KR20110106397A - Electronic devices having long lifetime - Google Patents

Abstract

An organic light emitting diode is provided having an anode, a cathode, and an organic active layer therebetween. The organic active layer comprises a deuterated compound and the device has a calculated half life of at least 5000 hours at 1000 nits.

Description

Electronic device with long life {ELECTRONIC DEVICES HAVING LONG LIFETIME}

Related application data

This application claims 35 U.S.C. US Application No. 12 / 643,459, filed December 21, 2009, pursuant to § 119 (e), US Provisional Application No. 61 / 139,834, filed December 22, 2008, filed February 27, 2009 US Provisional Application No. 61 / 156,181, filed April 3, 2009 US Provisional Application No. 61 / 166,400, filed May 7, 2009, US Provisional Application No. 61 / 176,141, May 19, 2009 U.S. Provisional Application No. 61 / 179,407, filed U.S. Provisional Application No. 61 / 228,689, filed July 27, 2009,

US Provisional Application No. 61 / 233,592, filed August 13, 2009, US Provisional Application No. 61 / 239,574, filed September 3, 2009, US Provisional Application No. 61 / 246,563, filed September 29, 2009 , US Provisional Application No. 61 / 256,012, filed October 29, 2009, and US Provisional Application No. 61 / 267,928, filed December 3, 2009, each of which is incorporated by reference in its entirety. Included herein.

The present invention relates to an electronic device having a long active life and having at least one layer with deuterated compounds.

Organic electronic devices that emit light, such as light emitting diodes that make up a display, exist in many different electronic equipment. In all such devices, an organic active layer is sandwiched between two electrical contact layers. At least one of the electrical contact layers is light transmissive such that light can pass through the electrical contact layer. The organic active layer emits light through the light transmissive electrical contact layer when applying electricity across the electrical contact layer.

It is well known to use organic electroluminescent compounds as active components in light emitting diodes. Simple organic molecules such as anthracene, thiadiazole derivatives, and coumarin derivatives are known to exhibit electroluminescence. Semiconductor conjugated polymers have also been used as electroluminescent components, for example, as disclosed in US Pat. No. 5,247,190, US Pat. No. 5,408,109, and published European Patent Application 443 861. In many cases the electroluminescent compound is present as a dopant in the host material. In many devices an organic charge-injection layer and / or a charge-transport layer is present between the light emitting layer and the anode and / or cathode.

There is a continuing need for electronic devices with longer lifetimes.

An organic light emitting diode is provided comprising an anode, a cathode, and an organic active layer therebetween, wherein the organic active layer comprises a deuterated compound, and the device has a calculated half-life of at least 5000 hours at 1000 nits.

Also provided is the above organic light emitting diode wherein the organic active layer comprises a deuterated conductive polymer and a fluorinated acid polymer.

Also provided is an organic light emitting diode wherein the organic active layer comprises a deuterated hole transport compound having at least two diarylamino moieties.

There is also provided the above organic light emitting diode, wherein the organic active layer comprises an electroluminescent compound selected from the group consisting of deuterated aminoanthracene, deuterated aminocrynes, deuterated metal quinolate complexes, and deuterated iridium complexes.

A host material selected from the group consisting of (a) deuterated arylanthracene, deuterated arylpyrene, deuterated arylcrisene, deuterated phenanthroline, deuterated indolocarbazole, and combinations thereof, and (b) There is also provided the above organic light emitting diode comprising an electroactive dopant capable of electroluminescence having a maximum emission between 380 and 750 nm.

Also provided is an organic light emitting diode wherein the organic active layer comprises an electron transport material selected from the group consisting of deuterated phenanthroline, deuterated indolocarbazole, and deuterated metal quinolate.

Embodiments are illustrated in the accompanying drawings to facilitate understanding of the concepts presented herein.
<Figure 1>
1 includes an example of an organic electronic device.
<FIG. 2>
2 includes another example of an organic electronic device.
Those skilled in the art recognize that the objects in the figures are illustrated for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some objects in the drawings may be exaggerated relative to other objects to facilitate understanding of the embodiments.

Many aspects and embodiments are disclosed herein and these are illustrative and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims. The detailed description first refers to the definition and explanation of terms, followed by the synthesis of organic light emitting devices, hole injection layers, hole transport layers, electroactive layers, electron transport layers, containment layers, other device layers, deuterated materials , And finally examples.

1. Definition and Explanation of Terms

Before discussing the details of the embodiments described below, some terms will be defined or explained.

The term "aliphatic ring" is intended to mean a cyclic group having no delocalized pi electrons. In some embodiments, aliphatic rings have no unsaturated. In some embodiments, the ring has one double bond or triple bond.

The term "alkoxy" refers to the group RO-, where R is alkyl.

The term "alkyl" is intended to mean a group derived from an aliphatic hydrocarbon having one point of attachment, and includes linear, branched or cyclic groups. This term is intended to include heteroalkyls. The term "hydrocarbon alkyl" refers to an alkyl group having no heteroatoms. The term "deuterated alkyl" is hydrocarbon alkyl wherein at least one available H is replaced by D. In some embodiments, an alkyl group has 1 to 20 carbon atoms. The term "branched alkyl" refers to an alkyl group having at least one secondary or tertiary carbon. The term "secondary alkyl" refers to a branched alkyl group having a secondary carbon atom. The term "tertiary alkyl" refers to a branched alkyl group having a tertiary carbon atom. In some embodiments, branched alkyl groups are attached through secondary or tertiary carbons.

The term "aryl" is intended to mean a group derived from an aromatic hydrocarbon having one point of attachment. The term "aromatic compound" is intended to mean an organic compound comprising at least one unsaturated cyclic group having unlocalized pi electrons. This term is intended to include heteroaryls. The term "hydrocarbon aryl" is intended to mean an aromatic compound having no heteroatoms in the ring. The term aryl includes groups having a single ring and groups having multiple rings which may be linked by a single bond or may be fused together. The term “deuterated aryl” refers to an aryl group in which at least one available H directly bonded to aryl is replaced with D. The term "arylene" is intended to mean a group derived from an aromatic hydrocarbon having two points of attachment. In some embodiments, aryl groups have 3 to 60 carbon atoms.

The term "aryloxy" refers to the group RO- group, wherein R is aryl.

The term "compound" is intended to mean an electrically uncharged substance consisting of molecules, where the molecule is further composed of atoms, wherein the atoms cannot be separated by physical means. The phrase "adjacent" when used to refer to a layer in a device does not necessarily mean that one layer is next to the other layer. On the other hand, the phrase “adjacent R groups” is used in the formula to refer to R groups next to each other (ie, R groups on atoms linked by bonds).

The term "conductive" or "electrically conductive", when referring to a material, is intended to mean a material that can be inherently or essentially electrically conductive without the addition of carbon black or conductive metal particles.

The term "deuterated" is intended to mean that at least one H has been replaced with D. Deuterium is present at least 100 times the natural abundance level. A "deuterated derivative" of compound X has the same structure as compound X but is accompanied by at least one D that replaces H. The terms "% deuterated" and "% deuterated" refer to the ratio of the protons to the sum of the protons and the protons as a percentage. Thus,% deuteration for compound C ₆ H ₄ D ₂ is:

2 / (4 + 2) × 100 = 33% deuterated.

The term "dopant" refers to a layer of the layer as compared to the wavelength (s) of the emission, reception, or filtration of the electronic property (s) or radiation of the layer in the absence of such material, in the absence of the host material. It is intended to mean a material that changes the electronic characteristic (s) or target wavelength (s) of emission, reception, or filtration of radiation.

The prefix "fluoro" and the term "fluorination" refer to a material in which at least one available H has been replaced with F.

When referring to a layer or material, the term "electroactive" is intended to mean a layer or material that exhibits electronic or electro-radiative properties. In electronic devices, the electroactive material electronically promotes the operation of the device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block charge, which may be electrons or holes, and materials that exhibit a change in concentration or emit radiation of an electron-hole pair when accepting radiation. It doesn't work. Examples of inert materials include, but are not limited to planarization materials, insulation materials, and environmental barrier materials. The organic electroactive layer comprises an organic compound as the electroactive material. The term "organic" as used herein includes organometallic materials.

The term "half life" is intended to mean the time it takes for the device brightness to reach half of its initial value. The "observation half-life" is the half-life of the device measured at a constant current of 7 mA. The “calculated half life” is the half life derived from the observed half life and calculated for 1000 nits initial brightness. Half-life is measured in hours.

The prefix "hetero" means that one or more carbon atoms have been replaced by a different atom. In some embodiments, the different atoms are N, O or S.

The term "host material" is intended to mean the material to which the dopant is added. The host material may or may not have electronic property (s) or the ability to emit, receive or filter radiation. In some embodiments, the host material is present at higher concentrations.

The term "layer" is used interchangeably with the term "film" and refers to a coating covering the desired area. This term is not limited by size. The area can be as large as the entire device, as small as a specific functional area, such as an actual visual display, or as small as a single sub-pixel. Layers and films can be formed by any conventional deposition technique, such as vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. have. Continuous deposition techniques include spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating And continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.

The term "organic electronic device" or sometimes only "electronic device" is intended to mean a device comprising one or more organic semiconductor layers or materials.

Unless otherwise indicated, all groups may be substituted or unsubstituted. In some embodiments, the substituents are selected from the group consisting of D, halides, alkyl, alkoxy, aryl, aryloxy, cyano, and NR ₂ , where R is alkyl or aryl.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

The IUPAC numbering system is used throughout, where the families of the periodic table are numbered 1 to 18 from left to right (CRC Handbook of Chemistry and Physics, 81st Edition, 2000).

2. organic light emitting diode

One example of an organic light-emitting diode (“OLED”) device structure is shown in FIG. 1. Device 100 has a first electrical contact layer, an anode layer 110 and a second electrical contact layer, a cathode layer 160, and an electroluminescent layer 140 therebetween. Adjacent to the anode, there may be a hole injection layer 120 comprising a hole injection material. Adjacent to the hole injection layer, there may be a hole transport layer 130 comprising a hole transport material. Adjacent to the cathode may be an electron transport layer 150 comprising an electron transport material. The device may use one or more additional hole injection or hole transport layers (not shown) next to anode 110 and / or one or more additional electron injection or electron transport layers (not shown) next to cathode 160. have.

In some embodiments, the light emitting layer is pixelated with subpixel units for each different color to achieve full color. An example of a pixelated element is shown in FIG. Device 200 has an anode 210, a hole injection layer 220, a hole transport layer 230, an electroluminescent layer 240, an electron transport layer 250, and a cathode 260. The electroluminescent layer is divided into subpixels 241, 242, 243, which are repeated across the layer. In some embodiments, the subpixels exhibit red, blue and green emission. Although three different subpixel units are shown in FIG. 2, two or more than three subpixel units may be used.

Different layers will be discussed further herein in connection with FIG. 1. However, the discussion also applies to FIG. 2 and other configurations.

Layers 120-150 are referred to individually and collectively as electroactive layers. At least one of the electroactive layers is an organic electroactive layer comprising deuterated material. Deuterated materials may be used alone or in combination with other deuterated or non-deuterated materials. In some embodiments, the deuterated material is at least 10% deuterated. This means that at least 10% of H is replaced by D. In some embodiments, the deuterated material is at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated. In some embodiments, the deuterated material is 100% deuterated.

In some embodiments, the deuterated material is a hole injection material in layer 120. In some embodiments, the at least one additional layer comprises deuterated material. In some embodiments, the additional layer is the hole transport layer 130. In some embodiments, the additional layer is electroactive layer 140. In some embodiments, the additional layer is electron transport layer 150.

In some embodiments, the deuterated material is a hole transport material in layer 130. In some embodiments, the at least one additional layer comprises deuterated material. In some embodiments, the additional layer is the hole injection layer 120. In some embodiments, the additional layer is electroactive layer 140. In some embodiments, the additional layer is electron transport layer 150.

In some embodiments, the deuterated material is a host material for the dopant material in the electroactive layer 140. In some embodiments, the dopant material is also deuterated. In some embodiments, the at least one additional layer comprises deuterated material. In some embodiments, the additional layer is the hole injection layer 120. In some embodiments, the additional layer is the hole transport layer 130. In some embodiments, the additional layer is electron transport layer 150.

In some embodiments, the deuterated material is an electron transport material in layer 150. In some embodiments, the at least one additional layer comprises deuterated material. In some embodiments, the additional layer is the hole injection layer 120. In some embodiments, the additional layer is the hole transport layer 130. In some embodiments, the additional layer is electroactive layer 140.

In some embodiments the electronic device has a deuterated material in any combination of layers selected from the group consisting of a hole injection layer, a hole transport layer, an electroactive layer, and an electron transport layer. In some embodiments, all organic active layers of the device include deuterated materials.

In some embodiments, the device has additional layers to aid in processing or to improve functionality. All or any of these layers may comprise deuterated materials. In some embodiments, all organic device layers comprise deuterated materials. In some embodiments, all organic device layers consist essentially of deuterated material.

In some embodiments, the organic light emitting diode comprises an anode, a cathode and has an organic layer therebetween, wherein the organic layer is a hole injection layer, a hole transport layer, an electroluminescent layer, an electron transport layer, and a cathode, At least two are essentially composed of deuterated material. In some embodiments, all the organic layers consist essentially of deuterated material.

In one embodiment, the different layers have a thickness in the following range: anode 110 is 500-5000 mm 3, in one embodiment 1000-2000 mm 3; Hole injection layer 120, 50-2000 mm 3, in one embodiment 200-1000 mm 3; Hole transport layer 130, 50-2000 mm 3, in one embodiment 200-1000 mm 3; Electroactive layer 140, 10-2000 kPa, in one embodiment 100-1000 kPa; Layer 150, 50-2000 mm 3, in one embodiment 100-1000 mm 3; Cathode 160 is 200-10000 mm 3, in one embodiment 300-5000 mm 3. The location of the electron-hole recombination zone in the device, ie the emission spectrum of the device, can be influenced by the relative thickness of each layer. The desired ratio of layer thicknesses will depend on the exact nature of the material used.

The observed half life of the devices described herein is at least 200 hours. In some embodiments, the observation half life is at least 400 hours; In some embodiments, at least 1000 hours.

The calculated half life of the devices described herein is at least 5000 hours. It is well known how to calculate the half-life at a given initial luminance. The method is described, for example, in Chu et. al., Appl. Phys. Lett. 89, 053503 (2006) and Wellmann et. al., SID Int. Symp. Digest Tech. Papers 2005,393. In some embodiments, the calculated half life is at least 10,000 hours; In some embodiments, at least 20,000 hours; In some embodiments, at least 50,000 hours.

2. hole injection layer

The hole injection layer 120 includes a hole injection material and enhances the planarization of the base layer, charge transport and / or charge injection characteristics, removal of impurities such as oxygen or metal ions, and performance of the organic electronic device in the organic electronic device. Or one or more functions, including but not limited to other aspects of improving. The hole injection material can be a polymer, oligomer, or small molecule. They may be deposited or deposited from a liquid, which may be in the form of a solution, dispersion, suspension, emulsion, colloid mixture or other composition.

In some embodiments, the hole injection layer comprises deuterated material. In some embodiments, the deuterated material comprises a deuterated electrically conductive polymer. "Deuterated electrically conductive polymer" means that the electrically conductive polymer itself, which does not contain the associated polymeric acid, is deuterated. In some embodiments, the deuterated material comprises an electrically conductive polymer doped with deuterated polymeric acid. In some embodiments, the deuterated material comprises a deuterated electrically conductive polymer doped with deuterated polymeric acid.

In some embodiments, the deuterated electrically conductive polymer is a deuterated polythiophene, deuterated poly (selenophene), deuterated poly (telurofen), deuterated polypyrrole, deuterated polyaniline, deuterated poly (4-amino- Indole), deuterated poly (7-amino-indole), and deuterated polycyclic aromatic polymers, respectively. The term "polycyclic aromatic" refers to a compound having more than one aromatic ring. Rings may be linked by one or more bonds or may be fused together. The term "aromatic ring" is intended to include heteroaromatic rings. A "polycyclic heteroaromatic" compound has at least one heteroaromatic ring. In some embodiments, the deuterated polycyclic aromatic polymer is deuterated poly (thienothiophene).

In some embodiments, the deuterated electrically conductive polymer is a deuterated poly (3,4-ethylenedioxythiophene), deuterated polyaniline, deuterated polypyrrole, deuterated poly (4-aminoindole), deuterated poly (7-amino Indole), deuterated poly (thieno (2,3-b) thiophene), deuterated poly (thieno (3,2-b) thiophene), and deuterated poly (thieno (3,4-b) Thiophene).

In some embodiments, the deuterated conductive polymer is at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated.

In some embodiments, the electrically conductive polymer is poly (D _6- 3,4- ethylene dioxythiophene), poly (D _5- pyrrole), poly (D _7- aniline), poly (Purdue Tero-4-amino-indole) , Poly (perdutero-7-aminoindole), poly (perdutero-thieno (2,3-b) thiophene), poly (perdutero-thieno (3,2-b) thiophene), and poly (Purdutero-thieno (3,4-b) thiophene).

In some embodiments, the deuterated conductive polymer is doped with a non-fluorinated polymeric acid. Any polymer with acidic groups accompanied by ionizable protons or protons can be used. Examples of acidic groups include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof. The acidic groups may all be the same, or the polymer may have more than one type of acidic group. In some embodiments, the acidic group is selected from the group consisting of sulfonic acid groups, sulfonimide groups, and combinations thereof. Sulfonimide groups have the general formula:

-SO _2- NH-SO _2- R

Where R is an alkyl group. Examples of suitable acids are poly (styrenesulfonic acid) (“PSSA”), poly (perdutero-styrenesulfonic acid) (“D _8- PSSA”), poly (2-acrylamido-2-methyl-1-propane Sulfonic acids) (“PAAMPSA”), poly (perduter-2-acrylamido-2-methyl-1-propanesulfonic acid) (“D _13- PAAMPSA”), and mixtures thereof. .

In some embodiments, the deuterated conductive polymer doped with non-fluorinated polymeric acid is further combined with a high-fluorinated acid polymer (“HFAP”).

In some embodiments, the fluorinated acid polymer is a high fluorinated acid polymer (“HFAP”) in which at least 80% of the available hydrogens bonded to carbon are replaced with fluorine. The high fluorinated acid polymer (“HFAP”) may be any polymer that is highly fluorinated and has acidic groups. The acidic groups supply ionizable protons, H ⁺ , or protons, D ⁺ . In some embodiments, the acidic group has a pKa of less than 3. In some embodiments, the acidic group has a pKa of less than zero. In some embodiments, the acidic group has a pKa of less than -5. Acidic groups may be attached directly to the polymer backbone or to the side chains on the polymer backbone. Examples of acidic groups include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof. The acidic groups may all be the same, or the polymer may have more than one type of acidic group. In some embodiments, the acidic group is selected from the group consisting of sulfonic acid groups, sulfonimide groups, and combinations thereof.

In some embodiments, HFAP is a deutero-acid with acidic protons.

In some embodiments, HFAP is at least 90% fluorinated; In some embodiments, at least 95% fluorinated; In some embodiments it is fully fluorinated. In some embodiments where the HFAP is not fully fluorinated, the HFAP is also deuterated.

In some embodiments, the acidic group is selected from the group consisting of sulfonic acid groups, sulfonimide groups, and combinations thereof. In some embodiments, the acidic group is on a fluorinated side chain. In some embodiments, the fluorinated side chains are selected from alkyl groups, alkoxy groups, amido groups, ether groups, and combinations thereof, all of which are fully fluorinated.

In some embodiments, the HFAP is a high-fluorinated olefin backbone with pendant high-fluorinated alkyl sulfonates, high-fluorinated ether sulfonates, high-fluorinated ester sulfonates, or high-fluorinated ether sulfonimide groups Has In some embodiments, HFAP is a perfluoroolefin with perfluoro-ether-sulfonic acid side chains. In some embodiments, the polymer is a copolymer of tetrafluoroethylene and perfluoro-3,6-dioxa-4-methyl-7-octensulfonic acid (“poly (TFE-PSEPVE)”). Deutero-acid analogs are abbreviated as D-poly (TFE-PSEPVE). In some embodiments, the polymer is 1,1-difluoroethylene and 2- (1,1-difluoro-2- (trifluoromethyl) allyloxy) -1,1,2,2-tetrafluoro It is a copolymer of ethanesulfonic acid. In some embodiments, the polymer is ethylene and 2- (2- (1,2,2-trifluorovinyloxy) -1,1,2,3,3,3-hexafluoropropoxy) -1,1 Copolymer of 2,2-tetrafluoroethanesulfonic acid. These copolymers can be converted to the sulfonic acid form after being prepared as corresponding sulfonyl fluoride polymers.

In some embodiments, the deuterated conductive polymer is doped with HFAP. Non-deuterated analogs of such materials are described, for example, in published US patent applications US 2004/0102577, US 2004/0127637, US 2005/0205860, and published PCT application WO 2009/018009. Described.

In some embodiments, the hole injection layer comprises deuterated poly (3,4-ethylenedioxythiophene) (“d-PEDOT”) doped with polystyrenesulfonic acid (“PSSA”). In some embodiments, the hole injection layer comprises poly (3,4-ethylenedioxythiophene) (“PEDOT”) doped with deuterated polystyrenesulfonic acid (“d-PSSA”). In some embodiments, the hole injection layer comprises deuterated poly (3,4-ethylenedioxythiophene) doped with deuterated polystyrenesulfonic acid. In some embodiments, d-PEDOT / d-PSSA is at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated. In some embodiments, the hole injection layer consists essentially of a material selected from the group consisting of d-PEDOT / PSSA, PEDOT / d-PSSA, and d-PEDOT / d-PSSA. In some embodiments, the hole injection layer is essentially composed of a poly (D _6- 3,4- ethylene dioxythiophene) doped with D _8- PSSA.

In some embodiments, the hole injection layer comprises deuterated polyaniline (“d-PANI”) doped with poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (“PAAMPSA”). In some embodiments, the hole injection layer comprises polyaniline (“PANI”) doped with deuterated poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (“d-PAAMPSA”). In some embodiments, the hole injection layer comprises deuterated polyaniline doped with deuterated poly (2-acrylamido-2-methyl-1-propanesulfonic acid). In some embodiments, d-PANI / d-PAAMPSA is at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated. In some embodiments, the hole injection layer consists essentially of a material selected from the group consisting of d-PANI / PAAMPSA, PANI / d-PAAMPSA, and d-PANI / d-PAAMPSA. In some embodiments, the hole injection layer consists essentially of poly (D _7- aniline) doped with D ₁₃ -PAAMPSA.

In some embodiments, the hole injection layer comprises deuterated polypyrrole (“d-PPy”) doped with polystyrenesulfonic acid (“PSSA”). In some embodiments, the hole injection layer comprises polypyrrole (“PPy”) doped with deuterated polystyrenesulfonic acid (“d-PSSA”). In some embodiments, the hole injection layer comprises deuterated polypyrrole doped with deuterated polystyrenesulfonic acid. In some embodiments, d-PPy / d-PSSA is at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated. In some embodiments, the hole injection layer consists essentially of a material selected from the group consisting of d-PPy / PSSA, PPy / d-PSSA, and d-PPy / d-PSSA. In some embodiments, the hole injection layer consists essentially of poly (D _5- pyrrole) doped with D _8- PSSA.

In some embodiments, the hole injection layer comprises deuterated conductive polymer and HFAP. In some embodiments, the hole injection layer comprises a deuterated conductive polymer doped with HFAP. In some embodiments, the hole injection layer consists essentially of the deuterated conductive polymer doped with HFAP. In some embodiments, the hole injection layer consists essentially of the deuterated conductive polymer doped with the perfluorinated sulfonic acid polymer. In some embodiments, the hole injection layer is poly-D- is essentially composed of a conductive polymer doped with a deuterated (TFE-PSEPVE), wherein the conducting polymer is poly (D _6- 3,4- ethylene dioxythiophene), poly (D _7- aniline) and poly (D _5- pyrrole).

In some embodiments, the hole injection layer comprises a charge transfer compound and the like, for example, copper phthalocyanine, tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ) and deuterated analogs thereof.

3. hole transport layer

Hole transport layer 130 includes a hole transport material. When referring to a layer, material, member, or structure, the term “hole transport” refers to the layer, material, member, or structure, while the layer, material, member, or structure is accompanied by relative efficiency and low charge loss. It is intended to mean to promote the transfer of positive charge through the thickness of the structure. Although the luminescent material may also have some hole transport properties, the term “hole transport layer, material, member, or structure” is not intended to include a layer, material, member, or structure whose primary function is luminescence.

The hole transport material can be a polymer, oligomer, or small molecule. They may be deposited or deposited from a liquid, which may be in the form of a solution, dispersion, suspension, emulsion, colloid mixture or other composition.

In some embodiments, the hole transport layer comprises deuterated material. In some embodiments, the hole transport material is at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated.

In some embodiments, the hole transport material is a deuterated compound having at least two diarylamino moieties per molecular unit. In some embodiments, the hole transport material is deuterated triarylamine polymer. Non-deuterated analogs of such materials are described, for example, in published PCT application WO 2009/067419. In some embodiments, the hole transport material is deuterated fluorene-triarylamine copolymer. Non-deuterated analogs of such materials are described, for example, in published US patent applications US 2008/0071049 and US 2008/0097076. Examples of non-deuterated analogs of crosslinkable hole transport polymers can be found in, for example, published US patent application 2005/0184287 and published PCT application WO 2005/052027.

In some embodiments, the hole transport material is selected from the group consisting of deuterated triarylamines, deuterated carbazoles, deuterated fluorenes, polymers thereof, copolymers thereof, and combinations thereof. In some embodiments, the hole transport material comprises deuterated polymeric triarylamine, deuterated polycarbazole, deuterated polyfluorene, deuterated polymeric triarylamine, conjugated moieties having conjugated portions in a non-planar configuration Deuterated copolymers of triarylamines, and combinations thereof. In some embodiments, the polymeric material is crosslinkable.

In some embodiments, the hole transport material has Formula I, Formula II, or Formula III:

Formula I

[Formula II]

[Formula III]

here,

Ar ¹ is the same or different at each occurrence and is selected from the group consisting of phenylene, substituted phenylene, naphthylene and substituted naphthylene;

Ar ² is the same or different at each occurrence and is an aryl group;

M is the same or different at each occurrence and is a conjugated portion;

T ¹ and T ² are independently the same or different at each occurrence and are conjugated parts;

a is the same or different at each occurrence and is an integer from 1 to 6;

b, c, and d are mole fractions such that b + c + d = 1.0, except c is not 0, at least one of b and d is not 0, and when b is 0, M is at least two triaryl An amine unit;

e is the same or different at each occurrence and is an integer from 1 to 6;

n is an integer greater than 1;

Wherein the compound is at least 10% deuterated.

Non-deuterated analogs of such materials are described in published PCT application WO 2009/067419.

In some embodiments of Formulas I-III, deuteration is present in a substituent group on an aryl ring. In some embodiments, substituent groups are selected from alkyl, aryl, alkoxy, and aryloxy. In some embodiments of Formulas I-III, deuteration is present in any one or more of the aryl groups Ar ¹ and Ar ² . In this case, at least one of Ar ¹ and Ar ² is a deuterated aryl group. In some embodiments of Formulas I through III, deuteration is present on the [T ^1- T ² ] group. In some embodiments, both T ¹ and T ² are deuterated. In some embodiments of Formulas I-III, deuteration is present in both substituent groups and in Ar ¹ and Ar ² groups. In some embodiments of Formulas I-III, deuteration is present in both [T ^1- T ² ] groups and Ar ¹ and Ar ² groups. In some embodiments of Formulas I-III, deuteration is present on a substituent group, a [T ^1- T ² ] group, and on an Ar ¹ and Ar ² group.

In some embodiments, at least one Ar ¹ is substituted phenyl with substituents selected from the group consisting of alkyl, alkoxy, silyl, and substituents having crosslinking groups. In some embodiments, a is 1 to 3. In some embodiments a is 1 to 2. In some embodiments, a is 1. In some embodiments, e is 1-4. In some embodiments, e is 1-3. In some embodiments, e is one. In some embodiments, at least one Ar ¹ has a substituent with a crosslinking group.

In some embodiments, at least one Ar ² has formula a:

(A)

here,

R ¹ is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, siloxane, and silyl; Adjacent R ¹ groups may be joined to form an aromatic ring;

f is the same or different at each occurrence and is an integer from 0 to 4;

g is an integer from 0 to 5;

m is an integer of 1-5.

In some embodiments, at least one Ar ² has formula b:

[Formula b]

here,

R ¹ is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, siloxane, and silyl; Adjacent R ¹ groups may be joined to form an aromatic ring;

f is the same or different at each occurrence and is an integer from 0 to 4;

g is an integer from 0 to 5;

m is an integer of 1-5.

In some embodiments of Formula a or b, at least one of f and g is not zero. In some embodiments, m is 1-3.

In some embodiments, Ar ² is selected from the group consisting of a group having the formula a, naphthyl, phenylnaphthyl, naphthylphenyl, and deuterated analogs thereof. In some embodiments, Ar ² is selected from the group consisting of phenyl, p-biphenyl, p-terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, and deuterated analogs thereof. In some embodiments, Ar ² is selected from the group consisting of phenyl, biphenyl, terphenyl, and deuterated analogs thereof.

Any aromatic ring of formulas (I) to (III) may be substituted at any position. Substituents may be present to improve one or more physical properties of the compound, eg, solubility. In some embodiments, the substituents are selected from the group consisting of C _1-12 alkyl groups, C _1-12 alkoxy groups, silyl groups, and deuterated analogs thereof. In some embodiments, crosslinking substituents are present on at least one Ar ² . In some embodiments, crosslinking substituents are present on at least one M moiety.

T ¹ and T ² are conjugated portions. In some embodiments, T ¹ and T ² are aromatic moieties. In some embodiments, T ¹ and T ² are deuterated aromatic moieties. In some embodiments, T ¹ and T ² are selected from the group consisting of phenylene, naphthylene, anthracenyl groups, and deuterated analogs thereof.

In some embodiments, the T ¹ -T ² groups introduce non-planarity into the backbone of the compound. Portion of the T ² T ¹ is directly connected to a part of the connection is to be oriented in different planes and part of T ² is T ¹ part it is connected. Other portions of the T ¹ unit, for example substituents, may lie in one or more different planes, but providing non-planarity is the plane of the connecting portion of T ^{1 and} the connecting portion of T ^{2 in} the compound backbone. Because of the non-planar T ¹ -T ² linkage, the compound is chiral. In general, the compound is formed as a racemic mixture. The compound may also be in enantiomerically pure form. Non-planarity can be regarded as a limitation on free rotation around the T ¹ -T ² bonds. Rotation around the bond causes racemization. The half life of racemization for T ¹ -T ² is greater than the half life for unsubstituted biphenyls. In some embodiments, the half life of racemization is at least 12 hours at 20 ° C.

In some embodiments, [T ^1- T ² ] is a substituted biphenylene group, or deuterated analog thereof. The term "biphenylene" is intended to mean a biphenyl group having two points of attachment to the compound backbone. The term "biphenyl" is intended to mean a group having two phenyl units linked by a single bond. The biphenylene group can be attached to one of the 2, 3-, 4-, or 5-positions and to one of the 2 ', 3'-, 4'-, or 5'-positions. Substituted biphenylene groups have at least one substituent in the 2-position. In some embodiments, biphenylene groups have substituents in at least 2- and 2'-positions.

In some embodiments, [T ^1- T ² ] is a binaphthylene group, or deuterated analog thereof. The term "binaftylene" is intended to mean a binafthyl group having two points of attachment to the compound backbone. The term "binaphthyl" is intended to mean a group having two naphthalene units connected by a single bond.

In some embodiments, [T ^1- T ² ] is a phenylene-naphthylene group, or deuterated analog thereof. In some embodiments, [T ^1- T ² ] is a phenylene-1-naphthylene group, which is one of the 3-, 4-, or 5-positions in phenylene and 3-, 4-, or of naphthylene Is attached to the compound backbone in one of the 5-positions. In some embodiments, [T ^1- T ² ] is a phenylene-2-naphthylene group, which is one of the 3-, 4-, or 5-positions in phenylene and the 4-, 5-, 6 of naphthylene -Is attached to the compound backbone in either the 7- or 8-position.

In some embodiments, biphenylene, binaphthylene, and phenylene-naphthylene groups are substituted at one or more positions.

In some embodiments, [T ^1- T ² ] is a 1,1-binaphthylene group, or a deuterated analog thereof, which is attached to the compound backbone at the 4 and 4 'positions, and 4,4'-(1, 1-binaphthylene). In some embodiments, 4,4 '-(1,1-binaftylene) is the only isomer present. In some embodiments, two or more isomers are present. In some embodiments, 4,4 '-(1,1-binaftylene) is present with up to 50% by weight of the second isomer. In some embodiments, the second isomer is 4,5 '-(1,1-binaftylene), 4,6'-(1,1-binaftylene), and 4,7 '-(1,1- Binaphthylene).

Formula III represents a copolymer having at least one [T ^1- T ² ] moiety and at least one other conjugated moiety, wherein the entire polymer is at least 10% deuterated. In some embodiments, deuteration is present in the first monomer unit with the subscript “b”. In some embodiments, deuteration is present in the second monomer unit having the subscript “c”. In some embodiments, deuteration is present in the third monomer unit having a subscript “d”. In some embodiments, deuteration is present in two monomer units. In some embodiments, one of the two monomer units is the first monomer unit. In some embodiments, deuteration is present in all three monomer units.

Some non-limiting examples of deuterated hole transport compounds include the following compounds HT1 to HT10.

Compound HT1:

Where x + y + z + p + q + r = 20-28.

compound HT2 :

Wherein x is 0 to 5; In some compounds Σ (x) = 10-44.

Compound HT3:

Wherein x is 0 to 6; In some compounds Σ (x) = 8-36.

Compound HT4:

Wherein x is 0 to 6; In some compounds Σ (x) = 8-36.

Compound HT5:

R ₁ = D _y- propyl; R ₂ = D _y- octyl,

Where x is 0 to 5 and Σ (x) = 10-50

y is 0 to 17 and Σ (y) = 0-32.

Compound HT6:

Where a = 0.4-0.8

b is 0.2 to 0.6

x is 0 to 5; In some compounds Σ (x) = 10-36.

Compound HT7:

Where a = 0.3-0.7

b = 0.3-0.5

c = 0.1-0.2

x is 0 to 5; In some compounds Σ (x) = 10-36.

Compound HT8:

Where a = 0.9-0.95

b = 0.05-0.10

x is 0 to 5; In some compounds Σ (x) = 20-62.

Compound HT9:

Where a = 0.7-0.99

b = 0.01-0.30

x is 0 to 5; In some compounds Σ (x) = 20-62.

Compound HT10:

Where x is 0-5 and Σ (x) = 15-42.

Compound HT11:

Where n is an integer greater than 1;

x is 0 to 5 and Σ (x) = 10-32.

Another example of a triarylamine polymer is compound HT12.

Compound HT12

Examples of non-deuterated analogs of other hole transport materials for layer 130 are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, Y. Wang. Other hole transport materials include N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD), 1,1 -Bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC), N, N'-bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl)-[1,1'- (3,3'-dimethyl) biphenyl] -4,4'-diamine (ETPD), tetrakis- (3-methylphenyl) -N, N, N ', N'-2,5-phenylenedia Min (PDA), a-phenyl-4-N, N-diphenylaminostyrene (TPS), p- (diethylamino) benzaldehyde diphenylhydrazone (DEH), triphenylamine (TPA), bis [4 -(N, N-diethylamino) -2-methylphenyl] (4-methylphenyl) methane (MPMP), 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (di Ethylamino) phenyl] pyrazoline (PPR or DEASP), 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB), N, N, N ', N'-tetrakis (4 -Methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TTB), N, N'-bis (naphthalen-1-yl) -N, N'-bis- (phenyl) benzidine (NPB), porphyrin-based compounds, for example Air, copper phthalocyanine, and is not limited thereto comprises a deuterated analog of any of the materials listed above. It is also possible to obtain hole transport polymers by doping hole transport molecules such as those mentioned above to polymers such as polystyrene, polycarbonates, and deuterated analogs thereof.

In some embodiments the hole transport layer is a p-dopant, for example tetrafluorotetracyanoquinodimethane, perylene-3,4,9,10-tetracarboxylic-3,4,9,10- Doped with dionhydride, and deuterated analogs thereof.

4. Electroluminescent Layer

Electroluminescent layer 140 includes an electroluminescent material. The term "electroluminescent material" refers to a material that emits light when activated by an applied voltage. In some embodiments, electroluminescent layer 140 consists essentially of electroluminescent material. In some embodiments, electroluminescent layer 140 includes one or more dopants and one or more host compounds. In some embodiments, electroluminescent layer 140 consists essentially of one or more dopants and one or more host compounds. Electroluminescent dopants are electroluminescent capable materials having a maximum emission between 380 and 750 nm. In some embodiments, the dopant emits red, green, or blue light. The host compound is typically a compound in the form of a layer, in which one or more dopants are dispersed and one or more dopants are emissive. The term "host material" refers to all of the host compounds present. The host material may or may not have electronic property (s) or the ability to emit, receive or filter radiation. In an electroluminescent layer comprising at least one dopant and a host material, light is emitted from the dopant. In some embodiments, the host material is present at a concentration higher than the sum of all dopants. In some embodiments, electroluminescent layer 140 consists essentially of one or more dopants and one or more host compounds. In some embodiments, electroluminescent layer 140 consists essentially of dopants and host compounds. In some embodiments, electroluminescent layer 140 consists essentially of dopant and two host compounds.

In some embodiments, the electroluminescent layer comprises a deuterated material selected from the group consisting of deuterated electroluminescent material, deuterated host material, and combinations thereof.

Materials for the electroluminescent layer can be polymers, oligomers, small molecules, or combinations thereof. They may be deposited or deposited from a liquid, which may be in the form of a solution, dispersion, suspension, emulsion, colloid mixture or other composition.

If a host is present, the total amount of dopant present in the electroluminescent composition is generally 3 to 20 weight percent, based on the total weight of the composition; In some embodiments, it is present in the range of 5-15% by weight. When two host compounds are present, the ratio of first host to second host is generally 1:20 to 20: 1; In some embodiments, 5:15 to 15: 5.

A. Electroluminescent Materials

The electroluminescent material can be selected from small molecule organic electroluminescent compounds, electroluminescent metal complexes, electroluminescent conjugated polymers, and mixtures thereof.

In some embodiments, the electroluminescent material is deuterated. In some embodiments, the electroluminescent material is at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated.

Examples of red luminescent materials include, but are not limited to, cyclometalated complexes of Ir with phenylquinoline or phenylisoquinoline ligands, periplanthene, fluoranthene, perylene, and deuterated analogs thereof. Non-deuterated red luminescent materials are disclosed, for example, in US Pat. No. 6,875,524 and published US application 2005-0158577.

Examples of green luminescent materials include, but are not limited to, cyclometalated complexes of Ir with phenylpyridine ligands, diaminoanthracene, polyphenylenevinylene polymers, and deuterated analogs thereof. Non-deuterated green light emitting materials are disclosed, for example, in published PCT application WO 2007/021117.

Examples of blue luminescent materials include cyclometalated complexes of Ir with diarylanthracene, diaminocrisene, diaminopyrene, diaminostyrenebene, phenylpyridine ligand, polyfluorene polymers, and deuterated analogs thereof It is not limited to this. Non-deuterated blue light emitting materials are disclosed, for example, in US Pat. No. 6,875,524, and in published US applications 2007-0292713 and 2007-0063638.

In some embodiments, the dopant is an organometallic complex. In some embodiments, the dopant is a cyclometalation complex of iridium or platinum. Such materials when not deuterated are disclosed, for example, in US Pat. No. 6,670,645 and published PCT applications WO 03/063555, WO 2004/016710, and WO 03/040257.

In some embodiments, the dopant is a complex having the formula Ir (L1) _x (L2) _y (L3) _z ; here,

L 1 is a monovalent anionic bidentate cyclometalated ligand coordinated via carbon and nitrogen;

L 2 is a monovalent anionic bidentate ligand that is not coordinated via carbon;

L3 is a monodentate ligand;

x is 1 to 3;

y and z are independently 0 to 2;

x, y, and z are chosen such that the iridium is six coordinating and the complex is electrically neutral.

Some examples of formulas include Ir (L1) ₃ ; Ir (L1) ₂ (L2); And Ir (L1) ₂ (L3) (L3 '), wherein L3 is anionic and L3' is nonionic.

Examples of L1 ligands include, but are not limited to, phenylpyridine, phenylquinoline, phenylpyrimidine, phenylpyrazole, thienylpyridine, thienylquinoline, thienylpyrimidine, and deuterated analogs thereof. The term "quinoline" as used herein includes "isoquinoline" unless otherwise specified. The fluorinated derivatives may have one or more fluorine substituents. In some embodiments, there are 1-3 fluorine substituents on the non-nitrogen ring of the ligand.

The monovalent anionic bidentate coordination ligand L2 is well known in the art of metal coordination chemistry. In general, these ligands have N, O, P, or S as coordinating atoms, and form 5- or 6-membered rings when coordinated with iridium. Suitable coordination groups include, but are not limited to, amino, imino, amido, alkoxides, carboxylates, phosphino, thiolates, and deuterated analogs thereof. Examples of suitable parent compounds for these ligands include β-dicarbonyls (β-enolate ligands), and N and S analogs thereof; Amino carboxylic acids (aminocarboxylate ligands); Pyridine carboxylic acid (iminocarboxylate ligand); Salicylic acid derivatives (salicylate ligands); Hydroxyquinoline (hydroxyquinolinate ligand) and its S analogs; Phosphinoalkanols (phosphinoalkoxide ligands); And deuterated analogs thereof.

Monodentate ligand L3 may be anionic or nonionic. Anionic ligands include, but are not limited to, ligands having H-("hydride") and C, O or S as coordinating elements. Coordinating groups include, but are not limited to, alkoxides, carboxylates, thiocarboxylates, dithiocarboxylates, sulfonates, thiolates, carbamates, dithiocarbamates, thiocarbazone anions, sulfonamide anions, and deuterated analogs thereof It doesn't work. In some cases, ligands listed above as L2, such as β-enolate and phosphinoalkoxide, may act as single-position coordination ligands. Single-position coordinating ligands may also be coordinating anions such as halides, cyanide, isocyanides, nitrates, sulfates, hexahaloantimonates and the like. These ligands are generally commercially available.

Monodentate coordinating L3 ligands can also be non-ionic ligands, such as CO, monodentate coordinating phosphine ligands, or deuterated monodentate coordinating phosphine ligands.

In some embodiments, the one or more ligands have at least one substituent selected from the group consisting of F and fluorinated alkyl.

For example, iridium complex dopants can be prepared using standard synthetic techniques similar to those described for non-deuterated analogs in US Pat. No. 6,670,645.

In some embodiments, the electroluminescent material is a small organic compound. Examples of small molecule luminescent compounds include chrysene, pyrene, perylene, rubrene, periplanthene, fluoranthene, stilbene, coumarin, anthracene, thiadiazole, derivatives thereof, deuterated analogs thereof, and mixtures thereof. One is not limited thereto.

In some embodiments, the electroluminescent material has one of the following structures:

Here, the structure may be unsubstituted or further substituted with alkyl or aryl groups and the compound is 10% to 100% deuterated.

In some embodiments, the dopant is selected from the group consisting of non-polymeric spirobifluorene compounds and fluoranthene compounds.

In some embodiments, the electroluminescent material is a compound having aryl amine groups. In some embodiments, the electroluminescent material is selected from the following formula:

here,

A is the same or different at each occurrence and is an aromatic group having 3 to 60 carbon atoms;

Q 'is a single bond or an aromatic group having 3 to 60 carbon atoms;

p and q are the same or different and each is an integer from 1 to 6.

The values of p and q in the above formulas can be defined by the available binding sites on the core Q 'group.

In some embodiments of the above formula, the compound is at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated.

In some embodiments of the above formula, at least one of A and Q 'in each formula has at least three condensed rings. In some embodiments, p and q are equal to one.

In some embodiments, Q 'is a styryl or styrylphenyl group.

In some embodiments, Q 'is an aromatic group having at least two condensed rings. In some embodiments, Q 'is naphthalene, anthracene, benz [a] anthracene, dibenz [a, h] anthracene, fluoranthene, fluorene, spirofluorene, tetracene, chrysene, pyrene, tetracene, xanthene , Perylene, coumarin, rhodamine, quinacridone, rubrene, substituted derivatives thereof, and deuterated analogs thereof.

In some embodiments, A is selected from the group consisting of phenyl, biphenyl, tolyl, naphthyl, naphthylphenyl, anthracenyl, and deuterated analogs thereof.

In some embodiments, the electroluminescent material has the structure:

Wherein A is an aromatic group, p is 1 or 2, and Q 'is selected from the group consisting of:

here,

R Is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy and aryl, wherein adjacent R groups can be linked together to form a 5- or 6-membered aliphatic ring;

Ar is the same or different and is selected from the group consisting of aryl groups;

Wherein the compound has at least one D.

The dashed line in the formula is intended to indicate that the R group (if present) may be present at any site on the core Q 'group.

In some embodiments, the electroluminescent material has the formula:

here,

Y is the same or different at each occurrence and is an aromatic group having 3 to 60 carbon atoms;

Q 'is an aromatic group, a divalent triphenylamine residue, or a single bond.

In some embodiments, the electroluminescent is aryl acene or deuterated analog thereof. In some embodiments, the electroluminescent material is a non-symmetric aryl acene or deuterated analog thereof.

In some embodiments, the electroluminescent material is an anthracene derivative having Formula IV:

[Formula IV]

here,

R ² is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy and aryl, wherein adjacent R ² groups can be linked together to form a 5- or 6-membered aliphatic ring;

Ar ³ to Ar ⁶ are the same or different and are selected from the group consisting of aryl groups and deuterated aryl groups;

h is the same or different at each occurrence and is an integer from 0 to 4;

Here, at least one D is present.

In some embodiments, the electroluminescent material is a chrysene derivative having Formula V:

here,

R ³ is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy aryl, fluoro, cyano, nitro, —SO ₂ R ⁴ , wherein R ⁴ is alkyl or perfluoroalkyl Wherein adjacent R ³ groups can be linked together to form a 5- or 6-membered aliphatic ring;

Ar ³ to Ar ⁶ are the same or different and are selected from the group consisting of aryl groups;

i is the same or different at each occurrence and is an integer from 0 to 5;

Here, at least one D is present.

In some embodiments of Formulas IV and V, deuteration is present in a substituent group on the aryl ring. Aryl groups having deuterated substituent groups include a core anthracene group of formula IV or a core chrysene group of formula V; Or aryl on nitrogen; Or a substituent aryl group. In some embodiments, the deuterated substituent group on the aryl ring is selected from alkyl, aryl, alkoxy, and aryloxy. In some embodiments, a substituent group is at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated.

In some embodiments of Formulas IV and V, deuteration is present in any one or more of the aryl groups Ar ³ to Ar ⁶ . In this case, at least one of Ar ³ to Ar ⁶ is a deuterated aryl group. In some embodiments, Ar ³ to Ar ⁶ are at least 10% deuterated. This means that at least 10% of all available H bonded to aryl C in Ar ³ to Ar ⁶ are replaced with D. In some embodiments, each aryl ring will have some D. In some embodiments, some but not all of the aryl rings have D. In some embodiments, Ar ³ to Ar ⁶ are at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated.

In some embodiments of Formula IV and V, deuteration is present in both substituent groups (R ² or R ³ ) and aryl groups.

In some embodiments, compounds of Formulas IV and V are at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated.

In some embodiments of Formulas IV and V, the compound is symmetric with respect to the amino group. In this case, Ar ³ = Ar ⁵ , Ar ⁴ = Ar ⁶ , where Ar ³ may be the same as or different from Ar ⁴ .

In some embodiments of Formulas IV and V, the compound is not symmetric with respect to the amino group. In this case, Ar ³ is different from both Ar ⁵ and Ar ⁶ . Ar ³ may be the same or different and Ar ^4, Ar ⁴ may be the same or different and each of Ar ⁵ and Ar ^6.

In some embodiments of Formula IV, h is both zero.

In some embodiments of Formula IV, at least one h is greater than zero. In some embodiments, at least one R ² is hydrocarbon alkyl. In some embodiments, R ² is deuterated alkyl. In some embodiments, R ² is selected from branched hydrocarbon alkyl and cyclic hydrocarbon alkyl.

In some embodiments of Formula IV, h is both 4 and R ² is D.

In formula (V), the bond to (R ³ ) _i is intended to mean that the R ³ group may be present at any one or more sites on two fused rings.

In some embodiments of Formula V, i is both zero.

In some embodiments of Formula V, at least one i is greater than zero. In some embodiments, at least one R ³ is hydrocarbon alkyl. In some embodiments, R ³ is selected from branched hydrocarbon alkyl and cyclic hydrocarbon alkyl.

In some embodiments of Formula V, i is both 5 and R ³ is D.

In some embodiments, at least one of Ar ³ to Ar ⁶ has formula a or formula b as indicated above.

In some embodiments, Ar ³ to Ar ⁶ are selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, and binaphthyl.

In some embodiments, Ar ³ to Ar ⁶ are perdeuterated.

In some embodiments Ar ³ to Ar ⁶ are superdeuterated, except for one or more alkyl groups on terminal aryl.

Some non-limiting examples of deuterated electroluminescent materials are shown below as E1 to E13:

Compound E1:

Compound E2:

compound E3 :

Compound E4:

Compound E5:

Compound E6:

Compound E7:

Compound E8:

Compound E9:

Compound E10:

Compound E11:

E12:

E13:

b. Host

A single host compound or two or more host compounds may be present as host material. Examples of non-deuterated host compounds are disclosed, for example, in US Pat. No. 7,362,796, and published US patent application 2006-0115676.

In some embodiments, the host material is at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated. In some embodiments, the host material is 100% deuterated.

In some embodiments, the host material is anthracene, chrysene, pyrene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, dibenzofuran, difuranobenzene, Metal quinolinate complexes, indolocarbazole, benzimidazole, triazolopyridine, diheteroarylphenyl, substituted derivatives thereof, deuterated analogs thereof, and combinations thereof. In some embodiments, the foregoing host compound has a substituent selected from the group consisting of aryl, alkyl, and deuterated analogs thereof. In some embodiments, heteroaryl groups are pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetraazine, quinazoline, quinoxaline, naphthylpyridine, heterobiaryl analogs thereof, heterotriaryl analogs thereof, and deuteration thereof Selected from the group consisting of analogs.

In some embodiments, the host is selected from structures 1-9, or deuterated analogs thereof, below.

Wherein R is selected from aryl, heteroaryl, and alkyl. In some embodiments, the heteroaryl group is selected from structures 10-20, or deuterated analogs thereof.

In some embodiments, the group is a heterobiaryl derivative or heterotriaryl derivative.

In some embodiments, the host material has one of the structures shown below:

Wherein R is selected from aryl, heteroaryl, and alkyl, and the compound may be deuterated. In some embodiments, the above structures are further substituted with aryl or heteroaryl groups. In some embodiments, the heteroaryl group is selected from structures 10-20, or deuterated analogs thereof.

In some embodiments, the host material has formula VI:

[Formula VI]

here,

Ar ⁷ is the same or different at each occurrence and is an aryl group;

Q is a polyvalent aryl group and

Selected from the group consisting of;

T is selected from the group consisting of (CR ′) _a , SiR ₂ , S, SO ₂ , PR, PO, PO ₂ , BR, and R;

R is the same or different at each occurrence and is selected from the group consisting of alkyl, and aryl;

R 'is the same or different at each occurrence and is selected from the group consisting of H, D, and alkyl;

a is an integer from 1 to 6;

n is an integer of 0-6.

While n may have a value from 0 to 6, it will be understood that for some Q groups the value of n is limited by the chemical nature of the group. In some embodiments n is 0 or 1.

In some embodiments of Formula VI, adjacent Ar groups are linked together to form a ring, such as carbazole. In Formula VI, "adjacent" means that the Ar group is bonded to the same N.

In some embodiments, Ar ⁷ is independently selected from the group consisting of phenyl, biphenyl, terphenyl, quarterphenyl, naphthyl, phenanthryl, naphthylphenyl, phenanthrylphenyl, and deuterated analogs thereof. Analogs higher than quarterphenyl, having 5 to 10 phenyl rings, may also be used.

In some embodiments, at least one Ar ⁷ has at least one substituent. Substituent groups may be present to alter the physical or electronic properties of the host material. In some embodiments, the substituents improve the processability of the host material. In some embodiments, the substituents increase the solubility and / or Tg of the host material. In some embodiments, the substituents are selected from the group consisting of D, alkyl groups, alkoxy groups, silyl groups, siloxanes, and combinations thereof.

In some embodiments, Q is an aryl group having at least two fused rings. In some embodiments, Q has 3 to 5 fused aromatic rings. In some embodiments, Q is anthracene, chrysene, pyrene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, dibenzofuran, difuranobenzene, indole Rocarbazole, substituted derivatives thereof, and deuterated analogs thereof.

In some embodiments, the host compound has formula VII:

[Formula VII]

here,

R ⁴ to R ¹¹ are the same or different at each occurrence and are selected from the group consisting of H, D, alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl;

Ar ⁸ and Ar ⁹ are the same or different and are selected from the group consisting of aryl groups;

Ar ¹⁰ and Ar ¹¹ are the same or different and are selected from the group consisting of H, D, and aryl groups,

Here, at least one D is present.

In some embodiments of Formula VII, at least one D is in a substituent group on the aryl ring. In some embodiments, substituent groups are selected from alkyl and aryl.

In some embodiments of Formula VII, at least one of R ⁴ to R ¹¹ is D. In some embodiments, at least two of R ⁴ to R ¹¹ are D. In some embodiments, at least three are D; In some embodiments, at least four are D; In some embodiments, at least 5 is D; In some embodiments, at least 6 is D; In some embodiments, at least seven are D. In some embodiments, all of R ⁴ to R ¹¹ are D.

In some embodiments, R ⁴ through R ¹¹ are selected from H and D. In some embodiments, one of R ⁴ to R ¹¹ is D and 7 is H. In some embodiments, two of R ⁴ to R ¹¹ are D and 6 are H. In some embodiments, three of R ⁴ to R ¹¹ are D and five are H. In some embodiments, ^{four of} R ⁴ to R ¹¹ are D and four are H. In some embodiments, 5 of R ⁴ to R ¹¹ are D and 3 are H. In some embodiments, six of R ⁴ to R ¹¹ are D and two are H. In some embodiments, 7 of R ⁴ to R ¹¹ are D and one is H. In some embodiments, 8 of R ⁴ to R ¹¹ are D.

In some embodiments, at least one of R ⁴ to R ¹¹ is selected from alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl, and the remaining of R ⁴ to R ¹¹ are selected from H and D. In some embodiments, R ⁵ is selected from alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl. In some embodiments, R ⁵ is selected from alkyl and aryl. In some embodiments, R ⁵ is selected from deuterated alkyl and deuterated aryl. In some embodiments, R ⁵ is selected from deuterated aryl having at least 10% deuteration. R ⁵ may, in some embodiments, be at least 20% deuterated; In some embodiments, at least 30% deuteration; In some embodiments, at least 40% deuteration; In some embodiments, at least 50% deuteration; In some embodiments, at least 60% deuteration; In some embodiments, at least 70% deuteration; In some embodiments, at least 80% deuteration; In some embodiments is selected from deuterated aryls having at least 90% deuteration. In some embodiments, R ² is selected from deuterated aryl having 100% deuteration.

In some embodiments of Formula VII, at least one of Ar ⁸ to Ar ¹¹ is deuterated aryl. In some embodiments, Ar ¹⁰ and Ar ¹¹ are selected from D and deuterated aryl.

In some embodiments of Formula VII, Ar ⁸ to Ar ¹¹ are at least 10% deuterated. In some embodiments of Formula VII, Ar ⁸ to Ar ¹¹ are at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated.

In some embodiments, the compound of Formula VII is at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated. In some embodiments, the compound is 100% deuterated.

In some embodiments, Ar ⁸ and Ar ⁹ are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, and deuterated analogs thereof. In some embodiments, Ar ⁸ and Ar ⁹ are selected from the group consisting of phenyl, naphthyl, and deuterated analogs thereof.

In some embodiments, Ar ¹⁰ and Ar ¹¹ are groups having phenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthylene, naphthylphenylene, deuterated derivatives thereof, and formula a or formula b as shown above Selected from the group consisting of.

In some embodiments, at least one of Ar ⁸ to Ar ¹¹ is a heteroaryl group. In some embodiments, the heteroaryl group is deuterated. In some embodiments, heteroaryl groups are at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated. In some embodiments, the heteroaryl group is 100% deuterated. In some embodiments, the heteroaryl group is selected from carbazole, benzofuran, dibenzofuran, and deuterated derivatives thereof.

In some embodiments of Formula VII, at least one of R ⁴ to R ¹¹ is D and at least one of Ar ⁸ to Ar ¹¹ is deuterated aryl. In some embodiments, the compound is at least 10% deuterated. In some embodiments, the compound is at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated. In some embodiments, the compound is 100% deuterated.

In some embodiments, the host compound has formula VIII:

(VIII)

here,

R ¹² is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, silyl, and siloxanes, or adjacent R ¹² groups can be linked together to form a 5- or 6-membered aliphatic ring,

Ar ¹² and Ar ¹³ are the same or different and are an aryl group,

j is an integer from 0 to 6;

k is an integer from 0 to 2;

l is an integer from 0 to 3;

Here, at least one D is present.

In some embodiments, R ¹² is D and at least one of j, k, and l is greater than zero. In some embodiments, R ¹² is D and j, k, and l are all greater than zero. In some embodiments R ¹² is D, j = 5-6, k = 1-2 and l = 2-3.

In some embodiments, at least one R ¹² is a branched alkyl group. In some embodiments, branched alkyl groups are 2-propyl groups, t-butyl groups, or deuterated analogs thereof.

In some embodiments, Ar ¹² and Ar ¹³ are phenyl groups having substituents selected from the group consisting of D, alkyl, silyl, phenyl, naphthyl, N-carbazolyl, and fluorenyl.

In some embodiments, Ar ¹² and Ar ¹³ are phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, 4-naphthylphenyl, 4-phenanthrylphenyl, deuterated analogs thereof, and formulas as shown above It is selected from the group consisting of a or a group having the formula (b).

In some embodiments, the host compound has formula IX:

(IX)

here,

R ¹³ is the same or different and is selected from the group consisting of phenyl, biphenyl, naphthyl, naphthylphenyl, triphenylamino, carbazolylphenyl, and deuterated analogs thereof;

Meets one of the following conditions:

(i) from the group consisting of R ¹⁴ = R ¹⁵ and consisting of H, D, phenyl, biphenyl, naphthyl, naphthylphenyl, arylanthracenyl, phenanthryl, triphenylamino, carbazolylphenyl, and deuterated analogs thereof Selected; or

(ii) R ¹⁴ is selected from the group consisting of H, D, phenyl, and deutero-phenyl;

R ¹⁵ is selected from the group consisting of phenyl, biphenyl, naphthyl, naphthylphenyl, arylanthracenyl, phenanthryl, triphenylamino, carbazolylphenyl, and deuterated analogs thereof;

Here, at least one D is present.

In some embodiments, the phenanthroline compound is symmetrical wherein R ¹³ is both the same and R ¹⁴ = R ¹⁵ . In some embodiments, R ¹³ = R ¹⁴ = R ¹⁵ . In some embodiments, the phenanthroline compound is asymmetrical, wherein two R ¹³ groups are different, R ¹⁴ ≠ R ^15, or both.

In some embodiments, the R ¹³ groups are the same and are selected from the group consisting of biphenyl, naphthyl, naphthylphenyl, triphenylamino, carbazolylphenyl, and deuterated analogs thereof. In some embodiments, the R ¹³ group is selected from the group consisting of phenyl, triphenylamino, carbazolylphenyl, and deuterated analogs thereof. In some embodiments, the R ¹³ group is selected from the group consisting of 4-triphenylamino, m-carbazolylphenyl, and deuterated analogs thereof.

In some embodiments, R ¹³ = R ¹⁴ and are selected from the group consisting of triphenylamino, naphthylphenyl, arylanthracenyl, m-carbazolylphenyl, and deuterated analogs thereof.

In some embodiments, the host has Formula X or Formula XI:

[Formula X]

(XI)

here,

R ¹⁶ is the same or different at each occurrence and is a group consisting of hydrogen, deuterium, phenyl, biphenyl, naphthyl, naphthylphenyl, phenanthryl, triphenylamino, carbazolyl, carbazolylphenyl, and deuterated derivatives thereof Is selected from;

R ¹⁷ is H or D;

Q 'is an aryl group;

Here, at least one D is present.

In some embodiments, Q 'is selected from the group consisting of phenylene, naphthylene, biphenylene, binaphthylene, and deuterated derivatives thereof. In some embodiments, Q 'is 1,4-phenylene, 2,6-naphthylene, 4,4'-biphenylene, 4,4'-(1,1'-binaphthylene), and heavy water thereof Selected from the group consisting of digested derivatives.

In one embodiment, the host is deuterated indolocarbazole having Formula XII or Formula XIII:

(XII)

(XIII)

here,

Ar ¹⁴ is an aromatic electron transport group;

Ar ¹⁵ is selected from the group consisting of aryl groups and aromatic electron transport groups;

R ¹⁸ and R ¹⁹ are the same or different at each occurrence and are selected from the group consisting of H, D and aryl;

Wherein the compound has at least one D.

In some embodiments of Formula XII and Formula XIII, deuterium is present on a portion selected from the group consisting of indolocarbazole cores, aryl rings, substituent groups on aryl rings, and combinations thereof.

Ar ¹⁴ is an aromatic electron transport group. In some embodiments, the aromatic electron transport group is a nitrogen-containing heteroaromatic group. Some examples of nitrogen-containing heteroaromatic groups that transport electrons include, but are not limited to, those shown below.

In the above formula:

Ar ¹⁶ is an aryl group;

R ²⁰ is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl;

m is an integer from 0 to 4;

n is an integer from 0 to 3;

o is an integer from 0 to 2;

p is an integer from 0 to 5;

q is 0 or 1;

r is an integer of 0-6.

The group can be bonded to the nitrogen on the core at any position indicated by the broken line.

In some embodiments, two or more of the same or different electron-withdrawing substituents are joined together to form oligomeric substituents. In some embodiments, R ²⁰ is selected from the group consisting of D and aryl. In some embodiments, R ²⁰ is a nitrogen-containing heteroaromatic electron transport group.

In some embodiments, Ar ¹⁵ is an aromatic electron transport group as discussed above. In some embodiments, Ar ¹⁵ is from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthylene, naphthylphenylene, deuterated derivatives thereof, and groups having formula a or formula b as discussed above Is selected.

In some embodiments, the host material is deuterated diarylanthracene, deuterated aminocricene, deuterated diaryrylcene, deuterated diarypyrene, deuterated indolocarbazole, deuterated phenanthroline, and combinations thereof Selected from the group consisting of.

Some non-limiting examples of deuterated host compounds include compounds H1 through H17 shown below.

Compound H1:

Where x + y + z + n = 1-26.

Compound H5:

Where x + y + z + p + n + q = 1-34.

Compound H8:

Compound H9:

Compound H13:

Compound H14:

Compound H15:

Compound H16:

Σ (a-f) = 1-25

Compound H17:

Σ (a-f) = 1-28

5. electron transport layer

Electron transport layer 150 includes an electron transport material. When referring to a layer, material, member, or structure, the term "electron transport" refers to the layer, material, member, or structure, while the layer, material, member, or structure is accompanied by relative efficiency and low charge loss. It is intended to mean that the movement of the negative charge through the thickness of. Although the luminescent material may also have some electron transport properties, the term “electron transport layer, material, member, or structure” is not intended to include a layer, material, member, or structure whose primary function is luminescence.

The electron transport material may be a polymer, oligomer, or small molecule. They may be deposited or deposited from a liquid, which may be in the form of a solution, dispersion, suspension, emulsion, colloid mixture or other composition.

In some embodiments, the electron transport layer comprises deuterated material. In some embodiments, the electron transport material is at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated.

In some embodiments, electron transport layer 150 comprises deuterated phenanthroline derivatives having Formula IX, Formula X, or Formula XI as discussed above. In some embodiments, electron transport layer 150 consists essentially of deuterated phenanthroline derivatives having Formula IX, Formula X, or Formula XI.

In some embodiments, electron transport layer 150 includes deuterated indolocarbazole derivatives having Formula XII or Formula XIII as discussed above. In some embodiments, electron transport layer 150 consists essentially of deuterated indolocarbazole derivatives having Formula XII or Formula XIII.

In some embodiments, the electron transport layer comprises a material selected from the group consisting of deuterated benzimidazole, deuterated triazolopyridine, and deuterated diheteroarylphenyl.

In some embodiments, electron transport layer 150 comprises a deuterated metal chelated oxynoid compound. Examples of such materials include deuterated metal quinolate derivatives, such as deuterated tris (8-hydroxyquinolato) aluminum (d-AlQ), deuterated bis (2-methyl-8-quinolinolato) ( p-phenylphenolrato) aluminum (d-BAlq), deuterated tetrakis- (8-hydroxyquinolato) hafnium (d-HfQ) and deuterated tetrakis- (8-hydroxyquinolato) zirconium (d- ZrQ).

In some embodiments, the electron transport layer comprises deuterated phenanthroline, deuterated indolocarbazole, deuterated benzimidazole, deuterated triazolopyridine, deuterated diheteroarylphenyl, deuterated metal quinolate, and their An electron transport material selected from the group consisting of combinations. In some embodiments, the electron transport layer comprises deuterated phenanthroline, deuterated indolocarbazole, deuterated benzimidazole, deuterated triazolopyridine, deuterated diheteroarylphenyl, deuterated metal quinolate, and their It consists essentially of electron transport materials selected from the group consisting of combinations.

Examples of other electron transport materials that can be used in the electron transport layer 150 are azole compounds, such as 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4 Oxadiazole (PBD), 3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ), and 1,3, 5-tri (phenyl-2-benzimidazole) benzene (TPBI); Quinoxaline derivatives such as 2,3-bis (4-fluorophenyl) quinoxaline; Triazines; Fullerenes; Deuterated analogs of any of the foregoing materials; And mixtures thereof. In some embodiments, the electron transport layer further comprises an n-dopant. N-dopant materials are well known. n-dopants include Group 1 and Group 2 metals; Group 1 and 2 metal salts such as LiF, CsF, and Cs ₂ CO ₃ ; Group 1 and 2 metal organic compounds such as Li quinolate; And molecular n-dopants such as leuco dyes, metal complexes such as W ₂ (hpp) ₄ , where hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido- [ 1,2-a] -pyrimidine) and cobaltocene, tetrathianaphthacene, bis (ethylenedithio) tetrathiafulvalene, heterocyclic radical or diradical, and dimers, oligomers, polymers, heterocytes Polycyclic and dispiro compounds of click radicals or diradicals, including but not limited to. n-dopant may also be deuterated.

Some non-limiting examples of deuterated electron transport compounds include compounds ET1 to ET4 shown below.

ET1:

ET2:

Σ (x + y + z) = 1-54

ET3:

ET4:

6. Chemical containment

To produce a display having a full-color image, each display pixel is divided into three sub-pixels each emitting one of the three-way display index red, green and blue. When different colors are applied by the liquid deposition technique, it is necessary to prevent the diffusion and mixing of the liquid coloring material (ie ink) from one subpixel to the next subpixel.

One way to prevent color mixing is to provide a chemical containment layer before applying the coloring ink. The term “chemical containment layer” is intended to mean a patterned layer that blocks or restricts the diffusion of liquid material through surface energy effects rather than physical barrier structures. When referring to a layer, the term "contained" is intended to mean that the layer does not diffuse significantly beyond the deposited area. The term "surface energy" is the energy required to create a unit area of surface from a material. A feature of surface energy is that liquid materials with a given surface energy do not wet surfaces with lower surface energy.

In some embodiments, the chemical containment layer comprises deuterated material. In some embodiments, the chemical containment material is at least 10% deuterated; In some embodiments, at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated.

In some embodiments, for devices fabricated starting from the anode side, a chemical containment layer is applied over the hole injection layer to block both the hole transport layer and the electroluminescent layer. In some embodiments, the chemical containment layer is applied over the hole transport layer to contain the electroluminescent layer. In devices fabricated starting from the cathode side, the chemical containment layer can be applied over the electron injection layer or the electron transport layer.

In some embodiments, a priming layer is used to form a chemical containment layer on the first layer, where the priming layer has a surface energy that is significantly different from the surface energy of the first layer. The priming layer is applied entirely on the first layer. The priming layer is then exposed to radiation in a pattern that forms the exposed and non-exposed areas. The priming layer is then developed to effectively remove the priming layer from the exposed or non-exposed areas. As a result, a patterned priming layer on the first layer is obtained. The patterned priming layer is a chemical containment layer. The terms "effectively remove" and "effectively remove" mean that the priming layer is essentially completely removed in the exposed or non-exposed areas. In addition, by partially removing the priming layer in another region, it is possible to make the remaining pattern of the priming layer thinner than the original priming layer.

In some embodiments, the pattern of the priming layer has a surface energy higher than the surface energy of the first layer. The second layer is formed by liquid deposition over the pattern of priming layers on the first layer.

In some embodiments, the pattern of the priming layer has a surface energy lower than the surface energy of the first layer. The second layer is formed by liquid deposition over the first layer in the region from which the priming layer is removed. Such process and non-deuterated materials are described in published US patent application US 2007/0205409.

One method of determining the relative surface energy is to compare the contact angle of a given liquid on the first organic layer to the contact angle of the same liquid on the priming layer (hereinafter referred to as the "developed priming layer") after exposure and development. As the surface energy decreases, the contact angle increases. Equipment for measuring contact angles is manufactured by various manufacturers.

In some embodiments, the surface energy of the first layer is more than the surface energy of the priming layer. In some embodiments, the contact angle for the anisole of the first layer is greater than 40 ° C .; In some embodiments, greater than 50 °; In some embodiments, greater than 60 °; In some embodiments, greater than 70 °. In some embodiments, the contact angle for the anisole of the developed priming layer is less than 30 °; In some embodiments, less than 20 °; In some embodiments, less than 10 °. In some embodiments, for a given solvent, the contact angle with the developed priming layer is at least 20 ° lower than the contact angle with the first layer; In some embodiments, for a given solvent, the contact angle with the developed priming layer is at least 30 ° lower than the contact angle with the first layer; In some embodiments, for a given solvent, the contact angle with the developed priming layer is at least 40 ° lower than the contact angle with the first layer.

The priming layer includes a composition that reacts when exposed to radiation to form a material that has a higher or lower removability from the underlying first layer than the unexposed priming material. This change should be sufficient to allow physical differentiation and development of the exposed and non-exposed areas.

In one embodiment, the priming layer comprises a radiation-hardenable composition. In this case, when exposed to radiation, the priming layer may become less soluble or dispersible, less tacky, less soft, less fluid, less mobile, or less absorbent in the liquid medium. have. Other physical properties can also be affected.

In one embodiment, the priming layer consists essentially of one or more radiation-sensitive materials. In one embodiment, the priming layer consists essentially of a material that, when exposed to radiation, cures, or becomes less soluble, expandable or dispersible, or less tacky or absorbent in a liquid medium. In one embodiment, the priming layer consists essentially of a material having a radiation polymerizable group. Examples of such groups include, but are not limited to, olefins, acrylates, methacrylates and vinyl ethers. In one embodiment, the priming material has two or more polymerizable groups that can cause crosslinking.

In one embodiment, the priming layer consists essentially of at least one reactive material and at least one radiation-sensitive material. The radiation-sensitive material, when exposed to radiation, generates active species that initiate the reaction of the reactive material. Examples of radiation-sensitive materials include, but are not limited to, those that generate free radicals, acids, or combinations thereof.

In one embodiment, the reactive material is polymerizable or crosslinkable. Material polymerization or crosslinking reactions are initiated or catalyzed by active species. In one embodiment, the reactive material is an ethylenically unsaturated compound and the radiation-sensitive material generates free radicals. Ethylenically unsaturated compounds include, but are not limited to, acrylates, methacrylates, vinyl compounds, and combinations thereof. Any known class of radiation-sensitive materials that generate free radicals can be used. Examples of radiation-sensitive materials that generate free radicals include quinones, benzophenones, benzoin ethers, aryl ketones, peroxides, biimidazoles, benzyl dimethyl ketals, hydroxyl alkyl phenyl acetophons, dialkoxy actophenones, trimethyl Benzoyl phosphine oxide derivatives, aminoketones, benzoyl cyclohexanol, methyl thiophenyl morpholino ketones, morpholino phenyl amino ketones, alpha halogenoacetophenones, oxalfonyl ketones, sulfonyl ketones, oxalfonyl ketones, Sulfonyl ketones, benzoyl oxime esters, thioxanthrones, campoquinones, ketocoumarins, and Michler's ketones. Alternatively, the radiation sensitive material may be a mixture of compounds, one of which provides free radicals when it is intended to provide free radicals by sensitizers activated by radiation. In one embodiment, the radiation sensitive material is sensitive to visible or ultraviolet radiation.

The radiation-sensitive material is generally present in an amount of 0.001% to 10.0% based on the total weight of the priming layer.

In one embodiment, the reactive material may undergo polymerization initiated by an acid and the radiation-sensitive material generates an acid. Examples of such reactive materials include, but are not limited to, epoxy. Examples of radiation-sensitive materials that generate acids include, but are not limited to, sulfonium and iodonium salts, such as diphenyliodonium hexafluorophosphate.

In one embodiment, the priming layer comprises a radiation-softenable composition. In this case, when exposed to radiation, the priming layer may become more soluble or dispersible in the liquid medium, may become more tacky, more soft, more fluid, more mobile, or more absorbent. . Other physical properties can also be affected.

In one embodiment, the priming layer consists essentially of a material that, when exposed to radiation, softens, increases solubility, expandability, or dispersibility, or becomes tacky or absorbent in a liquid medium.

In one example of the radiation-softening composition, the reactive material is a phenolic resin and the radiation-sensitive material is diazonaphthoquinone.

In one example of the radiation-softening composition the priming layer consists essentially of at least one polymer that undergoes skeletal degradation when exposed to far ultraviolet radiation having a wavelength in the range of 200 to 300 nm. Examples of polymers that undergo such degradation include, but are not limited to, polyacrylates, polymethacrylates, polyketones, polysulfones, copolymers thereof, and mixtures thereof.

Other radiation-sensitive systems known in the art can also be used.

In one embodiment, the priming layer reacts with the underlying area when exposed to radiation. The exact mechanism of this reaction will depend on the material used. After exposure to radiation, the priming layer is effectively removed in the unexposed areas by suitable development treatment. In some embodiments, the priming layer is removed only in the non-exposed areas. In some embodiments, the priming layer is partially removed even in the exposed areas, leaving thinner layers in these areas. In some embodiments, the priming layer remaining in the exposed area is less than 50 GPa thick. In some embodiments, the priming layer remaining in the exposure area is essentially a single layer in thickness.

In some embodiments, the priming material is deuterated. The term "deuterated" is intended to mean that at least one H has been replaced with D. The term “deuterated analog” refers to a structural analog of a compound or group in which one or more available hydrogens have been replaced with deuterium. In deuterated compounds or deuterated analogs, deuterium is present at least 100 times the natural abundance level. In some embodiments, the priming material is at least 10% deuterated. This means that at least 10% of hydrogen has been replaced with deuterium. In some embodiments, the priming material is at least 20% deuterated; In some embodiments, at least 30% deuterated; In some embodiments, at least 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, at least 70% deuterated; In some embodiments, at least 80% deuterated; In some embodiments, at least 90% deuterated; In some embodiments, 100% deuterated.

The priming layer can be applied by any known deposition process. In one embodiment, the priming layer is applied without adding it to the solvent. In one embodiment, the priming layer is applied by vapor deposition.

In one embodiment, the priming layer is applied by a condensation process. If the priming layer is applied by condensation from the vapor phase and the surface layer temperature is too high during vapor condensation, the priming layer may migrate into the pores or free volume of the organic substrate surface. In some embodiments, the organic substrate is maintained at a temperature below the glass transition temperature or melting temperature of the substrate material. The temperature can be maintained by any known technique, such as by placing a first layer on a surface that is cooled with a flowing liquid or gas.

In one embodiment, a priming layer is applied to the temporary support prior to the condensation step to form a uniform coating of the priming layer. This can be accomplished by any deposition method, including liquid deposition, deposition and thermal transfer. In one embodiment, the priming layer is deposited on the temporary support by continuous liquid deposition techniques. The choice of liquid medium for the deposition of the priming layer will depend on the exact nature of the priming layer itself. In one embodiment, the material is deposited by spin coating. The coated temporary support is then used as a source for heating to form a vapor for the condensation step.

Application of the priming layer can be accomplished using a continuous or batch process. For example, in a batch process, one or more devices may be simultaneously coated with a priming layer and then simultaneously exposed to a radiation source. In a continuous process, as the device moving on the belt or other transport device passes through the station, the device will be sequentially coated with a priming layer and then subsequently exposed to the radiation source sequentially past the station. Portions of the process may be continuous while other portions of the process may be batchwise.

In one embodiment, the priming material is liquid at room temperature and is applied by liquid deposition on the first layer. The liquid priming material may be film-forming or may be absorbed or adsorbed onto the surface of the first layer. In one embodiment, the liquid priming material is cooled to a temperature below its melting point to form a second layer over the first layer. In one embodiment, the priming material is not a liquid at room temperature, but is heated to a temperature above its melting point, deposited on the first layer and cooled to room temperature to form a second layer over the first layer. For liquid deposition, any of the above methods can be used.

In one embodiment, the priming layer is deposited from the second liquid composition. As above, the liquid deposition method may be continuous or discontinuous. In one embodiment, the priming liquid composition is deposited using a continuous liquid deposition method. The choice of liquid medium for the deposition of the priming layer will depend on the exact nature of the priming material itself.

After the priming layer is formed, it is exposed to radiation. The type of radiation used will depend on the sensitivity of the priming layer as discussed above. Exposure is a pattern system. The term "pattern mode" as used herein denotes that only selected portions of a material or layer are exposed. Patternwise exposure can be achieved using any known imaging technique. In one embodiment, the pattern is achieved by exposing through a mask. In one embodiment, the pattern is achieved by exposing only selected portions with a rastered laser. The exposure time can range from a few seconds to several minutes depending on the specific chemical nature of the priming layer used. When a laser is used, much shorter exposure times are used for each individual area, depending on the output of the laser. The exposure step can be carried out in air or in an inert atmosphere, depending on the sensitivity of the material.

In one embodiment, the radiation comprises a group consisting of ultraviolet radiation (10-390 nm), visible radiation (390-770 nm), infrared radiation (770-10 ⁶ nm), and combinations thereof, including simultaneous treatment and sequential treatment. Is selected from. In one embodiment, the radiation is selected from visible light radiation and ultraviolet radiation. In one embodiment, the radiation ranges from 300 nm to 450 nm in wavelength. In one embodiment, the radiation is far ultraviolet (200-300 nm). In another embodiment, the ultraviolet radiation has a wavelength of 300 nm to 400 nm. In another embodiment, the radiation ranges in wavelength from 400 nm to 450 nm. In one embodiment, the radiation is thermal radiation. In one embodiment, the exposure to radiation is performed by heating. The temperature and duration for the heating step is such that at least one physical property of the priming layer changes without damaging any underlying layer of the light emitting region. In one embodiment, the heating temperature is less than 250 ° C. In one embodiment, the heating temperature is less than 150 ° C.

After exposure to radiation in a patterned manner, the priming layer is developed. Development can be accomplished by any known technique. Such techniques have been widely used in photoresist and printing techniques. Examples of developing techniques include, but are not limited to, application of heat (evaporation), treatment with a liquid medium (washing), treatment with an absorbent material (blotting), treatment with an adhesive material, and the like. The developing step causes effective removal of the priming layer in the exposed or non-exposed areas. Thereafter, the priming layer remains in the unexposed or exposed areas, respectively. Although the priming layer may be partially removed in the unexposed or unexposed areas, a sufficient amount must remain in order for a wettability difference to exist between the exposed and unexposed areas. For example, the priming layer may be effectively removed in the non-exposed areas, and part of the thickness may be removed in the exposed areas. In some embodiments, the developing step results in effective removal of the priming layer in the non-exposed areas.

In one embodiment, exposure of the priming layer to radiation causes a change in the solubility or dispersibility of the priming layer in the solvent. In this case, development can be achieved by a wet development process. This treatment typically involves washing with a solvent that dissolves, disperses, or exfoliates one type of region. In one embodiment, patterned exposure to radiation causes insolubilization of the exposed area of the priming layer and treatment with the solvent causes removal of the unexposed area of the priming layer.

In one embodiment, the exposure of the priming layer to radiation causes a reaction that changes the volatility of the priming layer in the exposure area. In this case, development can be achieved by thermal development treatment. This treatment includes heating to a temperature higher than the volatilization or sublimation temperature of the more volatile material and below the temperature at which the material thermally reacts. For example, for polymerizable monomers, the material will be heated at a temperature above the sublimation temperature and below the thermal polymerization temperature. It will be appreciated that priming materials having thermal reaction temperatures close to or below the volatilization temperature may not be possible to develop in this manner.

In one embodiment, exposure of the priming layer to radiation causes a change in temperature at which the material melts, softens or flows. In this case, development can be achieved by a dry development process. The dry development treatment may include contacting the outermost surface of the element with the absorbent surface to absorb or exude the softer portion. This dry phenomenon can be carried out at elevated temperatures, as long as it does not further affect the properties of the residual region.

The developing step results in a region of the remaining priming layer and a region in which the underlying first layer is exposed.

In some embodiments, the priming layer comprises a hole transport material. In some embodiments, the priming layer comprises a material selected from the group consisting of triarylamine, carbazole, fluorene, polymers thereof, copolymers thereof, deuterated analogs thereof, and combinations thereof. In some embodiments, the priming layer is polymeric triarylamine, polycarbazole, polyfluorene, polymeric triarylamine with conjugated moieties connected in a non-planar configuration, copolymers of fluorene and triarylamine, heavy water thereof Digestive analogs, and combinations thereof. In some embodiments, the polymeric material is crosslinkable. In some embodiments, the priming layer comprises an electron transport material. In some embodiments, the priming layer comprises a metal chelated oxynoid compound. In some embodiments, the priming layer comprises a metal quinolate derivative. In some embodiments, the priming layer is tris (8-hydroxyquinolato) aluminum, bis (2-methyl-8-quinolinolato) (p-phenylphenolrato) aluminum, tetrakis- (8-hydroxyquinol Raito) hafnium, and tetrakis- (8-hydroxyquinolato) zirconium. In some embodiments, the priming layer consists essentially of a material selected from the group consisting of polymeric triarylamines, polycarbazoles, polyfluorenes, copolymers thereof, and metal quinolates.

In some embodiments, the hole injection layer comprises a conductive polymer doped with a fluorinated acid polymer and the priming layer consists essentially of the hole transport material. In some embodiments, the hole transport material is triarylamine polymer. Such polymers are described, for example, in published PCT applications WO 2008/024378, WO 2008/024379, and WO 2009/067419. In some embodiments, the priming material is a group consisting of polymeric triarylamines having conjugated moieties linked in a non-planar configuration, compounds having at least one fluorene moiety and at least two triarylamine moieties, and deuterated analogs thereof Is selected from. In some embodiments, the polymeric triarylamine has Formula I, Formula II, or Formula III as above.

Some exemplary compounds that can be used as the priming layer include deuterated fluorenes, deuterated polyfluorenes, deuterated polyvinylcarbazoles, compounds HT1 to HT12, ET3 and ET4.

7. Other device layers

Other layers in the device can be made of any material known to be useful for such layers.

Anode 110 is a particularly efficient electrode for injecting positive charge carriers. It may be made of a material comprising, for example, metals, mixed metals, alloys, metal oxides or mixed-metal oxides, or may be conductive polymers, or mixtures thereof. Suitable metals include Group 11 metals, metals in Groups 4-6, and Group 8-10 transition metals. If the anode is light transmissive, mixed-metal oxides of group 12, 13 and 14 metals, for example indium-tin-oxides, are generally used. Anode 110 is described in "Flexible light-emitting diodes made from soluble conducting polymer," Nature vol. 357, pp 477-479 (11 June 1992), may also include organic materials such as polyaniline. At least one of the anode and the cathode is preferably at least partially transparent so that the generated light can be observed.

The cathode 160 is an electrode that is particularly efficient for injecting electrons or negative charge carriers. The cathode can be any metal or nonmetal having a lower work function than the anode. Materials for the cathode may be selected from alkali metals of Group 1 (eg, Li, Cs), Group 2 (alkaline earth) metals, Group 12 metals (including rare earth elements and lanthanides and actinides). Combinations thereof can be used with materials such as aluminum, indium, calcium, barium, samarium and magnesium. In order to lower the operating voltage, Li- or Cs-comprising organometallic compounds, LiF, CsF, and Li ₂ O can also be deposited between the organic layer and the cathode layer.

It is known to have other layers in organic electronic devices. For example, a layer (not shown) that controls the amount of positive charge injected and / or provides band-gap matching of the layer or acts as a protective layer includes the anode 110 and the hole injection layer ( 120). Layers known in the art can be used, for example, ultrathin layers of metals such as copper phthalocyanine, silicon oxy-nitride, fluorocarbons, silanes, or Pt. Alternatively, some or all of the anode layer 110, active layer 120, 130, 140, 150, or cathode layer 160 may be surface treated to increase charge carrier transport efficiency. The selection of the material of each component layer is preferably determined to provide a device with high electroluminescence efficiency by balancing the positive and negative charges in the emitter layer. Any or all of these layers may comprise deuterated materials.

It is understood that each functional layer may consist of more than one layer.

The device can be fabricated by a variety of techniques including sequentially depositing individual layers on a suitable substrate. Substrates such as glass, plastic and metal can be used. Conventional deposition techniques such as thermal evaporation, chemical vapor deposition and the like can be used. Alternatively, organics may be derived from solutions or dispersions in suitable solvents using conventional coating or printing techniques including, but not limited to, spin coating, dip coating, roll-to-roll technology, inkjet printing, screen printing, gravure printing, and the like. The layer can be applied.

In some embodiments, the process of manufacturing the organic light emitting device includes the following steps:

Providing a substrate having a patterned anode thereon;

forming an electroactive layer by depositing a first liquid composition comprising (a) a deuterated electroactive material and (b) a liquid medium; And

Forming a cathode as a whole.

The term "liquid composition" refers to a liquid medium in which one or more materials are dissolved to form a solution, a liquid medium in which one or more materials are dispersed to form a dispersion, or a liquid medium in which one or more materials are suspended to form a suspension or emulsion. It is to be included.

In some embodiments of the process, the deuterated electroactive material is a deuterated hole injection material. In some embodiments of the process, the deuterated electroactive material is a deuterated hole transport material. In some embodiments of the process, the deuterated electroactive material is a deuterated electroluminescent material. In some embodiments of the process, the deuterated electroactive material is a deuterated host material. In some embodiments of the process, the deuterated electroactive material is a deuterated electron transporting material. In some embodiments of the process, the deuterated electroactive material is a deuterated chemical containment material.

In some embodiments, the process

And forming a second electroactive layer by depositing a second liquid composition comprising a second deuterated electroactive material in a second liquid medium.

In some embodiments, the second deuterated electroactive material consists of deuterated hole injection material, deuterated hole transport material, deuterated electroluminescent material, deuterated host material, deuterated electron transport material, and deuterated chemical containment material Selected from the group.

Any known liquid deposition technique or combination of techniques can be used, including continuous and discontinuous techniques. Examples of continuous liquid deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating, and continuous nozzle printing. Examples of discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing. In some embodiments, the electroactive layer is formed in a pattern by a method selected from continuous nozzle coating and ink jet printing. Although nozzle printing can be considered as a continuous technique, a pattern can be formed by placing the nozzle only over a desired area in forming a layer. For example, a pattern of consecutive rows can be formed.

Suitable liquid media for the particular compositions to be deposited can be readily determined by those skilled in the art. In some applications, it is desirable that the compound be dissolved in a non-aqueous solvent. Such non-aqueous solvents are relatively polar, such as C ₁ to C ₂₀ alcohols, ethers and acid esters, or relatively non- such as aromatics such as C ₁ to C ₁₂ alkanes, or toluene, xylene, trifluorotoluene and the like. It may be polar. As described herein, other suitable liquids used to prepare liquid compositions as solutions or dispersions comprising the novel compounds include chlorinated hydrocarbons (eg methylene chloride, chloroform, chlorobenzene), aromatic hydrocarbons (eg For example substituted or unsubstituted toluene or xylene (including trifluorotoluene), polar solvents (e.g. tetrahydrofuran (THF), N-methyl pyrrolidone (NMP)), esters (e.g. ethyl acetate ), Alcohols (eg isopropanol), ketones (eg cyclopentatone), or any mixture thereof. Examples of solvent mixtures for electroluminescent materials are described, for example, in published US application 2008-0067473.

After deposition, the material is dried to form a layer. Any conventional drying technique can be used, including heating, vacuum, and combinations thereof.

In some embodiments, the device is fabricated by liquid deposition of hole injection layers, hole transport layers and electroactive layers, and deposition of anodes, electron transport layers, electron injection layers and cathodes.

8. Synthesis of Deuterated Materials

Non-deuterated analogs of the compounds described herein can be prepared by known coupling and substitution reactions. In a similar manner using deuterated precursor materials, or more generally, Lewis acid H / D exchange catalysts such as aluminum trichloride or ethyl aluminum chloride, or acids such as CF ₃ COOD, DCl Novel deuterated compounds can be prepared by treating the non-deuterated compounds with deuterated solvents such as d6-benzene in the presence of the like. Exemplary preparations are provided in the Examples. Deuteration levels can be determined by NMR analysis and mass spectrometry, such as Atmospheric Solids Analysis Probe Mass Spectrometry (ASAP-MS).

Starting materials for overdeuterated or partially deuterated aromatic compounds or alkyl compounds can be purchased from commercial sources or obtained using known methods. Some examples of such methods can be found in the literature: a) "Efficient H / D Exchange Reactions of Alkyl-Substituted Benzene Derivatives by Means of the Pd / C-H2-D2O System" Hiroyoshi Esaki, Fumiyo Aoki, Miho Umemura, Masatsugu Kato, Tomohiro Maegawa, Yasunari Monguchi, and Hironao Sajiki Chem. Eur. J. 2007, 13, 4052-4063.] b) Aromatic H / D Exchange Reaction Catalyzed by Groups 5 and 6 Metal Chlorides GUO, Qiao-Xia, SHEN, Bao-Jian; GUO, Hai-Qing TAKAHASHI, Tamotsu Chinese Journal of Chemistry, 2005, 23, 341-344; c) A novel deuterium effect on dual charge-transfer and ligand-field emission of the cis-dichlorobis (2,2'-bipyridine) iridium (III) ion "Richard J. Watts, Shlomo Efrima, and Horia Metiu J Am. Chem. Soc., 1979, 101 (10), 2742-2743; d) "Efficient H-D Exchange of Aromatic Compounds in Near-Critical D20 Catalysed by a Polymer-Supported Sulphonic Acid" Carmen Boix and Martyn Poliakoff Tetrahedron Letters 40 (1999) 4433-4436; e) US3849458; f) See "Efficient C-H / C-D Exchange Reaction on the Alkyl Side Chain of Aromatic Compounds Using Heterogeneous Pd / C in D2O" Hironao Sajiki, Fumiyo Aoki, Hiroyoshi Esaki, Tomohiro Maegawa, and Kosaku Hirota Org. Lett., 2004, 6 (9), 1485-1487].

The compounds described herein can be formed into films using liquid deposition techniques. Surprisingly, these compounds have significantly improved properties when compared to similar non-deuterated compounds. Electronic devices comprising an active layer with a compound described herein have a greatly improved lifetime. In addition, the lifetime increase is achieved in combination with high quantum efficiency and good color saturation. In addition, the deuterated compounds described herein have greater air tolerance than non-deuterated analogs. This can lead to greater processing tolerances, both in the manufacture and purification of materials, and in the formation of electronic devices using the materials.

Example

The following examples illustrate certain features and advantages of the present invention. The examples are intended to illustrate the invention and are not intended to be limiting. All percentages are by weight unless otherwise indicated.

Synthesis Example 1

This example describes the production of deuterated hole injection material, D-HIJ-1.

a. Heavy water (D ₂ Preparation of Deutero-HFAP Dispersion in O).

Copolymers of tetrafluoroethylene ("TFE") and perfluoro-3,6-dioxa-4-methyl-7-octensulfonic acid ("PSEPVE") are deuterated and in D ₂ O in the following manner: Made into a colloidal dispersion. First, every 987 grams (weight of copolymer per acid site), using procedures similar to those of US Pat. No. 6,150,426, Example 1, Part 2, except that the temperature is approximately 270 ° C. Poly (TFE-PSEPVE) with protons in two sulfonic acids was made into an aqueous dispersion. Non-deuterated poly (TFE-PSEPVE) dispersions were converted to free flowing solid flakes of poly (TFE-PSEPVE) on trays having a liquid depth of 5/8 "(1.59 cm) or less. The tray was then less than 0 ° C. The water dispersion was first frozen, once it was frozen, it was placed under partial vacuum pressure up to 1 mm Hg until most of the water was removed, and then the partially dried solid was raised to about 30 ° C. under vacuum pressure. The moisture was completely removed without adhesion of the polymer.

21 g of solid flakes of non-deuterated poly (TFE-PSEPVE), which had been previously dried in a vacuum oven to remove water, were placed in a cylindrical metal tube previously purged with nitrogen. 150 g of D ₂ O, purchased from Cambridge Isotope Lab, Inc., was immediately added to the tube containing poly (TFE-PSEPVE). To ensure conversion from solid flakes to poly (TFE-PSEPVE) colloidal dispersion in D ₂ O, the tube was capped and heated to about 270 ° C. for a short period in a pressure lab and then cooled to RT. In addition, protons of poly (TFE-PSEPVE) were exchanged for deuterium in an overwhelming excess of deuterium to complete deuteration of poly (TFE-PSEPVE). Deuterated Poly (TFE-PSEPVE) in D ₂ O ("D-poly (TFE-PSEPVE)") dispersions were further processed to remove larger particles. The weight percent D-poly (TFE-PSEPVE) in the D ₂ O dispersion was determined to be 11.34 weight percent based on the total weight of the dispersion by the gravimetric method.

b. Deutero-HFAP and Heavy Water (D ₂ Direct process for preparing the deutero-HFAP dispersion in O).

The copolymer of tetrafluoroethylene ("TFE") and perfluoro-3,6-dioxa-4-methyl-7-octensulfonic acid ("PSEPVE") is deuterated and in D ₂ O in the following manner: It can be made into a colloidal dispersion. Every 987 grams (per acidic site) using a procedure similar to that of US Pat. No. 6,150,426, Example 1, Part 2, except that the temperature is approximately 270 ° C. and D ₂ O is used instead of water. Poly (TFE-PSEPVE) resin with one proton in sulfonic acid per weight of copolymer) can be made into a D2O dispersion.

c. Preparation of Deuterated Electrically Conductive Polymer Doped with Deuterated HFAP.

Deuterated pyrrole (“D _5- Py”) (Formula 72.12) was purchased from Aldrich Chemical Company (Milwaukee, Wis.). This brown liquid was fractionally distilled under reduced pressure before use. The colorless distillate was characterized by ¹³ C NMR spectroscopy to confirm its structure.

Polymerization of D _5- Py in D-poly (TFE-PSEPVE) / D ₂ O dispersion was carried out in the following manner. First, 70.2 g of D-poly (TFE-PSEPVE) / D ₂ O prepared in Example 1 was weighed into a 500 ml resin kettle, and then 14 g of D ₂ O was further added. The amount of D-poly (TFE-PSEPVE) / D ₂ O represents 8.14 mmol of acid. The kettle was covered with a glass lid with an overhead stirrer. While stirring D-poly (TFE-PSEPVE) / D ₂ O, 0.135 g (0.26 mmol) of ferric sulfate and 0.62 g (2.6 mmol) of Na ₂ S ₂ O ₈ were dissolved in 10 mL in advance. Added to poly (TFE-PSEPVE) / D ₂ O. After a while, 0.175 g (2.43 mmol) of D _5- Py, previously dissolved in 7 mL of D ₂ O, was added to the mixture for 1 minute. The polymerization started immediately after the addition of D _5- Py. The polymerization was allowed to proceed for 10 minutes. Addition and polymerization of the components took place under nitrogen. When 10 minutes had elapsed, Dowex M-43 resin was added to the resin kettle and mixed for approximately 5 minutes. After vacuum filtration with 417 filter paper, Dodds M-31 Na ⁺ resin was added to the mixture and mixed for 5 minutes. The resulting material was once again vacuum filtered using 417 filter paper. D- doped with poly (TFE-PSEPVE) deuterated polypyrrole ( "poly (D _{5 -} Py) / D- poly (TFE-PSEPVE)") adding the dispersion to reprocess the dispersion of D ₂ O in the ion exchange resin Purified with, it contained only 1.79 ppm of sulfate, and 0.79 ppm of chloride. The percent solids of the dispersion was determined to be 4.3% and the pH to 5.2. The electrical conductivity of the cast film calcined at 275 ° C. for 30 minutes in a dry box was measured at ˜1 × 10 ⁻⁶ S / cm at room temperature.

Synthesis Example 2

This example describes the production of deuterated hole transport material, HT5. This is indicated below, where R ¹ = n-propyl, R ² = n-octyl, y = 0 and x = 42:

The compound is prepared according to the following scheme.

Synthesis of Intermediate Compound Y1:

Under a nitrogen atmosphere, AlCl ₃ (0.17 g, 1.29 mmol) was dissolved in 2,2'-dioctyl-4,4'-dibromo-1,1'-binaftylene (2.328 g, 3.66 mmol) in C ₆ D _6. (100 mL) was added to the solution. The resulting mixture was stirred at rt for 30 min before D ₂ O (50 mL) was added. After separating the layers the aqueous layer was washed with CH ₂ Cl ₂ (2 × 30 mL). The combined organic layers were dried over magnesium sulphate and the volatiles were removed on a rotary evaporator. The crude product was purified by column chromatography. Compound Y1 was obtained as a white powder (1.96 g).

Synthesis of Intermediate Compound Y2:

Compound Y2 can be prepared from compound Y1 using a procedure similar to the preparation of intermediate compound C1. Chromatography is used to purify compound Y2.

Synthesis of Intermediate Compound Y3:

Under nitrogen, compound Y2 (2.100 g, 2.410 mmol) and dichloromethane (30 mL) were added to a 100 mL round bottom flask. It was allowed to stir for 5 minutes before trifluoroacetic acid (1.793 mL) was added and the reaction mixture was stirred overnight. Once the reaction was complete, it was quenched using saturated sodium carbonate solution. Water was removed, washed with CH 2 Cl 2 and the combined organic layers were evaporated to dryness. The residue was dissolved in diethyl ether and the product was washed with sodium carbonate, brine and water and dried using magnesium sulfate. Purification of compound Y3 using chromatography gave 1.037 g.

As shown in FIG. 2, the structure of the compound was confirmed by ¹ H NMR.

Synthesis of Intermediate Compound Y4:

A solution of 4-bromo-4'-propylbiphenyl (5.10 g, 18.53 mmol) in C6D6 (20 mL) was purged with nitrogen for 30 min. A 1.0 M solution of ethyl aluminum dichloride solution in hexane (4.0 mL, 4.0 mmol) was added dropwise via syringe and the reaction mixture was heated to reflux for 1.75 h under a nitrogen atmosphere. After cooling to room temperature under a nitrogen atmosphere, heavy water (20 mL) was added and the mixture was shaken to separate the layers. The aqueous layer was extracted with benzene (3 × 10 mL) and the combined organic phases were dried over magnesium sulphate, filtered and concentrated on a rotary evaporator. The above reaction conditions were further applied to the product thus obtained twice. After the third treatment, the crude product was recrystallized from ethanol (20 mL) to give compound Y4 (1.01 g) as a white solid. Mp 110.1 to 111.6 ° C. Purity (UPLC): 100%. The ¹ H NMR spectrum of Y4 was consistent with an average of 7.64 of the eight aromatic protons replaced by deuterium.

Synthesis of Intermediate Compound Y5:

Under nitrogen atmosphere, compound Y3 (1.04 g, 1.55 mmol), Y4 (0.80 g, 2.82 mmol), tris (dibenzylideneacetone) dipalladium (0) (81 mg, 0.09 mmol), tri-t-butylphosph Fin (42 mg, 0.21 mol%) and toluene (25 mL) were combined. Sodium t-butoxide (0.52 g, 5.41 mmol) was added and the reaction mixture was stirred at rt for 40 h. Then tris (dibenzylideneacetone) dipalladium (0) (50 mg, 0,05 mmol), tri-t-butylphosphine (30 mg, 0.15 mmol) and Y4 (196 mg, 0.69 mmol) were added. The reaction mixture was warmed to 50 ° C. After a further 72 h, the reaction mixture was filtered through a pad of celite, rinsing with CH 2 Cl 2 (50 mL). The filtrate was concentrated on a rotary evaporator and dried under vacuum. The product was purified by medium pressure liquid chromatography on silica gel (0-40% methylene chloride gradient in hexanes) to yield 0.99 g (59% yield) of a white solid. NMR analysis confirmed the structure of intermediate compound Y5 as a mixture of 4,4'- and 4,5'-regioisomers. Purity (UPLC): 99.3%.

Synthesis of Intermediate Compound Y6:

Step 1: Preparation of Deuterated 4-Bromobiphenyl.

A solution of 4-bromobiphenyl (4.66 g, 20.0 mmol) in C6D6 (20 mL) was purged with nitrogen for 30 min. A 1.0 M solution of ethyl aluminum dichloride solution in hexane (4.0 mL, 4.0 mmol) was added dropwise through a syringe and the reaction mixture was heated to reflux for 50 min under a nitrogen atmosphere. After cooling to room temperature under a nitrogen atmosphere, heavy water (20 mL) was added and the mixture was shaken to separate the layers. The organic phase was dried over magnesium sulphate, filtered and concentrated on a rotary evaporator. The product thus obtained was again subjected to the above reaction conditions four additional times. After the fifth treatment the crude product was recrystallized from ethanol (20 mL) to give the title compound (2.26 g) of step 1 as a white solid. Mp 92.8-94.1 ° C. Purity (UPLC): 98.14%. Mass spectra indicated that 6 to 9 deuterium atoms were incorporated.

Step 2: Preparation of Y6:

The product of step 1 (2.26 g, 9.36 mmol) and iodic acid (687 mg) were dissolved in acetic acid (40 mL). Iodine chips (1.56 g) were added followed by concentrated sulfuric acid (1.0 mL) and water (2.0 mL) and the reaction mixture was heated to reflux for 210 min. After cooling to room temperature, the precipitate was collected by filtration, washed with water and then with methanol (20 mL each). The crude product was crystallized from EtOH / EtOAc (1/1) to give Y6 (1.31 g) as a white solid. Mp 179.0-181.3 ° C. Purity (UPLC): 100%. Mass spectra showed an average of 6 to 7 deuterium atoms incorporated.

Synthesis of Intermediate Compound Y7:

In a nitrogen-purged glove box, Y5 (986 mg, 0.92 mmol), Y6 (1.30 g, in a three-neck round bottom flask equipped with a magnetic stirrer, thermometer, and a reflux condenser with gas inlet adapter in the closed position above 3.55 mmol), tris (dibenzylideneacetone) dipalladium (0) (124 mg, 14.8 mol%), bis (diphenylphosphinoferrocene) (151 mg, 29.6 mol%) and toluene (20 mL) Injected through the mortar. Sodium t-butoxide (0.30 g, 3.12 mmol) was added, the opening was capped and the reaction vessel removed from the glove box. A nitrogen bubbler hose was fitted to the gas inlet adapter and the cock stopper was turned to the open position under weak positive pressure nitrogen. The reaction mixture was heated to reflux. After 21 h, completion of the reaction was judged by UPLC analysis of an aliquot and the reaction mixture was cooled to room temperature. The reaction mixture was filtered through a pad of celite, rinsing with CH2Cl2. The filtrate was concentrated on a rotary evaporator. The crude product was dried under high vacuum and purified by medium pressure liquid chromatography on silica gel (0-40% methylene chloride gradient in hexanes) to afford 1.21 g of a white solid, which was triturated with boiling methanol for 2 h to give 0.975 g of Y7 was obtained. ¹ H NMR analysis showed the structure of intermediate compound Y7 as a mixture of 4,4'- and 4,5'-positional isomers, with an average of 14 aromatic protons remaining. This was evidenced by the parent ions (m / z 1550.3) in the mass spectrum where it was found that 36 of the 50 aromatic hydrogens were replaced by deuterium. Purity (UPLC):> 99%.

Synthesis of Compound Hole Transport Compound HT5:

Polymerization of intermediate compound Y7 was performed as described in Comparative Example A. The polymer was obtained in 68% yield (0.285 g) as a white solid. The molecular weight of the polymer was determined by GPC (THF mobile phase, polystyrene standard): M _w = 325,740; M _n = 139,748; M _w / M _n = 2.33.

Synthetic example  3

This example describes the preparation of a deuterated hole transport material, compound HT11, wherein Σ (x) = 18.

Synthesis of Compound 2

Under nitrogen atmosphere, 9,9-dioctyl-2,7-dibromofluorene (25.0 g, 45.58 mmol), phenylboronic acid (12.23 g, 100.28 mmol), Pd ₂ (dba) ₃ (at 250 mL round bottom) 0.42 g, 0.46 mmol), P ^t Bu ₃ (0.22 g, 1.09 mmol) and 100 mL of toluene were added. The reaction mixture was stirred for 5 minutes, then KF (8.74 g, 150.43 mmol) was added in 2 portions and the resulting solution was stirred overnight at room temperature. The mixture was diluted with 500 mL THF, filtered through a plug of silica and celite and the volatiles were removed from the filtrate under reduced pressure. The yellow oil was purified by flash column chromatography on silica gel using hexane as eluent. The product was obtained in 80.0% (19.8 g) as a white solid. NMR analysis showed the material to be compound 2 having the structure provided above.

Synthesis of Compound 3

A 250 ml 3-neck round bottom flask equipped with a condenser and a dropping funnel was flushed with N ₂ for 30 minutes. 9,9-dioctyl-2,7-diphenylfluorene (19.8 g, 36.48 mmol) was added and dissolved in 100 mL of dichloromethane. The clear solution was cooled to −10 ° C. and a solution of bromine (12.24 g, 76.60 mmol) in 20 mL dichloromethane was added dropwise. The mixture was stirred at 0 ° C. for 1 hour then allowed to warm to room temperature and stirred overnight. 100 mL of 10% Na ₂ S ₂ O ₃ aqueous solution was added and the reaction mixture was stirred for 1 hour. The organic layer was extracted and the aqueous layer was washed three times with 100 ml of dichloromethane. The combined organic layers were dried over Na ₂ SO ₄ , filtered and concentrated to dryness. Acetone was added to the resulting oil to give a white precipitate. Filtration and drying yielded a white powder (13.3 g, 52.2%). NMR analysis showed the material to be compound 3 having the structure provided above.

Synthesis of Compound 4

Under a nitrogen atmosphere, compound 3 (13.1 g, 18.70 mmol), aniline (3.66 g, 39.27 mmol), Pd ₂ (dba) ₃ (0.34 g, 0.37 mmol), P ^t Bu ₃ (0.15 g, 0.75 mmol) and 100 ml of toluene were added. The reaction mixture was stirred for 10 min before NaO ^t Bu (3.68 g, 38.33 mmol) was added and the reaction mixture was stirred at rt for 1 day. The resulting reaction mixture was diluted with 3 L of toluene and filtered through a plug of silica and celite. The dark brown oil obtained by evaporating the volatile components was purified by flash column chromatography on silica gel using a mixture of 1:10 ethyl acetate: hexane as eluent. The product was obtained in 50.2% (6.8 g) as light yellow powder. NMR analysis showed the material to be compound 4 having the structure provided above.

Synthesis of Compound 5

In a 250 mL 3-neck round bottom flask equipped with a condenser, compound 4 (4.00 g, 5.52 mmol), 1-bromo-4-iodobenzene (4.68 g, 16.55 mmol), Pd ₂ (dba) ₃ (0.30 g, 0.33 mmol) and DPPF (0.37 g, 0.66 mmol) were combined with 80 mL of toluene. The resulting mixture was stirred for 10 min. NaO ^t Bu (1.17 g, 12.14 mmol) was added and the mixture was heated to 80 ° C. for 4 days. The resulting reaction mixture was diluted with 1 L of toluene and 1 L THF and filtered through a plug of silica and celite to remove insoluble salts. The resulting brown oil upon evaporation of the volatiles was purified by flash column chromatography on silica gel using a 1:10 dichloromethane: hexane mixture as eluent. Yellow powder was obtained after drying (4.8 g, 84.8%). NMR analysis showed the material to be compound 5 having the structure provided above.

Synthesis of Compound 6

1 g of compound 5 was dissolved in C ₆ D ₆ (20 mL) under nitrogen atmosphere, and CF ₃ OSO ₂ D (1.4 mL) was added dropwise. The reaction mixture was allowed to stir overnight at room temperature and then quenched it with saturated Na ₂ CO ₃ / D ₂ O. The organic layer was isolated and dried over MgSO ₄ . The product was purified using silica chromatography (20% CH 2 Cl 2: hexane) to yield 0.688 g of material. In the MS spectrum of the isolated material, a structure with 18 aromatics D was identified.

Polymerization of Compound 6:

Unless otherwise indicated, all work was performed in a nitrogen purged glove box. Compound 6 (0.652 g, 0.50 mmol) was added to scintillation vials and dissolved in 16 mL of toluene. Bis (1,5-cyclooctadiene) nickel (0) (0.344 g, 1.252 mmol) was added to a clean, dry 50 ml Schlenk tube. 2,2'-dipyridyl (0.195 g, 1.252 mmol) and 1,5-cyclooctadiene (0.135 g, 1.252 mmol) were weighed into a flash vial and 3.79 g of N, N'-dimethylformamide Dissolved in. The solution was added to the Schlenk tube. The Schlenk tube was inserted into an aluminum block and the block was heated and stirred on a hotplate / stirrer at the set point causing the internal temperature to 60 ° C. The catalyst system was held at 60 ° C. for 45 minutes and then raised to 65 ° C. The monomer solution in toluene was added to the Schlenk tube and the tube was sealed. The polymerization mixture was briefly stirred at 65 ° C. while adjusting the viscosity by adding toluene (8 mL). The reaction mixture was allowed to cool to rt and 20 mL of concentrated HCl was added. The mixture was allowed to stir for 45 minutes. The polymer was collected by vacuum filtration, washed with additional methanol and dried under high vacuum. The polymer was purified by subsequent precipitation from toluene to acetone and MeOH to afford a white fibrous polymer (0.437 g, 79% yield). The molecular weight of the polymer was determined by GPC (THF mobile phase, polystyrene standard): M _w = 1,696,019; M _n = 873,259. NMR analysis confirmed the structure as a polymer, compound HT11.

Synthesis Example 4

This example illustrates the preparation of the deuterated electroluminescent material, E4, shown below.

, U.; Adam, M.;

, K. Chem. Ber. 1994, 127, 437-444)을 둥근 바닥 플라스크에 넣고 0.38 g(2.2 mM)의 다이(퍼듀테로페닐)아민 및 0.2 g의 소듐 tert-부톡사이드(2 mM)를 40 ㎖의 톨루엔과 함께 첨가하였다. 0.15 g의 Pd₂DBA₃(0.15 mM) 및 0.07 g의 P(t-Bu)3(0.3 mM)를 10 ㎖의 톨루엔에 용해시켜 제1 용액에 교반하면서 첨가하였다. 모든 재료가 혼합되면, 용액이 천천히 발열하면서 황갈색이 된다. 글러브 박스 내에서 질소 하에 80℃로 1 hr 동안 용액을 교반 및 가열하였다. 용액은 즉시 어두운 자주색이 되나, ~80℃에 달하면 뚜렷한 녹색 발광을 동반하는 어두운 황녹색이 된다. 실온으로 냉각시킨 후에 용액을 글러브 박스에서 꺼내고 톨루엔으로 용리하는 짧은 염기성-알루미나 플러그를 통해 여과하여 밝은 황녹색 밴드를 수득한다. 용매를 증발시키고 재료를 톨루엔/메탄올로부터 재결정하였다.. 수율, 0.55 g. ¹H nmr에 의해 구조를 확인하였다.0.45 g of 2,6-di-t-butyl-9,10-dibromoanthracene (1 mM) in a nitrogen filled glove box (

, U .; Adam, M .;

, K. Chem. Ber. 1994, 127, 437-444) were placed in a round bottom flask and 0.38 g (2.2 mM) of di (perduterophenyl) amine and 0.2 g of sodium tert-butoxide (2 mM) were added together with 40 ml of toluene. . 0.15 g of Pd ₂ DBA ₃ (0.15 mM) and 0.07 g of P (t-Bu) 3 (0.3 mM) were dissolved in 10 ml of toluene and added to the first solution with stirring. When all the materials are mixed, the solution slowly heats up to tan. The solution was stirred and heated to 80 ° C. for 1 hr under nitrogen in a glove box. The solution immediately becomes dark purple, but when it reaches ~ 80 ° C it becomes dark yellow-green with a pronounced green luminescence. After cooling to room temperature the solution is taken out of the glove box and filtered through a short basic-alumina plug eluting with toluene to give a bright yellow-green band. The solvent was evaporated and the material recrystallized from toluene / methanol. Yield, 0.55 g. ^The structure was confirmed by ¹ H nmr.

Synthesis Example 5

This example illustrates the preparation of a deuterated host compound, H14.

A non-deuterated analog compound, Comparative Compound A, was prepared first.

This compound can be prepared according to the following scheme:

Synthesis of Compound 2:

To a 3 L flask equipped with a mechanical stirrer, dropping funnel, thermometer and N ₂ bubbler was added 54 g (275.2 mmol) of anthrone in 1.5 L of dry methylene chloride. The flask was cooled in an ice bath and 83.7 mL (559.7 mmol) of 1,8-diazabicyclo [5.4.0] undes-7-ene ("DBU") was added over a dropping funnel over 1.5 hr. After the solution turned orange and became opaque, it turned dark red. To the solution still being cooled, 58 ml (345.0 mmol) of triple anhydride was added over about 1.5 hr via syringe while maintaining the temperature of the solution below 5 ° C. After allowing the reaction to proceed for 3 hr at room temperature, an additional 1 ml of tricyclic anhydride was added and stirring continued for 30 min at RT. 500 mL water was added slowly and the layers were separated. The aqueous layer was extracted with 3 × 200 mL of dichloromethane (“DCM”), the combined organic layers dried over magnesium sulfate, filtered and concentrated by rotary evaporation to give a red oil. Column chromatography on silica gel followed by recrystallization from hexanes gave 43.1 g (43%) of tan powder.

Synthesis of Compound 3

: Anthracene-9-yl trifluoromethanesulfonate (6.0 g, 18.40 mmol), naphthalen-2-yl-boronic acid (in a nitrogen-filled glove box, in a 200 ml Kjeldahl reaction flask with a magnetic stir bar) 3.78 g 22.1 mmol), tribasic potassium phosphate (17.50 g, 82.0 mmol), palladium (II) acetate (0.41 g, 1.8 mmol), tricyclohexylphosphine (0.52 g, 1.8 mmol) and THF (100 mL) Added. After taking out of the dry box, the reaction mixture was purged with nitrogen and degassed water (50 mL) was added by syringe. Then, a condenser was added and the reaction mixture was refluxed overnight. The reaction was monitored by TLC. When complete, the reaction mixture was cooled to room temperature. The organic layer was separated and the aqueous layer was extracted with DCM. The organic fractions were combined, washed with brine and dried over magnesium sulfate. The solvent was removed under reduced pressure. The resulting solid was washed with acetone and hexanes and filtered. Purification by column chromatography on silica gel gave 4.03 g (72%) of the product as a light yellow crystalline material.

Synthesis of Compound 4:

11.17 g (36.7 mmol) of 9- (naphthalen-2-yl) anthracene were suspended in 100 mL of DCM. 6.86 g (38.5 mmol) of N-bromosuccinimide were added and the mixture was stirred under illumination of a 100 W lamp. Precipitation occurred after the formation of a yellow clear solution. The reaction was monitored by TLC. After 1.5 h, the reaction mixture was partially concentrated to remove methylene chloride and then crystallized from acetonitrile to give 12.2 g of pale yellow crystals (87%).

Synthesis of Compound 7:

In a nitrogen-filled glove box, naphthalen-1-yl-1-boronic acid (14.2 g, 82.6 mmol), 1-bromo-2-iodobenzene (25.8 g, 91.2 mmol), tetrakis (triphenylphosphine) palladium (0) (1.2 g, 1.4 mmol), sodium carbonate (25.4 g, 240 mmol), and toluene (120 mL) were added. After taking out of the dry box, the reaction mixture was purged with nitrogen and degassed water (120 mL) was added by syringe. The reaction flask was then installed with a condenser and the reaction mixture was refluxed for 15 hours. The reaction was monitored by TLC. The reaction mixture was cooled to room temperature. The organic layer was separated and the aqueous layer was extracted with DCM. The organic fractions were combined and the solvent removed under reduced pressure to yield a yellow oil. Purification by column chromatography using silica gel gave 13.6 g of clear oil (58%).

Synthesis of Compound 6:

4-bromophenyl-1-naphthalene (28.4 g, 10.0 mmol), bis (pinacholate) diboron (40.8 g, 16.0) in a 1-liter flask equipped with a magnetic stir bar, reflux condenser connected to a nitrogen line and an oil bath mmol), Pd (dppf) ₂ Cl ₂ (1.64 g, 2.0 mmol) _, potassium acetate (19.7 g, 200 mmol), and DMSO (350 mL) were added. The mixture was bubbled with nitrogen for 15 min, then Pd (dppf) ₂ Cl ₂ (1.64 g, 0.002 mol) was added. The mixture gradually turned dark brown during the process. The reaction mixture was stirred at 120 ° C. (oil bath) for 18 h under nitrogen. After cooling the mixture was poured into ice water and extracted with chloroform (3 ×). The organic layer was washed with water (3x) and saturated brine (1x) and dried over MgSO4. After filtration and solvent removal, the residue was purified by chromatography on a silica gel column. Fractions containing product were combined and solvent removed by rotary evaporator. The resulting white solid was crystallized from hexane / chloroform and dried at 40 ° C. in a vacuum oven to afford the product as white crystalline flakes (15.0 g in 45% yield). 1 H and 13 C-NMR spectra match the expected structure.

Synthesis of Comparative Compound A

In a 250 mL flask in a glove box (2.00 g, 5.23 mmol), 4,4,5,5-tetramethyl-2- (4- (naphthalen-4-yl) phenyl) -1,3,2-dioxabo Rolan (1.90 g, 5.74 mmol), tris (dibenzylideneacetone) dipaldium (0) (0.24 g, 0.26 mmol), And toluene (50 mL) was added. The reaction flask was removed from the dry box and a condenser and nitrogen inlet were installed. Degassed aqueous sodium carbonate (2 M, 20 mL) was added via syringe. The reaction mixture was stirred and heated to 90 ° C. overnight. The reaction was monitored by HPLC. After cooling to room temperature, the organic layer was separated. The aqueous layer was washed twice with DCM, the organic layers combined and concentrated by rotary evaporation to give a gray powder. Purification by filtration on neutral alumina, hexane precipitation, and column chromatography on silica gel gave 2.28 g of white powder (86%).

The product was further purified as described in published US patent application 2008-0138655 to achieve HPLC purity of at least 99.9% and absorbance of impurities below 0.01.

¹ H NMR spectrum of Compound A is provided in FIG. 2.

Deuterated host compound H14 was prepared from Comparative Compound A.

Comparative Example A

AlCl ₃ (0.48 g, 3.6 mmol) was added to a solution of Purduterobenzene or benzene-D6 (C ₆ D ₆ ) (100 mL) of Comparative Compound A (5 g, 9.87 mmol) from Comparative Example A under a nitrogen atmosphere. It was. The resulting mixture was stirred at rt for 6 h before D ₂ O (50 mL) was added. After separating the layers the aqueous layer was washed with CH ₂ Cl ₂ (2 × 30 mL). The combined organic layers were dried over magnesium sulphate and volatiles were removed on a rotary evaporator. The crude product was purified by column chromatography. Deuterated product H1 (x + y + n + m = 21-23) was obtained as a white powder (4.5 g).

The product was further purified as described in published US patent application 2008-0138655 to achieve HPLC purity of at least 99.9% and absorbance of impurities below 0.01. From the above, the material was determined to have the same level of purity as that of Comparative Compound A.

¹ H NMR (CD ₂ Cl ₂ ) and ASAP-MS showed that the compound had the structure provided below:

Where "D / H" indicates that the probability of H or D at this atomic position is approximately equal. ^The structure was confirmed by ¹ H NMR, ¹³ C NMR, ² D NMR and ¹ H- ¹³ C HSQC (Heteronuclear Single Quantum Coherence).

Synthesis Example 6

This example illustrates the manufacture of deuterated electron transport material, ET2.

a) A trimethylene linked vasophenanthroline was prepared using the procedure of Yamada et al, Bull Chem Soc Jpn, 63, 2710, 1990 as follows: 20 g of 20 g of vasophenanthroline were taken It was placed in 1,3-dibromopropane and refluxed in air. After about 30 min, the dense orange slurry was cooled. Methanol was added to dissolve the solids, and then acetone was added to precipitate a light orange solid. It was filtered and washed with toluene and dichloromethane ("DCM") to give an orange powder in 2.8 g yield.

b) 2.8 g of the product from above are dissolved in 12 ml of water and added dropwise to an ice-cooled solution of 21 g potassium ferricyanide and 10 g sodium hydroxide in 30 ml over a route of about 30 min. Then, stirred for 90 min. It was ice cooled again and neutralized to a pH of about 8 with 60 ml of 4 M HCl. The pale tan / yellow solid was filtered off and dried by suction. The filtered solid was placed in a soxhlet and extracted with chloroform to extract a brown solution. It was evaporated to give a brownish oily solid, which was then washed with a small amount of methanol to give a pale brown solid (˜1.0 g 47%). The product can be recrystallized from chloroform / methanol to gold plate form by evaporating chloroform from the mixture. The structure was identified by the following diketone by NMR.

c) The total portions of the diketone from step (b) were combined and a total of 5.5 g (13.6 mM) was suspended in 39 ml of POCl ₃ and 5.4 g of PCl ₅ were added. It was degassed and refluxed for 8 hr under nitrogen. Excess POCl 3 was removed by evaporation. Ice was added to decompose the remaining chloride and the mixture was neutralized with ammonia solution. The brown precipitate was collected and dried in vacuo and the mother liquor extracted with methylene chloride. All brown materials were combined and evaporated to give a brown gum and methanol was added. After shaking and stirring a pale yellow solid was isolated, which was recrystallized from off-white needles from CHCl 3 and methanol (1:10). NMR analysis showed the structure to be 2,9-dichloro-4,7-diphenyl-1,10-phenanthroline shown below.

d) Non-deuterated analogs using Suzuki coupling of 2,9-dichloro-4,7-diphenyl-1,10-phenanthroline and boronic esters shown below The compound was prepared.

Take 1.0 g of dichloro-phene (2.5 mM) and add 3.12 g (6 mM) of boronic acid ester in the glove box. 0.15 g Pd ₂ DBA ₃ (DBA = dibenzylideneacetone) (0.15 mM), 0.1 g tricyclohexylphosphine (0.35 mM) and 2.0 g potassium phosphate (9 mM) are added and 30 ml Dissolve both in dioxane and 15 ml of water. Heat and mix at 100 C for 1 hr in the mantle in the glove box, then warm up under nitrogen overnight (minimum potentiometer setting). The solution immediately becomes dark purple, but at ~ 80 C it becomes a tan brown slurry, which slowly changes to a clear brown with a dense precipitate. The solution is refluxed (air condenser) to form a brown rubbery material. Cool, remove from glove box and work up by adding water. Extract into DCM and dry over magnesium sulfate. DCM is then chromatographed on a silica / florisil plug eluting with DCM / methanol 2: 1. The light yellow solution is collected and evaporated and the addition of methanol precipitates a white / light yellow solid. By NMR analysis, the structure was identified as the compound shown below.

e) Compound ET2 was prepared from non-deuterated analog compounds.

Under a nitrogen atmosphere, the compound from step (d) (1.925 g) was dissolved in C ₆ D ₆ (200 mL), and CF ₃ OSO ₂ D (13.2 mL) was added dropwise. The reaction mixture was allowed to stir overnight at room temperature and then quenched it with saturated Na ₂ CO ₃ / D ₂ O. The organic layer was isolated and dried over MgSO ₄ . The product was purified using silica chromatography (CH ₂ Cl ₂ : hexane) to afford 1.70 g of material. The NMR spectrum of the isolated material confirmed the structure to ET2 with 32 to 34 D replacing H.

Synthesis Example 7

This example illustrates the production of deuterated electron transport material, ET4.

Synthesis of Ligand D _6- 8- hydroxyquinoline

A mixture of 8-hydroxyquinoline (93.00 g, 20.667 mmol), D ₂ O (60 mL) and 10% Pd / C (0.200 g) was placed in a Parr reactor under a nitrogen atmosphere and heated to 180 ° C. for 16 hours. It was. The resulting mixture was added to diethyl ether (200 mL) and the layers separated and the organic layer was filtered through celite. After evaporation of volatile components, to give the resulting solid by chromatography (20% DCM / hexane) to give the D _6- 8- hydroxyquinoline product of 2.4 g (77% yield).

Synthesis of ET4

Mixing zirconium (IV) chloride in 1.0 g of dry methanol and 10 ㎖, dried was added to a stirred solution of methanol 10 ㎖ D _6- 8- hydroxyquinoline in 3.2 g. It was stirred and refluxed for 30 min under nitrogen. The Zr reagent immediately formed a dense yellow precipitate, which was stirred and heated to reflux for 30 min. To this was added 4.8 g of tri-n-butylamine and the reflux was continued for 15 min. The dark yellow precipitate was filtered off and washed with methanol and ammonia (IN). After it was dried, it was extracted as a light yellow solution using methylene chloride and reprecipitated by methanol addition. ^The structure was confirmed by ¹ H NMR.

Synthesis Example 8

This example illustrates the preparation of a deuterated electroluminescent compound, E13.

a) Yan et. al., J. Mater. Chem., 2004, 14, 2295-3000, to prepare compounds shown below.

b) A non-deuterated compound was prepared according to the following scheme.

Take 1.0 g bromotylbene (2.3 mM) in a glove box and add 0.74 g (2.3 mM) of the shown secondary amine and 0.24 g of t-BuONa (2.4 mM) with 10 ml of toluene. . 100 mg of Pd ₂ DBA ₃ , 40 mg of P (t-Bu) ₃ dissolved in toluene are added. Mix and heat at 80 ° C. for 1 hr under nitrogen in the mantle in the glove box. The solution immediately becomes dark purple, but when it reaches ˜80 ° C. it becomes dark yellow with a pronounced blue emission. The material was cooled, taken out of the glove box and purified by chromatography eluting with toluene. The blue luminescent material is very soluble and elutes as a pale yellow solution. The solution was evaporated to reduce volume and methanol was added to precipitate a pale yellow solid with bright blue PL. The structure was confirmed by NMR analysis.

c) Compound E13 was prepared by deuteration of the compound from step (b) using a similar procedure as in Synthesis Example 6.

Device Examples 1-6

The following non-deuterated materials were used:

HIJ-A and HIJ-B are aqueous dispersions of electrically conductive polymers and polymeric fluorinated sulfonic acids. Such materials are described, for example, in published US patent applications US 2004/0102577, US 2004/0127637, US 2005/0205860, and published PCT application WO 2009/018009.

Polymer Pol-A is a non-crosslinked arylamine polymer (20 nm).

ELM-A and ELM-B are electroluminescent bis (diarylamino) crisene compounds with blue emission.

Host A is a diarylanthracene compound.

ET-A is a metal quinolate derivative (10 nm).

In device example 1, the deuterated material was present in the hole injection layer. The hole injection layer was D _5- PPy / D-poly (TFE-PSEPVE) from Synthesis Example 1.

In device example 2, the deuterated material was present in the hole transport layer. The hole transport layer was HT5 from Synthesis Example 2.

In device example 3, the deuterated material was present in the electroluminescent layer. The electroluminescent material was E4 from Synthesis Example 4.

In device example 4, the deuterated material was present in the electroluminescent layer. The host in the electroluminescent layer was H14 from Synthesis Example 5.

In device example 5, the deuterated material was present in the electron transport layer. The electron transport layer was ET2 from Synthesis Example 6.

In device example 6, the deuterated material was present in the electron transport layer. The electron transport layer was ET4 from Synthesis Example 7.

For each device, the anode was indium tin oxide (ITO), the electron injection layer was CsF, and the cathode was Al (100 nm). In Examples 1, 2, 4, 5, and 6, the thickness of the anode was 50 nm; In Example 3, the anode thickness was 180 nm. In Examples 1 to 4 and 6, the thickness of the electron injection layer was 1 nm; In Example 5, the electron injection thickness was 0.7 nm. The materials and thicknesses of the other layers are summarized in Table 1 below.

TABLE 1

OLED devices were fabricated by a combination of solution processing and thermal evaporation techniques. A patterned indium tin oxide (ITO) coated glass substrate from Thin Film Devices, Inc. (Thin Film Devices, Inc) was used. These ITO substrates are based on Corning 1737 glass coated with ITO with a sheet resistance of 30 ohms / square and a light transmittance of 80%. The patterned ITO substrate was ultrasonically cleaned in an aqueous detergent solution and rinsed with distilled water. The patterned ITO was then ultrasonically washed in acetone, rinsed with isopropanol and dried in a nitrogen stream.

Immediately before device fabrication, the cleaned and patterned ITO substrates were treated with UV ozone for 10 minutes. Immediately after cooling, the aqueous dispersion of hole injection material was spin coated onto the ITO surface and heated to remove solvent. After cooling, the substrate was then spin coated with a solution of hole transport material and then heated to remove solvent. After cooling, the substrate was spin coated with an electroluminescent layer solution and heated to remove solvent. The substrate was masked and placed in a vacuum chamber. The electron transport layer was deposited by thermal evaporation followed by the deposition of a layer of CsF as the electron injection layer. The mask was then changed in vacuo and a layer of Al was deposited by thermal evaporation to form a cathode. The chamber was evacuated and the device encapsulated using a glass lid, desiccant, and UV curable epoxy.

OLED samples were characterized by measuring their (1) current-voltage (I-V) curves, (2) electroluminescence radiance versus voltage, and (3) electroluminescence spectrum versus voltage. All three measurements were performed simultaneously and controlled by computer. The current efficiency of the device at a given voltage is determined by dividing the electroluminescent emission luminance of the LED by the current required to operate the device. The unit is cd / A. Power efficiency is current efficiency multiplied by pi and divided by operating voltage. The unit is lm / W. Device data is provided in Tables 2 and 3.

TABLE 2

[Table 3]

In this example, the time to reach 70% luminance rather than the half-life was determined. However, the calculation half life will be longer than the calculation time to reach 70% luminance. Thus, the half life at 1000 nits clearly exceeds 10,000 hours.

Device Example 7

This embodiment describes an electronic device having a deuterated priming layer formed by liquid deposition, wherein the hole transport layer and the electroluminescent layer are also formed by liquid deposition.

The device had the following structure on a glass substrate:

Anode = ITO: 50 nm

Hole injection layer = HIJ-B (50 nm)

Primer layer: HT11 (20 nm)

Hole transport layer = Pol-A (20 nm)

Electroluminescent layer = 13: 1 weight ratio of host H14: dopant ELM-B (40 nm),

Electron transport layer = ET-A (10 nm)

Cathode = CsF / Al (1/100 nm)

OLED devices were fabricated by a combination of solution processing and thermal evaporation techniques. Thin film devices, a patterned indium tin oxide (ITO) coated glass substrate from Incorporated, were used. The ITO substrate is based on Corning 1737 glass coated with ITO having a sheet resistance of 30 ohms / square and a light transmittance of 80%. The patterned ITO substrate was ultrasonically cleaned in an aqueous detergent solution and rinsed with distilled water. The patterned ITO was then ultrasonically washed in acetone, rinsed with isopropanol and dried in a nitrogen stream.

Immediately before device fabrication, the cleaned and patterned ITO substrates were treated with UV ozone for 10 minutes. Immediately after cooling, the aqueous dispersion of HIJ-B was spin coated onto the ITO surface and heated to remove solvent. After cooling, a priming layer was formed by spin coating a toluene solution of HT11 on the hole injection layer. The priming layer was exposed imagewise at a dose of 100 mJ / cm ² at 248 nm. After exposure, the priming layer was developed by spraying with anisole for 60 s while rotating at 2000 rpm and then dried by rotation for 30 s. The substrate was then spin coated with a solution of hole transport material and then heated to remove the solvent. The electroluminescent layer was deposited by spin coating from methyl benzoate solution and then heated to remove the solvent. After cooling, the substrate was masked and placed in a vacuum chamber. After depositing the electron transport material by thermal evaporation, a layer of CsF was deposited. The mask was then changed in vacuo and a layer of Al was deposited by thermal evaporation. The chamber was evacuated and the device encapsulated using a glass lid, desiccant, and UV curable epoxy.

The OLED sample was characterized as above.

The generated device data is provided in Table 4.

[Table 4]

Device Example 8

This embodiment describes an electronic device having an electroluminescent layer comprising a deuterated host and a deuterated electroluminescent dopant.

The device had the following structure on a glass substrate:

Anode = ITO: 50 nm

Hole injection layer = HIJ-B (50 nm)

Hole transport layer = Pol-A (20 nm)

Electroluminescent layer = 86:14 weight ratio host H14: dopant E13 (40 nm),

Electron transport layer = ET-A (10 nm)

Cathode = CsF / Al (0.7 / 100 nm)

OLED devices were prepared as described in Device Example 1. The results are provided in Table 5.

TABLE 5

As evidenced by the data in the table, devices with at least one layer comprising deuterated material had a calculated half-life exceeding 5000 hours. In device example 3, the calculated half-life exceeds 50,000 hours.

Note that not all of the above actions may be required in a general technique or embodiment, some of the specific actions may not be required, and one or more additional actions may be performed in addition to those described. Also, the order in which the actions are listed is not necessarily the order in which they are performed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. Accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of present invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific implementations. However, any benefit, advantage, solution to a problem, and any feature (s) that can cause or become apparent any benefit, advantage, or solution are decisive or required of any or all claims. It should not be interpreted as an essential feature.

It should be appreciated that certain features may be described herein in the context of independent embodiments for clarity and may also be provided in combination with a single embodiment. Conversely, the various features described in connection with a single embodiment for the sake of simplicity may also be provided independently or in any subcombination.

The use of numerical values within the various ranges specified herein is specified as an approximation, such as by prefixing the word "about" with both the minimum and maximum values within the specified range. In this way, minor variations above and below the specified range may be used to achieve results substantially equal to values within the range. In addition, the disclosure of these ranges is intended as a continuous range that includes all values between the minimum and maximum average values, including fractional values that may result if some component of one value is mixed with others of different values. do. In addition, when a wider range and a narrower range are disclosed, matching the minimum value of one range with the maximum value of the other range is considered in the present invention and vice versa.

Claims (17)

An organic light emitting diode comprising an anode, a cathode, and an organic active layer therebetween, wherein the organic active layer comprises a deuterated compound and the device has a calculated half life of at least 5000 hours at 1000 nits. The organic light emitting diode of claim 1, wherein the organic active layer comprises a deuterated conductive polymer and a fluorinated acid polymer. The organic light emitting diode of claim 1, wherein the organic active layer comprises a deuterated hole transport compound having at least two diarylamino moieties per molecular unit. The deuterated polymeric triarylamine, fluorene according to claim 1, wherein the organic active layer has a conjugated moiety connected in a deuterated polymeric triarylamine, deuterated polycarbazole, deuterated polyfluorene, non-planar configuration. An organic light emitting diode comprising a material selected from the group consisting of a deuterated copolymer of triarylamine and a combination thereof. The organic active layer of claim 1, wherein the organic active layer is deuterated chrysene, deuterated pyrene, deuterated parylene, deuterated rubrene, deuterated periplanene, deuterated fluoranthene, deuterated stilbene, deuterated coumarin, An organic light emitting diode comprising an electroluminescent compound selected from the group consisting of deuterated anthracene, deuterated thiadiazole, deuterated spirobifluorene, derivatives thereof, and mixtures thereof. The organic light emitting diode of claim 1, wherein the organic active layer comprises at least 10% deuterated electroluminescent compound having one of the formula:

here,
A is the same or different at each occurrence and is an aromatic group having 3 to 60 carbon atoms;
Q 'is naphthalene, anthracene, benz [a] anthracene, dibenz [a, h] anthracene, fluoranthene, fluorene, spirofluorene, tetracene, chrysene, pyrene, tetracene, xanthene, perylene, coumarin , Rhodamine, quinacridone, rubrene, substituted derivatives thereof, and deuterated analogs thereof;
p and q are the same or different and each is an integer from 1 to 6. The electroactive compound of claim 1, wherein the organic active layer comprises an electroluminescent compound selected from the group consisting of deuterated aminoanthracene, deuterated aminocricene, deuterated aminostyrenebene, deuterated metal quinolate complex, and deuterated iridium complex. Organic light emitting diode. The organic active layer of claim 1 wherein the organic active layer comprises (a) deuterated anthracene, deuterated chrysene, deuterated pyrene, deuterated phenanthrene, deuterated triphenylene, deuterated phenanthroline, deuterated naphthalene, deuterated quinoline , Deuterated isoquinoline, deuterated quinoxaline, deuterated deuterated phenylpyridine, deuterated dibenzofuran, deuterated difuranobenzene, deuterated metal quinolinate complex, deuterated indolocarbazole, deuterated benzimi Electroluminescence having a maximum emission between 380 and 750 nm and at least one host material selected from the group consisting of doazole, deuterated triazolopyridine, deuterated diheteroarylphenyl, substituted derivatives thereof, and combinations thereof An organic light emitting diode comprising at least one dopant capable of this. The method of claim 8, wherein the host material is deuterated diarylanthracene, deuterated aminocricene, deuterated diaryrylcene, deuterated diarylpyrene, deuterated indolocarbazole, deuterated phenanthroline, and combinations thereof. An organic light emitting diode selected from the group consisting of. The organic active layer of claim 1 wherein the organic active layer is deuterated phenanthroline, deuterated indolocarbazole, deuterated benzimidazole, deuterated triazolopyridine, deuterated diheteroarylphenyl, deuterated metal quinolate, and An organic light emitting diode comprising an electron transport material selected from the group consisting of combinations thereof. The method of claim 1 wherein the active layer is a chemical containment layer formed using a priming layer, wherein the priming layer is deuterated polymeric triarylamine, deuterated polycarbazole, deuterated A material selected from the group consisting of polyfluorenes, deuterated polymeric triarylamines having conjugated moieties linked in a non-planar configuration, deuterated copolymers of fluorene and triarylamines, deuterated metal quinolate derivatives, and combinations thereof Organic light emitting diode comprising a. The organic light emitting diode of claim 1, further comprising a second active layer, wherein the second active layer comprises a deuterated compound. The organic light emitting diode of claim 1, wherein the calculated half life at 1000 nits is at least 10,000 hours. The organic light emitting diode of claim 1, wherein the calculated half life at 1000 nits is at least 20,000 hours. The organic light emitting diode of claim 1, wherein the calculated half life at 1000 nits is at least 50,000 hours. An anode, a cathode, and having an organic layer therebetween, wherein the organic layer is a hole injection layer, a hole transport layer, an electroluminescent layer, an electron transport layer, and a cathode, wherein at least two of the organic layers are deuterated materials Organic light emitting diode consisting essentially. The organic light emitting diode of claim 16, wherein all organic layers consist essentially of deuterated material.

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