of aperture. For hysteresis studies, different scan rates (0.1, 0.5 and 1Vs were used ^-1 ) The device is biased from-0.2V to 1.2V and vice versa in steps of 0.01V. The intensity correlation measurements were made by placing 0.1, 1, 10, 20, 50% neutral density filters (LOT QuantumDesign GmbH) between the light source and the device.

Furthermore, with respect to device fabrication, the ITO coated glass substrate was then washed with soap, water and isopropyl alcohol in an ultrasonic bath, followed by uv ozone treatment. Transfer them to an integrated nitrogen filled glove box (MBraun, H ₂ O and O ₂ <0.1 ppm) and evacuated to 1 x 10 ^-6 Pressure of mbar. The vacuum chamber is equipped with six temperature controlled evaporation sources (Creaphies) equipped with ceramic crucibles. The source is directed upward at an angle of about 90 deg. relative to the bottom of the evaporator. The distance from the substrate holder to the evaporation source was about 20cm. Three Quartz Crystal Microbalance (QCM) sensors were used, two sensors monitoring the deposition rate of each evaporation source, and the third sensor near the substrate holder monitored the total deposition rate.

For thickness calibration, hole transport materials according to Table 8 and 4,4',4"- ((1E, 1' E,1" E) -cyclopropane-1, 2, 3-trisilyltri (cyanomethyl subunit)) tris (2, 3,5, 6-tetrafluorobenzonitrile), C were first reacted ₆₀ And PhIm sublimate separately. The calibration factor is obtained by comparing the thickness deduced by the QCM sensor with the thickness measured using a mechanical profiler (Ambios XP 1). These materials were then brought from 150 ℃ to 190 ℃ for 4,4',4"- ((1 e,1' e,1" e) -cyclopropane-1, 2, 3-trisilyltris (cyanomethyl subunit)) tris (2, 3,5, 6-tetrafluorobenzonitrile) to the temperature of 150 ℃ to 190 ℃ for the hole transport materials and C according to table 8 ₆₀ Co-sublimating in the temperature range of 250-315 c and the evaporation rate is controlled and regulated by a separate QCM sensor to obtain the desired doping concentration. In general, hole transport materials and C according to Table 8 ₆₀ Is kept constant at a deposition rate ofOr->s ^-1 . To->4,4',4"- ((1E, 1' E,1" E) -cyclopropane-1, 2, 3-trisilyltri (cyanomethyl subunit)) tris (2, 3,5, 6-tetrafluorobenzonitrile). PhIm>Is deposited at a rate of (a).

Undoped hole transporting material according to Table 8And is not doped with C ₆₀ Layer(s)Is deposited at a rate of (a).

The ITO coated glass substrate was then washed with soap, water and isopropyl alcohol in an ultrasonic bath, and then subjected to ultraviolet ozone treatment to prepare an anode.

10 wt.% of 4,4',4"- ((1E, 1' E,1" E) -cyclopropane-1, 2, 3-trisilyltris (cyanomethyl subunit)) tris (2, 3,5, 6-tetrafluorobenzonitrile) and 90 wt.% of a hole transport material according to Table 8 were then co-deposited on the anode in vacuo to form a doped hole transport layer having a thickness of 40nm, wherein the hole transport material was at 250-315℃and 8X 10 °c ^- ⁶ Deposition at mbar.

Then, the same hole transport material (Table 8) as the doped hole transport layer was deposited on the doped hole transport layer in vacuum to form an undoped hole transport layer having a thickness of 10nm, wherein the hole transport material was at 250 to 315℃and 8X 10 ^-6 Deposition at mbar.

Once deposition on the ITO is complete, use dry N immediately ₂ The chamber is vented to deposit the precursor materials PbI2 and CH with the perovskite-type light absorbing layer ₃ NH ₃ I, replacing the crucible. The vacuum chamber is vacuumized again to 10 ^-6 The pressure of mbar then gives a perovskite film (light-absorbing layer) by co-deposition of the two precursors.

CH ₃ NH ₃ Calibration of the deposition rate of I is difficult because the soft nature of the non-uniform layers and materials prevents accurate thickness measurements. Thus, CH ₃ NH ₃ I source temperature was kept constant at 70℃and PbI was adjusted ₂ Deposition temperature, off-line control of CH using grazing incidence X-ray diffraction ₃ NH ₃ I:PbI ₂ Ratio. PbI ₂ Is 250 ℃ and CH ₃ NH ₃ The optimal deposition temperature for I is 70 ℃. After deposition of the 500nm thick perovskite film, the chamber was vented and the chamber was filled with a solution containing C ₆₀ And Phim, and then evacuating again to 10 ^-6 Pressure of mbar. This crucible exchange process is intended to minimize possible cross-contamination between the organic material and the perovskite precursor. A light absorbing layer (perovskite layer) is formed.

Then at 8X 10 ^-6 Pure C was taken up in mbar at 420 ℃ ₆₀ Deposited on the light absorbing layer (perovskite layer) to form an undoped electron transporting layer having a thickness of 10 nm.

Then, 30 wt% PhIm and 70 wt% C were added ₆₀ Co-depositing on an undoped electron transport layer having a thickness of 40nm to form a doped electron transport layer, wherein C ₆₀ At 8X 10 ^-6 Deposited at mbar and 420℃and PhIm at 150-190℃and 8X 10 ^-6 Deposition at mbar.

Five substrates (3×3 cm) each containing four cells were prepared during a single evaporation. Typically, one substrate is reserved for the reference configuration. Finally, transferring the substrate into a second vacuum chamber, whereinSilver electrodes (100 nm thick) are deposited for 20min and after 20min at 6 x 10 ^-6 At mbar 1.8 to +.>Is deposited at a rate of (a).

The detailed information of the lamination is given in table 6.

Technical effects

Table 1: calculated HOMO, LUMO and dipole moments of the compounds of formula (Ia) and formula (Ib)

HOMO and LUMO were calculated using the package turbo V6.5 (turbo GmbH, litzenhardtstrasse 19, 76135Karlsruhe, germany). By applying the hybrid functional B3LYP and 6-31G basis sets in the gas phase, the optimized geometry of the molecular structure and HOMO and LUMO energy levels were determined. If more than one conformation is present, the conformation with the lowest total energy is selected.

TABLE 1

Calculated HOMO, LUMO and dipole moments of the compounds of formula (Ia) and formula (Ib)

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TABLE 2

Glass transition temperatures of inventive and comparative compounds

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d.n. = data are particularly needed if the compound is still available

As is evident from Table 2, the glass transition temperature of the inventive compounds is much higher than that of the comparative compounds.

A high glass transition temperature may be beneficial to the stability of the organic electronic device and the fabrication process of the organic electronic device.

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As shown in table 3, devices containing the compound of formula (Ia) as HTL exhibit lower operating voltages, higher lifetimes, higher external quantum efficiencies, and/or lower increases in operating voltages over time.

The compounds according to the invention exhibit lower dipole moments, see table 4.

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Low operating voltages may be advantageous for reduced power consumption and improved battery life, particularly in mobile devices.

Improved external quantum efficiency may be beneficial in reducing power consumption and improving battery life, particularly in mobile devices.

The improved lifetime is beneficial for improving the long-term stability of the organic electronic device.

The increase in operating voltage over time decreases, indicating an increase in stability of the electronic device. The improvement of the lifetime is important for improving the stability of the electronic device.

Further details, features and advantages of the object of the invention are disclosed in the accompanying claims and in the following description of the various figures, which show by way of example preferred embodiments according to the invention. However, any embodiment does not necessarily represent the full scope of the invention, and reference is therefore made to the claims and herein for interpreting the scope of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed.

Table 6: list of compounds for solar cells

TABLE 6

Table 7: comparison of the stacks of the solar cell of the invention and the comparative example

TABLE 7

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After aging the inventive perovskite solar cell containing compound A3 at 85 ℃ for 450 hours, the power conversion efficiency remained unchanged, even improved, as shown in table 8 and fig. 5. In contrast, the comparative perovskite solar cell exhibited a strong decrease in power conversion efficiency when aged at 85 ℃ for 450 hours, as shown in table 8 and fig. 5.

Thus, inventive perovskite solar cells comprising the inventive compounds may exhibit unexpectedly high power conversion efficiencies even after aging for 450 hours at 85 ℃.

The fill factor FF of the inventive perovskite solar cell was constant even after aging for 450 hours at 85 ℃. In contrast, the fill factor FF of the comparative perovskite solar cell was significantly reduced after aging for 450 hours at 85 ℃ as shown in table 8.

Therefore, the inventive solar cell may be very robust or stable under very severe conditions.

Claims

1. A benzodiphenylfluorene compound represented by formula (I):

wherein Ar is ⁴ Represented by formula (Ia) or (Ib),

wherein the asterisks indicate the binding position of (Ia) and (Ib), an

Wherein the method comprises the steps of

At least one substituent on the condensed ring system is independently selected from C ₁ To C ₆ Alkyl, C ₆ To C ₁₂ Aryl and C ₂ To C ₁₂ Heteroaryl;

R ^e 、R ^f 、R ^g and R is ^h Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl groupC ₂ To C ₁₈ Heteroaryl;

X ¹ selected from O, S, NAr ^1a ；

Ar ^1a Selected from C ₆ To C ₁₂ An aryl group;

or (b)

X ² selected from O, S, NAr ^2b 、CR ^1b R ^2b 、SiR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

2. The benzodiphenylfluorene compound according to claim 1, wherein the compound of formula (I) is represented by the compound of formula (Ic), (Id) or (Ie), wherein

The formula (Ic) is:

wherein the method comprises the steps of

X ¹ selected from O, S, NAr ^1a ；

Ar ^1a Selected from C ₆ To C ₁₂ An aryl group;

or (b)

The formula (Id) is:

wherein the method comprises the steps of

Ar ² Selected from C ₆ To C ₁₂ Aryl or C ₅ To C ₂₅ Heteroaryl;

R ^a2 、R ^b2 、R ^c2 and R is ^d2 Independently selected from H, C ₁ To C ₆ Alkyl, C ₆ To C ₁₈ Aryl and C ₂ To C ₁₈ Heteroaryl, and R ^a2 、R ^b2 、R ^c2 Or R is ^d2 One of them represents a single bond to N of formula (Ib) selected from R ^a2 、R ^b2 、R ^c2 And R is ^d2 Optionally two adjacent substituents of (a) form a substituted or unsubstituted condensed ring system, wherein

X ² selected from O, S, NAr ^2b 、CR ^1b R ^2b 、SiR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

or (b)

The formula (Ie) is:

wherein the method comprises the steps of

Ar ³ Is selected from the group consisting of biphenyl groups,

X ³ selected from O, S、NAr ^2b 、CR ^1b R ^2b ；

Ar ^2b Selected from C ₆ To C ₁₂ An aryl group; and is also provided with

3. The benzodiphenylfluorene compound according to claim 1 or 2, wherein for formula (Ic), X ¹ Selected from O or NAr ² Preferably O; for formula (Id), X ² Selected from O, NAr ^2b 、CR ^1b R ^2b And SiR ^1b R ^2b Preferably selected from O and CR ^1b R ^2b Also preferably selected from CR ^1b R ^2b The method comprises the steps of carrying out a first treatment on the surface of the And for formula (Ie), X ³ Selected from O, S and SiR ^1b R ^2b Preferably selected from O and S, and also preferably selected from O.

4. A benzodiphenylfluorene compound according to any of the preceding claims 1 to 3, wherein for formula (Ic), ar ¹ Selected from substituted or unsubstituted C ₆ To C ₁₃ Aryl and substituted or unsubstituted C ₁₂ Heteroaryl, preferably Ar ¹ Selected from substituted C ₆ To C ₁₃ An aryl group; and for formula (Id), ar ² Selected from C ₆ To C ₁₀ Aryl, preferably Ar ² Selected from C ₆ Aryl groups.

5. Benzodiphenylfluorene compound according to any of the preceding claims 1 to 4, wherein

Ar、Ar ¹ And/or Ar ² A group selected from B1 to B13:

6. A benzodiphenylfluorene compound according to claim 5, wherein

-Ar ¹ A group selected from B1 to B12, preferably a group selected from B1, B2, B3, B4, B5, B6, and further preferably a group selected from B1, B2, B3;

-Ar ² the group selected from B1 to B12 is preferably a group selected from B1, B2, B3, B4, B5, B6, and more preferably a group selected from B1, B2, B3.

7. Benzodiphenylfluorene compound according to any of the preceding claims 1 to 5, wherein Ar ⁴ A group selected from D1 to D7:

8. Benzodiphenylfluorene compounds according to any of the preceding claims 1 to 7, wherein the compound of formula I is selected from A1 to a37:

9. an organic semiconductor layer comprising a benzodiphenylfluorene compound of formula I according to any of the preceding claims 1 to 8.

10. The organic semiconductor layer according to claim 8, wherein the semiconductor layer is a hole injection layer and/or a hole transport layer.

11. The organic semiconductor layer of claim 9 or 10, wherein the organic semiconductor layer further comprises an organic p-type dopant.

12. The organic semiconductor layer according to claim 11, wherein the organic p-type dopant is a pivotable compound.

13. The organic semiconductor layer according to claim 11 or 12, wherein the organic p-type dopant is an axial compound of formula (II)

Wherein in formula (II)

A ¹ Independently selected from the group (1)

if Ar is ¹ Is substituted, then one or more substituents are independentlySelected from electron withdrawing groups, F, CN, partially perfluorinated or perfluorinated alkyl, -NO ₂ ；

A ² And A ³ Independently selected from the group (2)

Ar ² And Ar is a group ³ Independently selected from substituted or unsubstituted C ₆ To C ₃₆ Aryl and substituted or unsubstituted C ₂ To C ₃₆ Heteroaryl; and is also provided with

Each R' is independently selected from electron withdrawing groups.

14. An organic electronic device comprising at least one semiconductor layer according to claims 9 to 13.

15. The organic electronic device of claim 14, comprising an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein at least one organic semiconductor layer is disposed between the anode layer and the cathode layer.

16. The organic electronic device according to claim 14 or 15, wherein the organic electronic device is an Organic Light Emitting Diode (OLED), a light emitting device, a thin film transistor, a battery, a display device, an organic photovoltaic cell (OPV), a solar cell, a perovskite solar cell, a photoconductor, a photodiode or a photodetector.

17. The organic electronic device according to claim 14 or 15, wherein the organic electronic device is an Organic Light Emitting Diode (OLED), a light emitting device, a thin film transistor, a battery, a display device, an organic photovoltaic cell (OPV).