Great research starts with great data.

Learn More
More >
Patent Analysis of

Thienothiophene—boron (donor-acceptor) based materials for organic light emitting diodes

Updated Time 12 June 2019

Patent Registration Data

Publication Number

US10000513

Application Number

US15/552492

Application Date

20 February 2015

Publication Date

19 June 2018

Current Assignee

TUBITAK

Original Assignee (Applicant)

TUBITAK

International Classification

C07F5/02,H01L51/00,C09K11/06,H01L51/50

Cooperative Classification

C07F5/025,C09K11/06,H01L51/0061,C09K2211/1018,H01L51/0003

Inventor

OZTURK, TURAN,TEKIN, EMINE,PIRAVADILI MUCUR, SELIN,GOREN, AHMET CEYHAN,TURKOGLU, GULSEN,CINAR, MEHMET EMIN,BUYRUK, ALI

Patent Images

This patent contains figures and images illustrating the invention and its embodiment.

US10000513 Thienothiophene—boron (donor-acceptor) materials 1 US10000513 Thienothiophene—boron (donor-acceptor) materials 2 US10000513 Thienothiophene—boron (donor-acceptor) materials 3
See all images <>

Abstract

The present invention discloses new molecules having defined structures of a series of thienothiophene (TT) and boron derivatives, light emitting devices of which are expected to be applied to organic light emitting diodes (OLED).

Read more

Claims

1. Compound of formula (I) wherein R1, R2 and R3 are independently or equally atom chain(s)/group(s) of about 1 atom to 100 atoms equally or independently have one or more of a group comprising branched or non-branched alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

2. Formulation comprising the compounds given in claim 1.

3. A method of using the formulation comprising the compound given in claim 1 as charge transport, electrically conducting, semiconducting, photoconducting or light emitting material in electronic, optical, electrooptical, electroluminescent or photoluminescent components or devices.

Read more

Claim Tree

  • 1
    1. Compound of formula (I) wherein
    • R1, R2 and R3 are independently or equally atom chain(s)/group(s) of about 1 atom to 100 atoms equally or independently have one or more of a group comprising
  • 2
    2. Formulation comprising
    • the compounds given in claim 1.
  • 3
    3. A method of using the formulation comprising
    • the compound given in claim 1 as charge transport, electrically conducting, semiconducting, photoconducting or light emitting material in electronic, optical, electrooptical, electroluminescent or photoluminescent components or devices.
See all independent claims <>

Description

FIELD OF INVENTION

The present invention relates to thienothiophene and boron derivatives with specified structures. They have potential of application to organic light emitting diodes (OLED).

BACKGROUND OF THE INVENTION

Organic electronic and optoelectronic materials have the attention of growing number of, particularly, physics and chemistry researchers for more than 50 years, the main mason of which is the higher possibility of modifying the chemical structures of the organic compounds. Thus, the properties of the materials could directly be affected. Until the mid-1980s, stability and performance of the devices made of organic materials fell short of those devices based on materials such as silicon or gallium arsenide. This has been changed with the appearance of a low voltage and efficient thin film light emitting diode. It provided the possibility of using organic thin films for a new generation of electronic and optoelectronic devices. It has now been proven that organic thin films are useful in various applications and organic light emitting device (OLED) is the most successful one, which is used now in full-color displays.

Generally, two groups of organic materials, small molecules and polymers, are used in electronic and optoelectronic devices and both can be processed from solutions and allow low cost fabrication of devices. Small molecule and polymer electro-luminescent devices are described, for example, C. W. Tang, Appl. Phys. Letters, 1987, 51, 913-915; J. H. Burroughes, Nature, 1990, 347, 539; U.S. Pat. No. 6,727,008, U.S. Pat. No. 7,133,032, WO 2007/134280A1; US2005/01184A1; WO90/13148; US005399502; U.S. Pat. No. 4,356,429.

Designing high performance optical and electronic organic devices requires understanding of their electronic structures, and even some small tunings in the structure or composition of an organic material can alter its original properties enormously. Modification of the structures of the conjugated organic materials to tune their optoelectronic properties is a challenging topic. Thiophene-based organic materials are among the most promising compounds with tunable functional properties by proper molecular engineering. For example, converting oligothophenes into the corresponding oligothiophene-S,S-dioxides has been shown to be useful for increasing both thin film photoluminescence efficiencies and molecular energy levels.

Recently, boron has been applied to alter the properties of organic electronic and optoelectronic materials, which gave interesting results. Presence of empty pz orbital of boron, which behaves as strong electron withdrawing atom when it makes three bonds, is the main reason for altering the properties. It delocalizes electrons strongly when it is integrated to “π” systems, and conjugated organoboranes are now considered as new class of organic materials with their widespread applications in electronics, optoelectronics and sensors.

Materials, having the combinations of different functional building blocks like thiophene, thiophene derivatives and boron, tend to emit bright white light from a single active molecular material (M. Mazzeo, Adv. Mater. 2005, 17, 34). The AIE (Aggregation-Induced Emission) nature and hole-transport capability of a material, comprised of tetraphenylethylene and triphenylamine, have enabled the fabrication of OLEDs devices with simple structures and low-cost but good performance (Tang Z. B. Adv. Mater. 2010, 22, 19). AIE-Active materials incorporated with an inherently electron-deficient group, dimesitylboryl, enable them to serve simultaneously as bifunctional materials of light emitter and electron transporting layer in OLEDs (Tang Z. B. Adv. Functional Mater. 2014, 24, 3611-3630). Thus, it would be desirable developing materials having thiophene, thiophene derivatives and boron to obtain various emissions for organic light emitting diodes.

DISCLOSURE OF THE INVENTION

The invention discloses the compounds that are useful when employed as organic light emitting materials, i. e. organic light emitting diodes (OLED). They have potential of being employed as charge transport materials in electronic devices such as organic field effect transistors (OFET), organic photovoltaic diodes and the like. The invention discloses the compounds having the formulas (I).

wherein

R1, R2 and R3 are independently or equally atom chain(s)/group(s) of about 1 atom to 100 atoms. They may equally or independently have one or more of a group comprising branched or non-branched alkyl, aryl, alkenyl, alkynyl, amine, ester, carbonate ester, carbonyl, sulphide, organosilane and thiolate.

Thienothiophenes I (TT) was synthesized following the literature procedure (T. Ozturk, et al. Tetrahedron, 2005, 61, 11055; E. Ertas, et al. Tetrahedron Lett. 2004, 45, 3405; I. Osken, Tetrahedron, 2012, 68, 1216; P. Dundar, Synth. Met. 2012, 162, 1010; I. Osken, Thin Solid Films, 2011, 519, 7707; O. Sahin, Synth. Met. 2011, 161, 183; O. Mert, J. Electroanal. Chem. 2006, 591, 53; A. Capan, Macromolecules 2012, 45, 8228; I. Osken, Macromolecules 2013, 46, 9202). The TTs I were produced by lithiation of bromo-TTs II with n-BuLi, which was followed by addition of aryldimethoxyborane.

EXAMPLE

A Procedure for the Synthesis of 4-(5-(mesityl(methoxy)boranyl)-3-(4-methoxyphenyl)thieno[3,2-b]thiophen-2-yl)-N,N-diphenylaniline (I*)

To a solution of 4-(3-(4-methoxyphenyl)thieno[3,2-b]thiophen-2-yl)-N,N-diphenylaniline (123 mg, 240 μmol) in 30 mL of dry THF was added n-BuLi (185 μL, 290 μmol) dropwise at −78° C. under nitrogen atmosphere. The reaction mixture was stirred at same temperature for 1 h. Then MesB(OMe)2 (51.0 μL, 240 μmol) was added at −78° C. and the solution was heated slowly up to room temperature and then stirred for another 12 h. The product was extracted with dichloromethane (3×20 mL). The solution was washed with brine and H2O, and then dried over NaSO4. After removal of the solvent under atmospheric, the crude product was purified by column chromatography over silica gel using a mixture of n-hexane/dichloromethane (6:1) as eluent. The product was obtained as a green solid in 45% yield; Rf=0.85; M.p. 179-180° C.; 1H NMR (500 MHz, CDCl3) δ 7.74 (s, 1H), 7.38 (d, J=9.0 Hz, 2H), 7.26 (t, J=8.0 Hz, 4H), 7.18 (d, J=9.0 Hz, 2H), 7.11 (d, J=7.5 Hz, 4H), 7.05 (t, J=7.5 Hz, 2H), 6.92 (dd, J=8.0, 2.5 Hz 4H), 6.82 (s, 2H), 3.83 (s, 3H), 2.32 (s, 3H), 2.10 ppm (s, 6H); 13C NMR (125 MHz, CDCl3): δ 158.9, 152.5, 147.6, 1472, 146.7, 144.3, 137.6, 136.6, 136.5, 132.5, 131.5, 130.2, 129.8, 129.4, 129.3, 127.8, 127.6, 126.9, 124.9, 123.4, 122.1, 114.2, 55.2, 28.1, 22.3 ppm.

Example of a Device Fabrication:

Organic light emitting devices were fabricated by coating the molecules from their solution onto electrically conductive substrates. The molecule (I) was dissolved in a mixture of toluene/dichlorobenzene (8 mg/ml). Indium thin oxide (ITO), coated (15 ohms/sq.) on a glass, was employed as an anode electrode. PEDOT:PSS, as a hole injection layer, was spin-coated on ITO, which was dried at 110° C. for 10 min. Subsequently, molecule film, as an active layer, was coated by spin coating. Finally, LiF (1 nm) and aluminum (Al, 100 nm) was deposited under vacuum (˜10−6 mbar) by thermal evaporation technique to assemble the cathode electrodes.

DESCRIPTION OF DRAWINGS

FIG. 1. UV-Vis spectrum of molecule (I) in tetrahydrofuran (THF) solution at room temperature

FIG. 2. Fluorescence spectrums of molecule (I) in tetrahydrofuran solution (THF) and in the solid state (on ITO coated glass) at room temperature

FIG. 3. a) Electroluminescent spectrum of the fabricated device of the molecule (I) (device layout: PEDOT/Molecule(I*)/LiF/Al), b) CIE coordinates of the fabricated device of the molecule (I) at different voltages. The electroluminescent spectrum covers the region almost from 400 nm to 650 nm. Color coordinates are in the region for blue-green color according to the CIE 1931 Chromaticity Diagram.

FIG. 4. OLED device characteristics: a) voltage-current b) luminance-voltage c) luminous efficiency-current density and d) external quantum efficiency-current density.

Read more
PatSnap Solutions

Great research starts with great data.

Use the most comprehensive innovation intelligence platform to maximise ROI on research.

Learn More

Patent Valuation

$

Reveal the value <>

23.36/100 Score

Market Attractiveness

It shows from an IP point of view how many competitors are active and innovations are made in the different technical fields of the company. On a company level, the market attractiveness is often also an indicator of how diversified a company is. Here we look into the commercial relevance of the market.

48.0/100 Score

Market Coverage

It shows the sizes of the market that is covered with the IP and in how many countries the IP guarantees protection. It reflects a market size that is potentially addressable with the invented technology/formulation with a legal protection which also includes a freedom to operate. Here we look into the size of the impacted market.

64.58/100 Score

Technology Quality

It shows the degree of innovation that can be derived from a company’s IP. Here we look into ease of detection, ability to design around and significance of the patented feature to the product/service.

15.0/100 Score

Assignee Score

It takes the R&D behavior of the company itself into account that results in IP. During the invention phase, larger companies are considered to assign a higher R&D budget on a certain technology field, these companies have a better influence on their market, on what is marketable and what might lead to a standard.

19.65/100 Score

Legal Score

It shows the legal strength of IP in terms of its degree of protecting effect. Here we look into claim scope, claim breadth, claim quality, stability and priority.

More like this

Title Current Assignee Application Date Publication Date
Organic light emitting element having high efficiency SFC CO., LTD. 28 July 2016 09 February 2017
Light-emitting material, preparation method therefor and organic light-emitting diode using same SHENZHEN CHINA STAR OPTOELECTRONICS TECHNOLOGY CO.,LTD. 17 August 2016 25 January 2018
Organic light emitting element having high efficiency SFC CO., LTD. 27 May 2016 15 December 2016
Light-emitting material, preparation method therefor and organic light-emitting diode using light-emitting material SHENZHEN CHINA STAR OPTOELECTRONICS TECHNOLOGY CO., LTD. 17 August 2016 25 January 2018
Precursor based method of synthesis and fabrication of hybrid lighting phosphors with high quantum efficiency, and significantly enhanced thermal and photostability RUTGERS, THE STATE UNIVERSITY OF NEW JERSEY 15 May 2017 30 November 2017
Organic light-emitting element capable of low-voltage drive and having long life SFC CO., LTD. 15 January 2016 11 August 2016
Heterocyclic compound and organic light emitting element comprising same LG CHEM, LTD. 26 October 2016 04 May 2017
Light-emitting element, display device, electronic device, and lighting device SEMICONDUCTOR ENERGY LABORATORY CO., LTD. 24 April 2017 09 November 2017
Π-conjugated boron compound, electronic device, and methods respectively for producing triarylborane and intermediate thereof KONICA MINOLTA, INC.,TOHOKU UNIVERSITY 17 March 2017 28 September 2017
Compound for organic light emitting diode, and organic light emitting diode including same SFC CO., LTD. 15 April 2016 15 December 2016
Organic conductive materials and devices MASSACHUSETTS INSTITUTE OF TECHNOLOGY 23 March 2016 29 September 2016
Heterocyclic compound and organic light emitting element using same HEESUNG MATERIAL LTD. 08 November 2016 26 May 2017
Organic molecules having two non-conjugated bridges between a donor and an acceptor for effective thermally activated delayed fluorescence for use in optoelectronic devices YERSIN, HARTMUT,CZERWIENIEC, RAFAL,MATARANGA-POPA, LARISA 28 July 2016 02 February 2017
Highly efficient organic light-emitting element SFC CO., LTD. 08 July 2016 19 January 2017
Organic semiconducting compounds MERCK PATENT GMBH 06 July 2017 11 January 2018
Organic red electroluminescent chromophores, method for the production and use thereof SIEMENS AKTIENGESELLSCHAFT 15 February 2002 04 May 2005
Heterocyclic compound and organic light emitting element comprising same LG CHEM, LTD. 23 August 2016 02 March 2017
Organic light-emitting element LG CHEM, LTD. 01 June 2017 07 December 2017
Spiro compound and organic light-emitting element comprising same LG CHEM, LTD. 17 November 2016 26 May 2017
Heterocyclic compound and organic light emitting diode using same HEESUNG MATERIAL LTD. 27 July 2016 11 May 2017
See all similar patents <>

More Patents & Intellectual Property

PatSnap Solutions

PatSnap solutions are used by R&D teams, legal and IP professionals, those in business intelligence and strategic planning roles and by research staff at academic institutions globally.

PatSnap Solutions
Search & Analyze
The widest range of IP search tools makes getting the right answers and asking the right questions easier than ever. One click analysis extracts meaningful information on competitors and technology trends from IP data.
Business Intelligence
Gain powerful insights into future technology changes, market shifts and competitor strategies.
Workflow
Manage IP-related processes across multiple teams and departments with integrated collaboration and workflow tools.
Contact Sales
Clsoe
US10000513 Thienothiophene—boron (donor-acceptor) materials 1 US10000513 Thienothiophene—boron (donor-acceptor) materials 2 US10000513 Thienothiophene—boron (donor-acceptor) materials 3