TW201434802A - Tetraphenylene ethylene based compound and OLED device containing the same - Google Patents

Abstract

The present disclosure provides a composition, a film containing the composition, and an electronic device containing the composition. The composition comprises a tetraphenylene ethylene with the structure of any of Examples 1-25, a tetraphenylene ethylene of Structure (I), a tetraphenylene ethylene of Structure (IA), or a combination thereof: wherein for each structure (I) and (IA), R1, R2, R3, and R4 are the same or different, and wherein R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof.

Description

Tetrastyrene-based compound and OLED device containing the same Field of invention

The present invention claims priority to PCT/CN2012/088034, filed on Dec. 31, 2012, the entire disclosure of which is hereby incorporated by reference.

The present invention relates to a tetrastyrene-based compound and an OLED device comprising the same.

Background of the invention

An OLED (organic light-emitting diode) is a light emitting diode (LED), wherein the emissive electroluminescent layer is a film of an organic compound that emits light in response to a current. A typical OLED has a multilayer structure and typically includes an indium tin oxide (ITO) anode and a metal cathode. There are several organic layers sandwiched between the ITO anode and the metal cathode, such as a hole injection layer (HIL), a hole transport layer (HTL), an luminescent material layer (EML), an electron transport layer (ETL), and an electron injection. Layer (EIL). To aid in hole injection and achieve a smooth surface, a motorized injection layer (HIL), located between the ITO anode and a hole transport layer, is often desired. most common The HIL material used was poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid) complex (PEDOT/PSS). However, OLEDs prepared by PEDOT/PSS exhibit a very short life due to corrosion and are caused by the high acidity of PEDOT/PSS. In addition, PEDOT/PSS solutions are often water based. When used in OLEDs, the traces of moisture remaining in the film cause corrosion to the circuit and cause the device to decay. Therefore, there is a continuing need for HIL materials, particularly non-aqueous HIL compositions, for OLED applications.

Existing multilayer OLED devices are prepared by thermal deposition. Thermal deposition, however, has its drawbacks. Thermal deposition requires thermal evaporation under high vacuum, which increases manufacturing complexity and makes the utilization of expensive OLED materials very inefficient (typically less than 20%). Furthermore, the use of evaporation masking pixelation limits the scalability and resolution of OLED devices.

Solution processes such as, for example, inkjet and nozzle printing, become feasible An alternative to the thermal deposition process technology for preparing OLED devices. Unfortunately, existing OLED materials such as N,N'-di-[(1-naphthyl)-N,N'-diphenyl]-1,1'-biphenyl)-4,4'-di Amine (NPB), and 4,4',4'-tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA), due to poor film morphology and crystallization during spin casting Not suitable for solution process.

Therefore, there is a need for an OLED material that can be used in a solution process to prepare an OLED device. There is also a need for OLED materials that are commonly used in thermal deposition and solution processes to make OLED devices.

Summary of invention

The present invention provides a composition comprising one having a table 2 Tetrastyrene (TPE) of any of the structures of Examples 1-25.

In one embodiment, the present invention provides a composition comprising a tetra-styrene of structure (I), a tetra-styrene of structure (IA), or combinations thereof, as shown below.

For each of the structures (I) and (IA), R ₁ , R ₂ , R ₃ and R ₄ are the same or different. R ₁ , R ₂ , R ₃ and R 4 are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; or R ₁ and R ₂ are each independently selected from hydrogen, hydrocarbon, and a substituted hydrocarbon, or a combination thereof, and R ₃ and R ₄ form a cyclic structure; or R ₃ and R ₄ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or the like; And R ₁ and R ₂ form a cyclic structure; or R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

The present invention also provides a film formed from the composition of the present invention comprising the tetra-styrene of the structure (I), the tetra-styrene of the structure (IA), or a combination thereof.

The present invention also provides an electronic device comprising at least one component formed from the composition of the present invention, the composition comprising the tetra-styrene of the structure (I), the tetra-styrene of the structure (IA), or A combination of the same.

An advantage of the composition of the present invention is that it can be used in both thermal evaporation and solution processes.

1 is a current-voltage graph of an OLED device in accordance with an embodiment of the present invention.

2 is a graph showing luminous efficiency of an OLED device according to an embodiment of the present invention.

3 is a graph showing attenuation of luminance intensity over time of an OLED device in accordance with an embodiment of the present invention.

Detailed description of the preferred embodiment Composition

The present invention provides a composition comprising a tetra-styrene (TPE) having the structure of any of Embodiments 1-25 of Table 2.

In one embodiment, the present invention provides a composition comprising the following: a tetra-styrene of structure (I), a tetra-styrene of structure (IA), or combinations thereof, as shown below .

For each of the structures (I) and (IA), R ₁ , R ₂ , R ₃ and R ₄ are the same or different. R _1, R _2, R ₃ and R ₄ are each independently selected from hydrogen, a hydrocarbon, substituted hydrocarbon, or a combination of the like; or R ₁ and R ₂ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof, and R ₃ and R ₄ form a cyclic structure; or R ₃ and R ₄ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof. And R ₁ and R ₂ form a cyclic structure; or R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₁ and R ₂ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or combinations thereof; and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₃ and R ₄ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or combinations thereof; and R ₁ and R ₂ form a cyclic structure.

In one embodiment, R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

Non-identifying substituents of structure (I) and structure (IA) may be selected From hydrogen, hydrocarbons, substituted hydrocarbons, cyclic structures such as phenyl, naphthyl, anthracenyl, and biphenyl, or combinations thereof. In one embodiment, the non-identifying substituents of structures (I) and (IA) are hydrogen.

"hydrocarbon", as used herein, means only a compound of hydrogen and carbon. The hydrocarbon contains from 1 to 50 carbon atoms. The hydrocarbon may be (i) branched or unbranched, (ii) saturated or unsaturated or aromatic, (iii) cyclic or acyclic, and (iv) (i) to (iii) Any combination. The term "hydrocarbon" encompasses "hydrocarbyl group" (or "hydrocarbonyl group"), which is a valence (usually monovalent) hydrocarbyl substituent. In one embodiment, the hydrocarbon comprises from 1 to 30 carbon atoms a sub, or 1 to 24 carbon atoms, or 1 to 20 carbon atoms, or 1 to 12 carbon atoms, or 1 to 6 carbon atoms.

A "substituted hydrocarbon", as used herein, refers to a hydrocarbon containing one or more heteroatoms. "Hetero atom" means an atom other than carbon or hydrogen. Non-limiting examples of heteroatoms include: fluorine, chlorine, bromine, nitrogen, oxygen, phosphorus, boron, sulfur, antimony, bismuth, aluminum, tin, arsenic, selenium, and antimony.

An "unsubstituted hydrocarbon" means a hydrocarbon that does not contain a hetero atom.

A "cyclic structure", as used herein, is a ring composed of a hydrocarbon or a substituted hydrocarbon, and the cyclic structure may be saturated or unsaturated, and the cyclic structure may comprise one, or Two, or more than two rings.

In one embodiment, the composition comprises a tetra-styrene having the structure (I) and isomers thereof. Structure (I) is provided below.

R ₁ , R ₂ , R ₃ and R ₄ are the same or different. R ₁ -R ₄ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof.

In one embodiment, R ₁ -R ₄ are each independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and combinations thereof.

An "alkyl group" is linear, branched or unbranched, saturated Hydrocarbon group. Suitable alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl (or 2-methylpropyl), hexyl, octyl and the like. In one embodiment, the alkyl group has from 1 to 30, or from 1 to 24, or from 1 to 20, or from 1 to 12, or from 1 to 6 carbon atoms.

The term "substituted alkyl" as used herein refers to The alkyl group just described wherein the hydrocarbon group comprises one or more heteroatoms.

An "aryl group" is an aromatic substituent which may be a single aromatic ring Or a plurality of aromatic rings are fused together, covalently linked, or linked to a common group such as a methylene moiety or an ethylene moiety. The (equal) aromatic ring may include a phenyl group, a naphthyl group, a fluorenyl group, a biphenyl group, and the like. In a particular embodiment, the aryl group has from 6 to 50, or from 6 to 30, or from 6 to 24, or from 6 to 20, or from 6 to 12 carbon atoms.

The term "substituted aryl", as used herein, means The aryl group just described has an aromatic substituent comprising one or more heteroatoms.

In one embodiment, the composition of the invention comprises structure (I) Isomer. The TPE of structure (I) includes Z-isomers, E-isomers, and combinations thereof.

This Z-isomer has the structure (I) shown below. In one embodiment, the composition comprises structure (I) wherein R ₁ , R ₂ , R ₃ and R ₄ are as defined above.

This E-isomer has the structure (IA) shown below. In one embodiment, the composition comprises structure (IA) wherein R ₁ , R ₂ , R ₃ and R ₄ are as defined above.

Compositions of the invention may comprise from greater than zero, or from 1 wt% to 99 Wt% Z-isomer (Structure I) and from less than 100 wt%, or 99 wt% to 1 wt% E-isomer (Structure IA).

In one embodiment, the composition comprises greater than zero, or 1 wt%, or 10 wt%, or 25 wt%, or 50 wt%, or 75 wt%, or 90 wt%, or 99 wt% Z-isomer; and from less than 100 wt%, or 99 Wt%, or 90 wt%, or 75 wt%, or 50 wt%, or 25 wt%, or 10 wt%, or 1 wt% E-isomer. The weight percentage is based on the total weight of the composition.

In one embodiment, one, some, or all of R ₁ to R ₄ comprise one or more aryl groups. In a further embodiment, each R ₁ -R ₄ comprises at least one or more aryl groups.

In one embodiment, R ₁ and R ₂ form a cyclic structure. In a further embodiment, each of R ₁ and R ₂ includes an aryl group, and R ₁ and R ₂ form a cyclic structure.

In one embodiment, R ₃ and R ₄ form a cyclic structure. In a further embodiment, each of R ₃ and R ₄ includes an aryl group, and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form another cyclic structure. In a further embodiment, each of R ₁ and R ₂ includes an aryl group, and R ₁ and R ₂ form a cyclic structure, and each of R ₃ and R ₄ includes an aryl group, and R ₃ and R ₄ forms a ring structure.

In one embodiment, the TPE has a structure selected from Table 2 Structure of 1-25.

In one embodiment, the TPE has a structure selected from Table 2 Structures of 1-5, 7-8, 10-11, and 13-25.

In one embodiment, the TPE has a structure selected from Table 2 The structure of 1, 2, and 3.

In one embodiment, the TPE has a structure selected from Table 2 Structures 1-3, and 6-25.

In one embodiment, the TPE has a structure selected from Table 2 Structures of 1-3, 7-8, 10-11, and 13-25.

In one embodiment, each of R ₁ to R ₄ is phenyl. In a further embodiment, the TPE has the following structure (II).

In one embodiment, each of the TPE of R ₁ to R ₄ is phenyl. In a further embodiment, the TPE is a mixture of Z-isomer (II) and E-isomer (IIA) as shown below.

In one embodiment, structure (I), structure (IA), or the like a combination of TPE, having from -4.30 eV, eV) to -5.20 eV, or by Highest Occupied Molecular Orbital (HOMO) energy level calculated from -4.3eV to -4.9eV.

In one embodiment, structure (I), structure (IA), or the like The combined TPE has a calculated HOMO energy level from -4.3 eV to -4.6 eV.

In one embodiment, the TPE of structure (I) has from 700 to Molecular weight (MW) of 1300 g/mole. In a further embodiment, the TPE of structure (I) has a molecular weight of from 800 to 1200 g/mole.

In one embodiment, comprising structure (I), structure (IA), or The TPE of the combination has a weight average molecular weight (Mw) of from 500 to 1500 g/mole.

In one embodiment, the composition is a solution. The solution An aromatic solvent and a TPE composition of the invention are included. The TPE has a combination of structure (I), structure (IA), or the like. The TPE is dissolved in the solvent. In one embodiment, the aromatic solvent is selected from the group consisting of xylene, toluene, benzene, anisole, or combinations thereof.

Compositions of the invention may comprise two or more of the groups disclosed herein An embodiment.

2. Film

The present invention provides a film formed from a composition comprising: the TEP having any of the structures of Examples 1-25, the TEP of the structure (I), the TEP of the structure (IA), or the like combination. The TEP of structure (I) and the TEP of structure (IA) may be any corresponding TEP as described above.

In one embodiment, the film comprises a structure (I) of the The TEP, the TEP of a structure (IA), or a combination thereof, has the following structure.

For each structure (I) and structure (IA), R ₁ , R ₂ , R ₃ and R ₄ are the same or different. R _1, R _2, R ₃ and R ₄ are each independently selected from hydrogen, a hydrocarbon, substituted hydrocarbon, or a combination of the like; or R ₁ and R ₂ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof, and R ₃ and R ₄ form a cyclic structure; or R ₃ and R ₄ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof. And R ₁ and R ₂ form a cyclic structure; or R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₁ and R ₂ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or combinations thereof; and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₃ and R ₄ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or combinations thereof; and R ₁ and R ₂ form a cyclic structure.

In one embodiment, R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

In one embodiment, the film comprises at least two layers, layer A and layer B. The A layer comprises or alternatively is formed from a TPE composition of the invention comprising the TPE of structure (I), the TPE of structure (IA), or a combination thereof. In a further embodiment, R ₁ to R ₄ are each independently selected from the group consisting of hydrogen, a hydrocarbon, a substituted hydrocarbon, and the like.

In one embodiment, the A layer is a hole injection layer. In a In a further embodiment, the A layer is an electrospray layer formed of a composition comprising the TEP of structure (I), the TEP of structure (IA), or a combination thereof, and the composition The object has a HOMO energy level from -4.3 eV to -4.6 eV.

In one embodiment, layer B is a hole transport layer.

In one embodiment, the thickness of layer A is from 5 nm to 500 nm, or from 5 nm to 100 nm, or from 5 nm to 50 nm, and the thickness of the B layer is from 5 nm to 500 nm, or from 5 nm to 100 nm, or from 5 nm to 50 nm.

In one embodiment, the A layer further comprises a p-type dopant (p-type dopant). In a further embodiment, the p-type dopant is an organometallic compound or an organometallic salt.

In one embodiment, the p-type dopant is an organometallic salt comprising at least one phenyl group. In a further embodiment, the anionic component of the organometallic salt comprises a boron atom. In another further embodiment, the organometallic salt has a structure selected from one of the following: , or a combination thereof.

In one embodiment, the organometallic salt has the structure:

In one embodiment, the amount of dopant in layer A is from 1 weight percent (wt%) to 99 wt%, or from 1 wt% to 50 wt%, or from 1 wt% to 30 wt%, based on the weight of the composition.

The films of the present invention may comprise two or more embodiments as disclosed herein.

3. Electronic device

The present invention provides an electronic device comprising at least one component formed of a composition comprising tetra-styrene having the structure of any of embodiments 1-25, tetra-styrene of structure (I), structure (IA) Tetrastyrene, or a combination thereof. The TEP of structure (I) and the TEP of structure (IA) may be any corresponding TEP as described above.

In one embodiment, the electronic device includes the TEP of the structure (I), the TEP of a structure (IA), or a combination thereof, and has the following structure.

For each structure (I) and structure (IA), R ₁ , R ₂ , R ₃ and R ₄ are the same or different. R _1, R _2, R ₃ and R ₄ are each independently selected from hydrogen, a hydrocarbon, substituted hydrocarbon, or a combination of the like; or R ₁ and R ₂ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof, and R ₃ and R ₄ form a cyclic structure; or R ₃ and R ₄ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof. And R ₁ and R ₂ form a cyclic structure; or R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₁ and R ₂ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or combinations thereof; and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₃ and R ₄ are each independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or combinations thereof; and R ₁ and R ₂ form a cyclic structure.

In one embodiment, R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

In an embodiment, the electronic device includes at least one A layer of a composition of the invention comprising the TPE of structure (I), the TPE of structure (IA), or a combination thereof.

In an embodiment, the electronic device includes a first electrical pole.

In an embodiment, the electronic device includes a a second electrode on the first electrode.

In an embodiment, the electronic device includes a An organic layer between the first electrode and the second electrode. The organic layer comprises a composition comprising the TPE of structure (I), the TPE of structure (IA), or a combination thereof, according to the invention.

In one embodiment, the organic layer is an A layer and the A layer is an electric Hole injection layer.

In an embodiment, the electronic device includes a second B Floor.

In one embodiment, layer B is a hole transport layer.

In one embodiment, layer A is in contact with layer B.

In an embodiment, the electronic device includes a light emitting layer (emitting layer).

In one embodiment, the thickness of layer A is from 1 nm to 1000 nm, or from 2 nm to 500 nm, or from 5 nm to 200 nm. The thickness of the B layer is from 1 nm to 1000 nm, or from 2 nm to 500 nm, or from 5 nm to 200 nm.

In one embodiment, the electronic device is an OLED (organic Light-emitting diode).

In one embodiment, the electronic device includes an ITO The first electrode of the layer. The electronic device further includes an HIL layer, the A layer, which is a TPE composition comprising the TPE of the structure (I) of the invention, the TPE of the structure (II), or a combination thereof. The electronic device further includes an HTL layer and a B layer. The TPE composition of the A layer has a HOMO energy level between the HOMO energy level of the ITO layer and the HOMO energy level of the HTL material. In one embodiment, the A layer TPE composition has a calculated HOMO value from -4.3 eV to -4.6 eV.

The electronic device of the present invention may comprise two or more of the above disclosed A combination of various embodiments.

definition

All parts and percentages are by weight unless otherwise indicated by the contrary, implied by context, or customary in the art. For the purposes of the U.S. Patent Practice, the disclosure of any of the patents, patent applications, or disclosures herein is hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in its entirety in its entirety in particular in its Inconsistent with any definition specifically provided by this application, and the disclosure of general knowledge.

The terms "including", "comprising", "having" and their derivatives are used without the exclusion of any additional components, steps or processes, whether or not they are specifically disclosed. In order to avoid any doubt, the use of the term "comprising", unless otherwise indicated, includes any additional additive, adjuvant, or compound, whether polymeric or otherwise. Conversely, except those that are not necessary for operational performance, The phrase "consisting essentially of" excludes any additional components, steps or processes from the scope of any of the following. The term "consisting of" excludes any component, step or process not specifically described or listed.

"Doping agent" and the like, when referring to an electron acceptor or The donor is added to the organic layer as an additive to increase the conductivity of the organic layer of the organic electronic device. The conductivity of the organic semiconductor can be similarly affected by doping. Such an organic semiconductor host material can be made of any compound having electron donor characteristics or a compound having electron acceptor properties.

"Lighting layer" and similar terms refer to a subject and A layer composed of a dopant. The host material can be bipolar or unipolar and can be used alone or in combination of two or more host materials. The optoelectronic properties of the host material may vary depending on the type of dopant used (phosphorescence or fluorescence). For fluorescent dopants, the auxiliary host material should have a spectral overlap between the adsorption of the dopant and the emission of the host to induce good Foester transfer to the dopant. For phosphorescent dopants, the auxiliary host material should have a high triplet energy to limit the triplet of the dopant.

"Electrical Transfer Layer (HTL)" and similar terms mean a A layer made of material that transfers holes. High hole mobility is recommended for OLED devices. The HTL is a path for helping to block electrons transmitted through the light-emitting layer. Small electron affinities are often required to block electrons. The HTL should ideally have a larger triplet to prevent migration of excitons from adjacent EML layers. Examples of HTL compounds include, but are not limited to, two (pairs) Di(p-tolyl)aminophenyl]cyclohexane) (TPAC), N,N-diphenyl-N,N-bis(3-methylphenyl)-1, 1'-Biphenyl-4,4-diamine (N,N-diphenyl-N,N-bis(3-methylphenyl)-1,1-biphenyl-4,4-diamine) (TPD) and N,N' -diphenyl-N,N'-bis(1-naphthyl)-(1,1'-biphenyl)-4,4'-diamine (N,N'-diphenyl-N, N'-bis ( 1-naphthyl)-(1,1'-biphenyl)-4,4'-diamine) (NPB).

Some embodiments of the invention are now described in detail in the following examples.

Example Material

The materials used in the following examples are shown in Table 1.

2. Nature

Nuclear Magnetic Resonance ( ¹ H and ¹³ C NMR): These samples were dissolved in a suitable deuterated solvent at a concentration of 10 mg/mL. Magnetic resonance spectra were recorded on a Varian Mercury Plus 400 MHz spectrometer. Chemical shifts are reported relative to tetramethylsilane.

Liquid chromatography/mass spectrometry (LC/MS): The sample was dissolved in THF at about 1 mg/mL. 1 μL of the solution was injected for LC/MS analysis.

Instrument: Agilent 1220 HPLC/G6224A TOF mass spectrometer

Column: Agilent eclipse-C18 4.6*50mm, 1.7μm

Column heater temperature: 30 ° C

Solvent: A: THF; B: 0.1% FA in water / THF 95/5

Gradient: 0-6 minutes 40-80% A, maintained for 9 minutes

Flow rate: 0.3mL/min

UV detector: Diode Array 254nm

MS conditions: capillary voltage: 3900kV (Neg), 3500kV (Pos)

Mode: Neg and Pos

Scan: 100-2000 amu

Rate: 1s/scan

Desolvent temperature: 300 ° C

High pressure liquid chromatography (HPLC): A sample of about 50 mg was weighed and diluted with 10 g of tetrahydrofuran. The sample solution was filtered through a 0.45 μm syringe filter and 5 μl of the filtrate was injected into the HPLC system.

Cyclic voltammetry (CV): The CV of the compound is carried out in a CHI voltammetric analyzer with a Pt counter electrode, a Hg/Hg ₂ Cl ₂ reference electrode, and a platinum electrode plate in a three-electrode cell at a scan rate of 10 mV/s and 0.1 M tetrabutylammonium hexafluorophosphate as a supporting electrolyte. Ferrocene was added as an internal standard. The potential value is calculated based on the peak difference of the oxidation peak of the hole injection material and the ferrocene standard.

Atomic Force Microscopy (AFM): AFM applied to imaged surfaces Morphology and determination of the surface roughness and film thickness of the spin-coated HIL film. The AFM measurement was performed in a tapping mode by a Dimension V instrument manufactured by Veeco.

The amplitude (A) of the vertical deviation is used to calculate the roughness of the surface. The amplitude constants R _a and R _q are used to describe the surface roughness. R _a is the arithmetic mean of the absolute amplitude values, and R _q is the root mean square of the amplitude values, which are described as:

Where A _i is the amplitude (height or depth) of one pixel i (point on the surface) in the AFM image, and n is the total number of pixels in the image.

In order to determine the thickness of the spin coating film, a part of the film is used as a front The blade is removed from the ITO substrate and then scanned in a cantilever. The thickness of the film is known from the difference between the two parts.

3. Synthesis of four-stretch styrene materials

A. Synthesis of 1,2-bis(4-bromophenyl)-1,2-diphenylethenes (1)

4-Bromobenzophenone (5 g, 19.2 mmol) and zinc powder (2.5 g, 38.2 mmol) were placed in a 250 mL two-necked round bottom flask equipped with a reflux condenser. After evacuating under vacuum and rinsing three times with dry nitrogen, 100 mL of THF was added. The mixture was cooled to 0-5 ° C in an ice water bath, and 2.1 mL (19.2 mmol) of TiCl ₄ was slowly added using a syringe. The mixture was slowly warmed to room temperature, and after stirring for 0.5 hour, it was refluxed for 12 hours. After cooling to room temperature, the reaction mixture was poured into ice water and extracted three times with dichloromethane. The solvent was evaporated under vacuum and the residue was washed with ethylamine to afford white powder (yield 70%).

¹ H-NMR (CDCl ₃ , 400 MHz): 7.19-7.25 (m, 3H), 7.06-7.13 (m, 7H), 6.96-7.03 (m, 5H), 6.85-6.90 (m, 3H).

B. Synthesis of 1,2-bis[4-(N-phenyl)aminophenyl]-1,2-di-stilbene (1,2-bis[4-(N-phenyl)aminophenyl]-1, 2-diphenylethenes)(2)

(1) (4.90 g, 10 mmol), Pd ₂ (dba) ₃ (0.549 g, 0.6 mmol), t-BuOK (4.49 g, 40 mmol) and BINAP were placed in a 250 ml 3-neck round bottom flask under a nitrogen atmosphere. (0.747 g, 1.2 mmol). After evacuating under vacuum and rinsing three times with dry nitrogen, aniline (2.32 g, 25 mmol) and 60 mL of anhydrous tolu. The mixture was heated to 80 ° C overnight and allowed to cool to room temperature. The mixture was centrifuged, and the supernatant was concentrated and purified on a cerium oxide column using a mixture of petroleum ether and ethyl acetate (10:1) as a washing liquid. The product (2) was a pale yellow powder (yield 40%).

^{1 H-NMR (d 6 -DMSO} , 400MHz), δ (TMS, ppm): 8.10-8.18 (d, 2H), 7.15-7.23 (m, 6 H), 7.05-7.15 (m, 4H), 6.95- 7.07 (m, 6H), 6.75-6.88 (m, 10 H).

C. Synthesis of 1,2-bis(4-{N,N-[4-(N,N-diphenylamino)phenyl] Phenyl}amino)-1,2-diphenylene [1,2-bis(4-{N,N-[4-(N,N-diphenylamino)phenyl]phenyl}amino)-1,2-diphenylethene ](3)

(2) (1.54 g, 3 mmol), Pd ₂ (dba) ₃ (0.137 g, 0.15 mmol) and t- BuOK (1.35 g, 12 mmol) were added to a 250 ml 3-neck round bottom flask under a nitrogen atmosphere. After evacuating under vacuum and rinsing three times with dry nitrogen, a toluene solution of P(t-Bu) ₃ (100 mg/mL) (0.9 mL, 0.45 mmol) and 20 mL of anhydrous toluene were sequentially added by syringe. The mixture was heated to 80 ° C overnight and allowed to cool to room temperature. The mixture was centrifuged and the supernatant was concentrated and purified on a cerium oxide column using a mixture of petroleum ether and dichloromethane (2:1) as eluent. The product (3) was a bright yellow powder (yield 60%). The yellow powder was purified by sublimation at 360 ° C to obtain a pure product having an HPLC purity of 99.4% (Z isomer: 55.7%, E isomer: 46.7%).

¹ H-NMR (CD ₂ Cl ₂ , 400 MHz), δ (TMS, ppm): 6.5-7.5 (m) ¹³ C-NMR (CD ₂ Cl ₂ , 100 MHz), δ (ppm): 122.27, 122.41, 123.78, 123.95, 125.34, 125.46, 126.34, 127.62, 129.20, 131.46, 132.21

HRMS (ESI, m/z ): 1001.45 (M+H ⁺ )

Non-limiting examples of TPEs having structure (I), structure (IA) of the present invention are provided in Table 2 below.

4.HOMO energy level

HOMO calculation

Density functional calculations are performed using the Gaussian09 program group. The ground state geometry of each molecule uses the B3LYP function and the 6-31G(d) basis, respectively. The group is optimized from HOMO molecular orbital value extraction in units of electron volts (eV).

The geometry of each molecule in the neutral and triplet states is like The same method and the basis set for the calculation in the ground state are optimized, and thus the calculation of the ground state, the triplet energy is calculated from the energy difference between the neutral triplet state and the ground state energy.

The procedure described in one document ( J. Phys. Chem. A, 2003 , 107, 5241-5251) was used to calculate the recombination energy of each molecule as an indicator of electron and hole mobility.

Table 3 below compares the HOMO energy level of Example 1 (from Table 2) with He extended the HOMO level of the styrene compound (Inv-invention and Comp=comparative).

5. Film

ITO glass (soda lime glass: 2 cm * 2 cm) was pretreated by applying ultrasonic waves in soapy water, acetone, ethanol, and isopropyl alcohol, and thoroughly dried in the air. This composition (3) was prepared according to the synthesis example (described above) and dissolved in anisole at a concentration of 5 mg/mL. The solution was then spin coated onto clean ITO. The surface roughness of the spin-coated film of Compound 3 on ITO was characterized by atomic force microscopy (AFM) (shown in Table 4). It has a surface roughness of 5.3 nm with respect to the original ITO, and after the spin coating of the compound 3 on the ITO, the surface roughness (R _q ) is reduced to 0.5 nm after spin coating of the compound 3 on the ITO.

6. Device example A. Device example 1

All organic materials were purified by sublimation before being deposited. The OLED (Organic Light Emitting Diode) was prepared as an anode on an ITO coated glass substrate and covered with an aluminum cathode. All of the organic layers were thermally deposited by chemical vapor deposition at a base pressure of less than 1 x 10 ^-7 Torr in a vacuum chamber. The deposition rate of the organic layer is maintained at 0.1 to 0.05 nm/s. The aluminum cathode was deposited at 0.5 nm/s. The active area of the OLED device is "3 mm x 3 mm" which is defined by a cathodic deposited shadow mask. The glass substrate (20 mm x 20 mm) having an ITO layer having a thickness of 1500 angstroms was purchased from Samsung Corning.

The ITO glass (2 cm x 2 cm) was cleaned as described in the film examples above and treated with oxygen plasma. Compound 3 was prepared in the synthesis example (previously described) and dissolved in anisole at a concentration of about 20 mg/ML. The solution of Compound 3 was spin-coated on ITO as a HIL in a glove box. The film was annealed at 80 ° C for 20 minutes. The film substrates were then transferred to a thermal evaporator at a vacuum of about 1 x 10 ^-7 Torr. The following layers were deposited in sequence: HTL1, HTL2, Fl blue EML, Aluminum 8-Hydroxyquinolinate (Alq ₃ ) and Lithium quinolate (Liq), thickness: 5 nm, 25 nm 20 nm, 30 nm and 2 nm. The deposition rate of the organic layer is maintained at 0.1 to 0.05 nm/s. The deposition rate of the organic layer is maintained at 0.1 to 0.05 nm/s. The aluminum cathode was deposited at 0.5 nm/s. The OLED device has a campus area of "3mm x 3mm" as defined by the shadow mask of the cathode deposition.

Finally the device was sealed with epoxide prior to testing. The structure of the device is as follows: Compound 3 (40 nm) / HTL1 (5 nm) / HTL 2 (25 nm) / Fl Blue ML (20 nm) / Alq ₃ (30 nm) / Liq (2 nm)

B. Device example 2

The process was the same as described in Device Example 1, except that the composition (3) was vacuum deposited on ITO instead of spin coating. The structure of the device is as follows: Compound 3 (40 nm) / HTL1 (5 nm) / HTL 2 (25 nm) / Fl Blue ML (20 nm) / Alq ₃ (30 nm) / Liq (2 nm)

C. Comparative Example 3 - Device

This process was the same as described in Device Example 1, except that 2-TNATA was vacuum evaporated as HIL instead of Compound 3.

D. Comparative Example 4 - Device

This process was the same as that described in Example 1, except that polythiophene (Plextronics) was spin coated as HIL instead of Compound 3.

E. Testing

The current-voltage-luminance (J-V-L) characterization of the OLED is performed by a source measurement unit (KEITHLY 238) luminometer (MINOLTA CS-100A). The EL spectra of these OLED devices are collected by a calibrated CCD spectrograph.

The current-voltage curves, luminous efficiency curves, and luminescence decay curves of the apparatus examples 1 and 2 of the present invention, and the comparative samples 3 and 4 are shown in Figs. 1, 2, and 3, respectively. The data for the drive voltage (at 1000 Cd/ ^m2 ), current efficiency (at 1000 Cd/ ^m2 ) and service life (4000 Cd/ ^m2 , after 600 min) for these devices are listed in Table 5.

Figures 1-3 and Table 5 show inventive devices 1 and 2 using the inventive composition (3) as HIL (whether in thermal evaporation deposition or solution processes), and Comparative Examples 3 and 4 exhibit comparable drive Voltage and efficiency. However, Device Examples 1 and 2 exhibited a better service life than the comparative examples. After using the initial luminance of 4000 Cd/m ² for 600 minutes, the device (device example 1) containing the compound 3 applied by the evaporation process maintained the same brightness (100%) as the start, and contained the compound 3 applied by the solution process. The brightness of the device (device example 2) became slightly brighter (102.3%) than the initial brightness. However, the apparatus containing the polythiophene (Comparative Example 3) and 2-TNATA (Comparative Example 4) as the HIL was reduced to 91.3% and 97.3%, respectively, after the same period.

In the present invention, the applicant has developed the inclusion structure (I) A hole injecting material formed by the composition of the TPE, the TPE of the structure (IA), or a combination thereof. The TPE compositions of the present invention are all suitable for thermal evaporation and solution processes. The device containing this material as the HIL exhibits a driving voltage and efficiency comparable to those of the polythiophene and 2-TNATA for the HIL, but has a longer lifetime than those using the polythiophene and 2-TNATA for the HIL.

It is to be noted that the invention is not limited to the embodiments and illustrations contained herein, but includes modifications of those embodiments, including combinations of elements in the embodiments and elements of different embodiments, such as falling into the following application Within the scope of the patent.

Claims (18)

A composition comprising: a tetra-styrene of structure (I), a tetra-styrene of structure (IA), or a combination thereof: Wherein, for each of the structures (I) and (IA), R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and wherein R ₁ , R ₂ , R ₃ and R 4 are each independently selected from hydrogen a group consisting of a hydrocarbon, a substituted hydrocarbon, or a combination thereof, or wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a hydrocarbon, a substituted hydrocarbon, or the like. And R ₃ and R ₄ form a cyclic structure; or wherein R ₃ and R ₄ are each independently selected from the group consisting of hydrogen, a hydrocarbon, a substituted hydrocarbon, or the like, And R ₁ and R ₂ form a cyclic structure; or wherein R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure. The composition of claim 1, comprising a group selected from the group consisting of The isomer of structure (I): a Z-isomer, an E-isomer, or a combination thereof. The composition of claim 1, wherein R ₁ to R ₄ each comprise at least one aryl group. The composition of claim 1, wherein each of R ₁ to R ₄ is a phenyl group. The composition of claim 1, wherein the tetra-styrene of the structure (I), the tetra-styrene of the structure (IA), or a combination thereof, has a calculated value of from -4.3 eV to -4.6 eV. HOMO energy level. The composition of claim 1, wherein the tetrastyrene of the structure (I) has a molecular weight of from 700 g/mol to 1300 g/mol. The composition of claim 1 further comprises an aromatic solvent. The composition of claim 7, wherein the aromatic solvent is selected from the group consisting of xylene, toluene, benzene, anisole, or a combination thereof. A film comprising at least two layers, an A layer and a B layer, and wherein the A layer is formed by the composition of claim 1. The film of claim 9, wherein the layer A is a hole injection layer. The film of claim 10, wherein the composition has a calculated HOMO energy level from -4.3 eV to -4.6 eV. The film of claim 9, wherein the layer B is a hole transport layer. An electronic device comprising at least one component formed from the composition of claim 1. The electronic device of claim 13, further comprising a first electrode. The electronic device of claim 13-14 further includes a second electrode disposed on the first electrode. The electronic device of claim 13, wherein the component comprises the composition as An organic layer disposed between the first electrode and the second electrode. The electronic device of claim 13, wherein the component is a hole injection layer comprising the composition. The electronic device of claim 17, wherein the composition has a calculated HOMO energy level from -4.3 eV to -4.6 eV.