JP2012513688A - Long-life electronic devices - Google Patents

Abstract

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

Description

Related Application Information S. C. Based on §119 (e), US patent application Ser. No. 12 / 643,459, filed Dec. 21, 2009, US provisional patent application No. 61/139, filed Dec. 22, 2008, No. 834, U.S. Provisional Patent Application No. 61 / 156,181 filed on Feb. 27, 2009, U.S. Provisional Patent Application No. 61 / 166,400 filed on Apr. 3, 2009. Specification, US Provisional Patent Application No. 61 / 176,141, filed May 7, 2009, US Provisional Patent Application No. 61 / 179,407, filed May 19, 2009 US provisional patent application 61 / 228,689 filed on July 27, 2009, US provisional patent application 61 / 233,592 filed on August 13, 2009, 2009 On September 3, US Provisional Patent Application No. 61 / 239,574, filed September 29, 2009, US Provisional Patent Application No. 61 / 246,563, filed October 29, 2009 US Provisional Patent Application No. 61 / 256,012 and US Provisional Patent Application No. 61 / 267,928 filed on Dec. 3, 2009. Each of which is incorporated herein by reference.

  The present invention relates to an electronic device having at least one layer containing a deuterium compound and having a long active lifetime.

  Organic electronic devices that emit light (such as light-emitting diodes that make up displays) exist in many types of 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 so that light can pass through the electrical contact layer. When electricity is passed from the electrical contact layer to the electrical contact layer, the organic active layer emits light through the light transmissive electrical contact layer.

  The use of organic electroluminescent compounds as the active component of light emitting diodes is well known. Simple organic molecules such as anthracene, thiadiazole derivatives, and coumarin derivatives are known to exhibit electroluminescence. Semiconducting conjugated polymers have also been used as electroluminescent components, for example, US Pat. No. 5,247,190, US Pat. No. 5,408,109, And EP-A-443861. 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.

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

  There is also provided an organic light emitting diode as described above, wherein the organic active layer comprises a deuterated conductive polymer and a fluorinated acid polymer.

  There is also provided the organic light emitting diode as described above, wherein the organic active layer comprises a hole transport deuterium compound having at least two diarylamino moieties.

  The organic active layer is also an electroluminescent compound selected from the group consisting of deuterated aminoanthracenes, deuterated aminocricenes, deuterated metal quinolate complexes, and deuterated iridium complexes. An organic light emitting diode as described above is also provided.

  The organic active layer comprises (a) deuterated arylanthracenes, deuterated arylpyrenes, deuterated arylchrysene, deuterated phenanthrolines, deuterated indolocarbazoles, and combinations thereof There is also provided an organic light emitting diode as described above, comprising a host material selected from: (b) an electroactive capable electroluminescent dopant having an emission maximum between 380 and 750 nm.

  Also provided is the above organic light emitting diode, wherein the organic active layer comprises an electron transport material selected from the group consisting of deuterated phenanthrolines, deuterated indolocarbazoles, and deuterated metal quinolates.

  The embodiments are described in the accompanying drawings so that the concepts presented herein may be better understood.

An explanatory view of an example of an organic electronic device is included. It includes another illustration of an organic electronic device.

  Those skilled in the art will appreciate that the objects in the figures are illustrated for simplicity and clarity and are not necessarily drawn to scale. For example, the size of some objects in the figures may be exaggerated in relation to other objects to help better understand the embodiments.

  Many aspects and embodiments are disclosed herein and are exemplary and not limiting. After reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible within the scope of the invention.

  Other features and advantages of any one or more of the embodiments will be apparent from the following detailed description and from the claims. The detailed description first deals with definitions and explanations of terms, then organic light emitting devices, hole injection layers, hole transport layers, electrically active layers, electron transport layers, confinement layers, other device layers, deuterium Synthesis of chemicals, and finally examples.

1. Definition and Explanation of Terms Before addressing details of embodiments described below, some terms are defined and explained.

  The term “aliphatic ring” is intended to mean a cyclic group having no delocalized pi electrons. In some embodiments, the aliphatic ring is not unsaturated. In some embodiments, the ring has one double or triple bond.

  The term “alkoxy” refers to a RO— group, wherein R is alkyl.

  The term “alkyl” is intended to mean a group derived from an aliphatic hydrocarbon having one point of attachment, and includes a linear group, a branched group, or a cyclic group. . This term is intended to include heteroalkyl. The term “hydrocarbon alkyl” refers to an alkyl group having no heteroatoms. The term “deuterated alkyl” is a hydrocarbon alkyl in which at least one available H is replaced with D. In some embodiments, the alkyl group has 1-20 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, the branched alkyl group is attached via a secondary or tertiary carbon.

  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 delocalized pi electrons. This term is intended to include heteroaryl. The term “hydrocarbon aryl” is intended to mean an aromatic compound having no heteroatoms in the ring. The term aryl includes groups having one ring and groups having multiple rings that can be fused or joined with a single bond. The term “deuterated aryl” refers to an aryl group in which at least one available H directly attached to aryl is substituted with D. The term “arylene” is intended to mean a group derived from an aromatic hydrocarbon having two points of attachment. In some embodiments, the aryl group has 3 to 60 carbon atoms.

  The term “aryloxy” refers to the RO— group, where R is aryl.

  The term “compound” is intended to mean an uncharged substance composed of molecules (molecules are further composed of atoms and cannot be separated by physical means). The phrase “adjacent” when used to describe a layer in a device does not necessarily mean that one layer is immediately adjacent to another layer. On the other hand, the phrase “adjacent R groups” is used to represent adjacent R groups in a chemical formula (ie, an R group in an atom connected by a single bond).

  The term “conductive” or “conductive” when referring to a substance means that the substance is essentially (or originally) conductive without the addition of carbon black or conductive metal particles. Intended.

The term “deuterated” is intended to mean that at least one H is replaced with D. Deuterium is present at least 100 times its natural level. A “deuterated derivative” of Compound X has the same structure as Compound X, but includes at least one D that replaces H. The terms “% deuterated” and “% deuterated” refer to the ratio of deuterons to the sum of protons and deuterons (expressed as a percentage). Thus, in the case of compound C ₆ H ₄ D ₂ , the deuteration% is as follows:
2 / (4 + 2) × 100 = 33% deuteration.

  The term “dopant” refers to a material in a layer that contains a host material, compared to the electronic properties or wavelength of the radiation emission, acceptance, or filtering of the layer in the absence of such material. It is intended to mean a substance in a layer that causes the electronic properties or target wavelengths of radiation emission, acceptance or filtering to be different.

  The terms “fluoro” and “fluorinated” prefixes refer to materials in which at least one available H is replaced with F.

  The term “electrically active” when referring to a layer or material is intended to mean a layer or material that exhibits electronic or electro-radiative properties. In electronic devices, the operation of the device is electronically facilitated by the electrically active material. Examples of electroactive materials include materials that conduct, inject, transport or block charge (the charge can be either an electron or a hole), and emit radiation or the concentration of electron-hole pairs. Although there is a substance that shows a change of (when receiving radiation), it is not limited to these. Examples of inert materials include, but are not limited to, planarizing materials, insulating materials, and environmental barrier materials. The organic electroactive layer includes an organic compound as an electroactive material. As used herein, the term “organic” includes organometallic materials.

  The term “half-life” is intended to mean the time required for the brightness of the device to be half its initial value. The term “observed half-life” is the half-life of the device measured at a constant current of 7 mA. “Calculated half-life” is the half-life obtained from the observed half-life and calculated for an initial luminance of 1000 nits. The unit of measurement for half-life is time.

  The prefix “hetero” indicates that one or more carbon atoms have been replaced with a different atom. In some embodiments, the different atom is N, O, or S.

  The term “host material” is intended to mean a material to which a dopant is added. The host material may or may not have electronic properties or its ability to emit, accept, or filter radiation. In some embodiments, the host material is present at a high concentration.

  The term “layer” is used synonymously with the term “film” and refers to a coating covering an area of interest. The term is not limited by size. This area may be as large as the entire device, as small as a specific functional area such as an actual display device, or as small as a single subpixel. Layers and films can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. Continuous deposition techniques include, but are not limited to, 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 just “electronic device” is intended to mean a device comprising one or more organic semiconductor layers or organic semiconductor materials.

All groups may be substituted or unsubstituted unless otherwise specified. In some embodiments, the substituent is selected from the group consisting of D, halide, 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 relates. 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, such materials, methods, and examples are illustrative only and not intended to be limiting.

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

2. Organic Light Emitting Diode One illustration of an organic light emitting diode (“OLED”) device structure is shown in FIG. The device 100 has an anode layer 110 that is a first electrical contact layer, a cathode layer 160 that is a second electrical contact layer, and an electroluminescent layer 140 therebetween. Next to the anode, there may be a hole injection layer 120 containing a hole injection material. Next to the hole injection layer, there may be a hole transport layer 130 containing a hole transport material. Next to the cathode, there may be an electron transport layer 150 containing an electron transport material. In the device, one or more further hole injection layers or hole transport layers (not shown) next to the anode 110 and / or one or more further electron injection or electron transport layers next to the cathode 160. (Not shown) may be used.

  In some embodiments, in order to achieve full color, the light emitting layer is pixelated and there are sub-pixel units of different colors. An illustration of a pixelated device 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 sub-pixels 241, 242, 243 which are repeated from end to end of the layer. In some embodiments, the subpixels emit red, blue, and green light. Although three different subpixel units are shown in FIG. 2, two types of subpixel units or more than three types of subpixel units may be used.

  The various layers are further described herein with reference to FIG. However, the description also applies to FIG. 2 and other configurations.

  Layers 120-150 are referred to as electrically active layers, both individually and collectively. At least one of the electrically active layers is an organic electrically active layer that includes a deuterated material. The deuterated material 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% is deuterated, and in some embodiments, at least 40% is deuterated. And in some embodiments, at least 50% is deuterated, in some embodiments, at least 60% is deuterated, and in some embodiments, at least 70% is deuterated. , In some embodiments, at least 80% is deuterated, and in some embodiments, at least 90% deuterated. In some embodiments, the deuterated material is 100% deuterated.

  In some embodiments, the deuterated material is the hole injection material of layer 120. In some embodiments, at least one additional layer includes a deuterated material. In some embodiments, the additional layer is a hole transport layer 130. In some embodiments, the further layer is an electrically active layer 140. In some embodiments, the additional layer is an electron transport layer 150.

  In some embodiments, the deuterated material is the hole transport material of layer 130. In some embodiments, at least one further layer includes a deuterated material. In some embodiments, the additional layer is a hole injection layer 120. In some embodiments, the further layer is an electrically active layer 140. In some embodiments, the additional layer is an electron transport layer 150.

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

  In some embodiments, the deuterated material is an electron transport material in layer 150. In some embodiments, at least one further layer includes a deuterated material. In some embodiments, the additional layer is a hole injection layer 120. In some embodiments, the additional layer is a hole transport layer 130. In some embodiments, the further layer is an electrically active 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 electrically active layer, and an electron transport layer. In some embodiments, all organic active layers of the device include a deuterated material.

  In some embodiments, the device has additional layers to aid in processing or to enhance functionality. Some or all of such layers can include deuterated materials. In some embodiments, all layers of the organic device include a deuterated material. In some embodiments, all layers of the organic device consist essentially of deuterated material.

  In some embodiments, the organic light emitting diode includes an anode and a cathode, and further has an organic layer therebetween, the organic layer including a hole injection layer, a hole transport layer, an electroluminescent layer, an electron transport. A layer, and a cathode, wherein at least two of the organic layers consist essentially of deuterated material. In some embodiments, all of the organic layer consists essentially of deuterated material.

  In one embodiment, the thickness ranges of the various layers are as follows: the anode 110 is 500-5000 inches, and in one embodiment 1000-2000 inches; the hole injection layer 120 is 50-2000 inches. In one embodiment, it is 200-1000 ；; the hole transport layer 130 is 50-2000 Å, in one embodiment 200-1000 ；; the electrically active layer 140 is 10-2000 で は, in one embodiment Layer 150 is 50 to 2000 inches, in one embodiment 100 to 1000 inches; cathode 160 is 200 to 10,000 inches, and in one embodiment 300 to 5000 inches. The location of the electron-hole recombination zone in the device (and thus the emission spectrum of the device) can be affected by the relative thickness of each layer. The desired ratio of layer thickness will depend on the exact nature of the materials used.

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

  The calculated half-life of the devices described herein is at least 5000 hours. Methods for calculating the half-life at a given initial luminance are well known. The method is described, for example, by 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, and in some embodiments, at least 50,000 hours.

2. Hole Injection Layer The hole injection layer 120 includes a hole injection material and may have one or more roles in the organic electronic device. Its roles include planarization of the underlying layers, charge transport and / or charge injection properties, removal of impurities (such as oxygen or metal ions), and other aspects that facilitate or improve the performance of organic electronic devices. There are, but are not limited to them. The hole injection material can be a polymer, oligomer, or small molecule. They can be deposited or deposited from a liquid which can be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

  In some embodiments, the hole injection layer includes a deuterated material. In some embodiments, the deuterated material comprises a deuterated conductive polymer. By “deuterated conductive polymer” is meant that the conductive polymer itself (without the associated polymer acid) is deuterated. In some embodiments, the deuterated material comprises a conductive polymer doped with a deuterated polymeric acid. In some embodiments, the deuterated material comprises a deuterated conductive polymer doped with a deuterated polymer acid.

  In some embodiments, the deuterated conductive polymers are deuterated polythiophenes, deuterated polyselenophenes, deuterated polytellurophenes, deuterated polypyrroles, deuterated polyanilines, deuterated. Each selected from the group consisting of poly (4-amino-indoles), deuterated poly (7-amino-indoles), and deuterated polycyclic aromatic polymers. The term “polycyclic aromatic” refers to a compound having multiple aromatic rings. The rings may be connected by one or more bonds or may be fused. The term “aromatic ring” is intended to include heteroaromatic rings. “Polycyclic heteroaromatic” compounds have at least one heteroaromatic ring. In some embodiments, the deuterated polycyclic aromatic polymer is a deuterated polythienothiophene.

  In some embodiments, the deuterated conductive polymer is deuterated poly (3,4-ethylenedioxythiophene), deuterated polyaniline, deuterated polypyrrole, deuterated poly (4-aminoindole), deuterated Hydrogenated poly (7-aminoindole), deuterated poly (thieno (2,3-b) thiophene), deuterated poly (thieno (3,2-b) thiophene), and deuterated poly (thieno ( 3,4-b) selected from the group consisting of thiophene).

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

In some embodiments, the conductive polymer is poly (D ₆ -3,4-ethylenedioxythiophene), poly (D ₅ -pyrrole), poly (D ₇ -aniline), poly (perdeutero-4- Amino (indole), poly (perdeutero-7-aminoindole), poly (perdeutero-thieno (2,3-b) thiophene), poly (perdeutero-thieno (3,2-b) thiophene), and poly (perdeutero-thieno) It is selected from the group consisting of (3,4-b) thiophene).

In some embodiments, the deuterated conductive polymer is doped with a non-fluorinated polymeric acid. Any polymer having acidic groups with ionizable protons or deuterons 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 multiple types of acidic groups. In some embodiments, the acidic group is selected from the group consisting of a sulfonic acid group, a sulfonimide group, and combinations thereof. The sulfonimide group has the following formula:
—SO ₂ —NH—SO ₂ —R
[Wherein R is an alkyl group]. Examples of suitable acids include polystyrene sulfonic acid (“PSSA”), poly (perdeutero-styrene sulfonic acid) (“D ₈ -PSSA”), poly (2-acrylamido-2-methyl-1-propanesulfonic acid) ( "PAAMPSA"), poly (Perujuutero 2-acrylamido-2-methyl-1-propanesulfonic acid) ( "D ₁₃ -PAAMPSA"), and mixtures thereof, without limitation.

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

In some embodiments, the fluorinated acid polymer is a highly fluorinated acid polymer (“HFAP”) in which at least 80% of the available hydrogen bonded to the carbon is replaced with fluorine. A highly fluorinated acid polymer (“HFAP”) may be any polymer that is highly fluorinated and has acidic groups. The acidic group supplies ionizable protons (H ⁺ ) or deuterons (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. The acidic group may be directly attached to the polymer backbone or may be attached to a side chain 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 multiple types of acidic groups. In some embodiments, the acidic group is selected from the group consisting of a sulfonic acid group, a sulfonimide group, and combinations thereof.

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

  In some embodiments, HFAP is at least 90% fluorinated, in some embodiments, at least 95% fluorinated, and in some embodiments, fully fluorinated. In some embodiments, when HFAP is not fully fluorinated, HFAP is also deuterated.

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

  In some embodiments, the HFAP has a highly fluorinated olefin backbone that includes pendant highly fluorinated alkyl sulfonate groups, highly fluorinated ether sulfonate groups, highly fluorinated. With ester sulfonate groups or highly fluorinated ether sulfonimide groups. In some embodiments, HFAP is a perfluoroolefin having a perfluoro-ether-sulfonic acid side chain. In some embodiments, the polymer is a copolymer of tetrafluoroethylene and perfluoro-3,6-dioxa-4-methyl-7-octene sulfonic acid (“poly (TFE-PSEPVE)”). This deutero acid analog is abbreviated as D-poly (TFE-PSEPVE). In some embodiments, the polymer is a copolymer of 1,1-difluoroethylene and 2- (1,1-difluoro-2- (trifluoromethyl) allyloxy) -1,1,2,2-tetrafluoroethanesulfonic acid. It is. In some embodiments, the polymer is ethylene and 2- (2- (1,2,2-trifluorovinyloxy) -1,1,2,3,3,3-hexafluoropropoxy) -1,1,2. , 2-tetrafluoroethanesulfonic acid copolymer. Such copolymers can be made as the corresponding sulfonyl fluoride polymer and then converted to the sulfonic acid form.

  In some embodiments, the deuterated conductive polymer is doped with HFAP. Non-deuterated analogs of such materials are described, for example, in US Patent Application Publication No. 2004/0102577, US Patent Application Publication No. 2004/0127637, US Patent Application Publication No. 2005/0205860. , And published PCT application WO 2009/018009.

In some embodiments, the hole injection layer comprises deuterated poly (3,4-ethylenedioxythiophene) (“d-PEDOT”) doped with polystyrene sulfonic acid (“PSSA”). In some embodiments, the hole injection layer comprises poly (3,4-ethylenedioxythiophene) (“PEDOT”) doped with deuterated polystyrene sulfonic acid (“d-PSSA”). In some embodiments, the hole injection layer comprises deuterated poly (3,4-ethylenedioxythiophene) doped with deuterated polystyrene sulfonic acid. In some embodiments, d-PEDOT / d-PSSA is at least 50% deuterated, in some embodiments at least 60% deuterated, and in some embodiments at least 70% Deuterated, in some embodiments at least 80% deuterated, in some embodiments at least 90% deuterated, and in some embodiments 100% deuterated Has been. 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 consists essentially of poly (D ₆ -3,4-ethylenedioxythiophene) 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% is deuterated, and in some embodiments, at least 70% is deuterated. Hydrogenated, in some embodiments at least 80% deuterated, in some embodiments at least 90% deuterated, and in some embodiments 100% deuterated. ing. 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 polystyrene sulfonic acid (“PSSA”). In some embodiments, the hole injection layer comprises polypyrrole (“PPy”) doped with deuterated polystyrene sulfonic acid (“d-PSSA”). In some embodiments, the hole injection layer comprises deuterated polypyrrole doped with deuterated polystyrene sulfonic acid. In some embodiments, d-PPy / d-PSSA is at least 50% deuterated, in some embodiments at least 60% deuterated, and in some embodiments at least 70% Deuterated, in some embodiments at least 80% deuterated, in some embodiments at least 90% deuterated, and in some embodiments 100% deuterated Has been. 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 includes a 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 a deuterated conductive polymer doped with HFAP. In some embodiments, the hole injection layer consists essentially of a deuterated conductive polymer doped with a perfluorinated sulfonic acid polymer. In some embodiments, the hole injection layer consists essentially of D- poly (TFE-PSEPVE) is doped deuterated electrically-conductive polymer, its conductive polymer, poly (D _6-3,4- Selected from the group consisting of (ethylenedioxythiophene), poly (D ₇ -aniline) and poly (D ₅ -pyrrole).

  In some embodiments, the hole injection layer includes a charge transfer compound such as copper phthalocyanine, tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ) and their deuterated analogs, and the like.

3. Hole Transport Layer The hole transport layer 130 includes a hole transport material. The term “hole transport” when referring to a layer, material, member, or structure refers to a positively charged, relatively efficient and low charge loss, by such layer, material, member, or structure. It is intended to mean that movement through such a layer, material, member, or thick part of the structure is facilitated. Although the luminescent material may also have some hole transport properties, the term “hole transport layer, material, member, or structure” refers to a layer, material, member, or structure whose primary function is light emission. Not intended to be included.

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

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

  In some embodiments, the hole transport material is a deuterium compound having at least two diarylamino moieties per molecular formula unit. In some embodiments, the hole transport material is a 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 a deuterated fluorene-triarylamine copolymer. Non-deuterated analogs of such materials are described, for example, in US Patent Application Publication No. 2008/0071049 and US Patent Application Publication No. 2008/0097076. Examples of non-deuterated analogs of crosslinkable hole transporting polymers can be found, for example, in US Patent Application Publication No. 2005/0184287 and published PCT application WO 2005/052027. it can.

  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 is a deuterated polymeric triarylamine, deuterated polycarbazole, deuterated polyfluorene, deuterated having a conjugated moiety bonded in a non-planar configuration. It is selected from the group consisting of polymeric triarylamines, deuterated copolymers of fluorene and triarylamine, 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:

In the above formula,
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 moiety;
T ¹ and T ² are independently the same or different at each occurrence and are conjugated moieties;
a is the same or different at each occurrence, and is an integer of 1 to 6;
b, c, and d are mole fractions such that b + c + d = 1.0, provided that c is not zero, at least one of b and d is not zero, and b is zero , Provided that M contains at least two triarylamine units;
e is the same or different at each occurrence and is an integer from 1 to 6; and n is an integer greater than 1;
Here, at least 10% of the compound is deuterated.
Non-deuterated analogs of such materials are described in published PCT application WO 2009/067419.

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

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

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

In the above formula,
R ¹ is the same or different at each occurrence, and is selected from the group consisting of D, alkyl, alkoxy, siloxane and silyl; or adjacent R ¹ groups may combine to form an aromatic ring ;
f is the same or different at each occurrence, and is an integer of 0 to 4;
g is an integer from 0 to 5; and m is an integer from 1 to 5.

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

In the above formula,
R ¹ is the same or different at each occurrence, and is selected from the group consisting of D, alkyl, alkoxy, siloxane and silyl; or adjacent R ¹ groups may combine to form an aromatic ring ;
f is the same or different at each occurrence, and is an integer of 0 to 4;
g is an integer from 0 to 5; and m is an integer from 1 to 5.

  In some embodiments of formula a or b, at least one of f and g is not zero. In some embodiments, m = 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 their deuterated analogs.

Any aromatic ring in Formulas I-III may be substituted at any position. Substituents may be present to improve one or more physical properties (such as solubility) of the compound. In some embodiments, the substituents are alkyl groups of C 1 _{~ 12,} alkoxy group of C 1 _{~ 12,} a silyl group, and is selected from the group consisting of those of deuterated analogs. In some embodiments, a bridging substituent is present on at least one Ar ² . In some embodiments, a bridging substituent is present in at least one M moiety.

T ¹ and T ² are conjugated moieties. 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 a phenylene group, a naphthylene group, an anthracenyl group, and deuterated analogs thereof.

In some embodiments, the T ¹ -T ² group provides non-planarity to the backbone of the compound. The part in T ¹ that is directly connected to the part in T ² is connected such that the T ¹ part is placed in a different plane from the part in T ² to which the T ¹ part is connected. Although other sites (eg, substituents) of the T ¹ unit may be in one or more different planes, it is the non-planarity that results in binding moieties in T ¹ in the compound backbone and in T ² It is a plane of a joint part. The compound is chiral because of the non-planar T ¹ -T ² bond. In general, they occur as racemic mixtures. Such compounds can also be in enantiomerically pure form. Non-planarity can be viewed as limiting free rotation about the T ¹ -T ² bond. Rotation around the bond results in racemization. The half life of racemization of T ¹ -T ² is longer than that of unsubstituted biphenyl. In some embodiments, the half-life or racemization is 12 hours or more at 20 ° C.

In some embodiments, [T ¹ -T ² ] is a substituted biphenylene group or a 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 joined by a single bond. The biphenylene group can be linked at one of the 2-position, 3-position, 4-position or 5-position and can be linked at one of the 2′-position, 3′-position, 4′-position or 5′-position. The substituted biphenylene group has at least one substituent at the 2-position. In some embodiments, the biphenylene group has substituents at least at the 2 and 2 ′ positions.

In some embodiments, [T ¹ -T ² ] is a binaphthylene group, or a deuterated analog thereof. The term “binaphthylene” is intended to mean a binaphthyl group that has two points of attachment to the compound backbone. The term “binaphthyl” is intended to mean a group having two naphthalene units joined by a single bond.

In some embodiments, [T ¹ -T ² ] is a phenylene-naphthylene group, or a deuterated analog thereof. In some embodiments, [T ¹ -T ² ] is a compound backbone at one of the 3-, 4-, or 5-positions in phenylene and at one of the 3-, 4-, or 5-positions in naphthylene. And a phenylene-1-naphthylene group. In some embodiments, [T ¹ -T ² ] is ^one of the 3rd, 4th, or 5th position in phenylene and the 4th, 5th, 6th, 7th, or 8th position in naphthylene. And a phenylene-2-naphthylene group bonded to the compound skeleton.

  In some embodiments, the biphenylene group, binaphthylene group, and phenylene-naphthylene group 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 attached to the compound backbone at the 4 and 4 ′ positions (4,4 ′-( 1,1-binaphthylene)). In some embodiments, 4,4 ′-(1,1-binaphthylene) is the only isomer present. In some embodiments, there are two or more isomers. In some embodiments, 4,4 ′-(1,1-binaphthylene) is present up to 50% by weight of the second isomer. In some embodiments, the second isomer is 4,5 ′-(1,1-binaphthylene), 4,6 ′-(1,1-binaphthylene), and 4,7 ′-(1,1-binaphthylene). Selected from the group consisting of:

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

Among the non-limiting examples of hole transporting deuterium compounds are the following compounds HT1-HT10.
Compound HT1:

[Wherein, x + y + z + p + q + r = 20 to 28]
Compound HT2:

[Wherein x is 0 to 5 and depending on the compound, Σ (x) = 10 to 44]
Compound HT3:

[Wherein x is 0-6, and depending on the compound, Σ (x) = 8-36]
Compound HT4:

[Wherein x is 0-6, and depending on the compound, Σ (x) = 8-36]
Compound HT5:

R ₁ = D _y -propyl, R ₂ = D _y -octyl [where x is 0-5, Σ (x) = 10-50,
y is 0 to 17, and Σ (y) = 0 to 32]
Compound HT6:

[Wherein, a = 0.4 to 0.8
b = 0.2-0.6
x is 0-5, and depending on the compound, Σ (x) = 10-36]
Compound HT7:

[Where a = 0.3 to 0.7
b = 0.3-0.5
c = 0.1-0.2
x is 0-5, and depending on the compound, Σ (x) = 10-36]
Compound HT8:

[Where a = 0.9 to 0.95
b = 0.05-0.10
x is 0-5, and depending on the compound, Σ (x) = 20-62]
Compound HT9:

[Where a = 0.7 to 0.99
b = 0.01-0.30
x is 0-5, and depending on the compound, Σ (x) = 20-62]
Compound HT10:

[Wherein x is 0 to 5 and Σ (x) = 15 to 42]
Compound HT11:

[Wherein n is an integer greater than 1,
x is 0 to 5, and Σ (x) = 10 to 32]

Another example of a triarylamine polymer is compound HT12.
Compound HT12

  Examples of non-deuterated analogs of other hole transport materials in layer 130 are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. et al. Summarized in 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-phenylenediamine (PDA), a-phenyl 4-N, N-diphenylaminostyrene (TPS), p- (diethylamino) benzaldehyde diphenylhydrazone (DEH), triphenylamine (TPA), bis [4- (N, N-diethylamino)- -Methylphenyl] (4-methylphenyl) methane (MPMP), 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) 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 compounds (such as copper phthalocyanine), and the aforementioned substances There are, but are not limited to, any of the deuterated analogs. It is also possible to obtain hole transporting polymers by doping hole transporting molecules (such as those described above) into polymers such as polystyrene, polycarbonate, and their deuterated analogs.

  In some embodiments, the hole transport layer comprises tetrafluorotetracyanoquinodimethane, perylene-3,4,9,10-tetracarboxylic acid-3,4,9,10-dianhydride, and their deuterium. A p-dopant, such as a chemical compound, is doped.

4). Electroluminescent Layer The 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, the electroluminescent layer 140 consists essentially of an electroluminescent material. In some embodiments, the electroluminescent layer 140 includes one or more dopants and one or more host compounds. In some embodiments, the electroluminescent layer 140 consists essentially of one or more dopants and one or more host compounds. An electroluminescent dopant is a material capable of electroluminescence having an emission maximum between 380 and 750 nm. In some embodiments, the dopant emits red, green, or blue light. The host compound is usually a compound in the form of a layer in which one or more dopants are dispersed and in which one or more dopants emit light. The term “host material” refers to the total of all host compounds present. The host material may or may not have electronic properties or its ability to emit, accept, or filter radiation. In an electroluminescent layer that includes at least one dopant and a host material, light emission results from the dopant. In some embodiments, the host material is present at a concentration that is higher than the sum of all dopants. In some embodiments, the electroluminescent layer 140 consists essentially of one or more dopants and one or more host compounds. In some embodiments, the electroluminescent layer 140 consists essentially of one type of dopant and one type of host compound. In some embodiments, the electroluminescent layer 140 consists essentially of one type of dopant and two types of host compounds.

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

  The material of the electroluminescent layer may be a polymer, oligomer, small molecule, or a combination thereof. They can be deposited or deposited from a liquid which can be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

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

a. Electroluminescent Material 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, and in some embodiments, at least 30% deuterated. And in some embodiments, at least 40% is deuterated, in some embodiments, at least 50% is deuterated, and in some embodiments, at least 60% is deuterated. , In some embodiments, at least 70% is deuterated, in some embodiments, at least 80% is deuterated, and in some embodiments, at least 90% is deuterated. In some forms, 100% is deuterated.

  Examples of red luminescent materials are cyclometallated complexes of Ir having phenylquinoline or phenylisoquinoline ligands, periflatenes, fluoranthenes, perylenes, and their deuterated analogs. However, it is not limited to these. Non-deuterated red luminescent materials are disclosed, for example, in US Pat. No. 6,875,524 and US Patent Application Publication No. 2005-0158577.

  Examples of green luminescent materials include, but are not limited to, Ir cyclic metallated complexes with phenylpyridine ligands, diaminoanthracenes, polyphenylene vinylene polymers, and their deuterated analogs. Non-deuterated green luminescent materials are disclosed, for example, in published PCT application WO 2007/021117.

  Examples of blue emitting materials include diarylanthracenes, diaminochrysene, diaminopyrenes, diaminostilbenes, cyclic metallated complexes of Ir with phenylpyridine ligands, polyfluorene polymers, and their deuterated analogs However, it is not limited to these. Non-deuterated blue luminescent materials are disclosed, for example, in US Pat. No. 6,875,524 and US Patent Application Publication Nos. 2007-0292713 and 2007-0063638.

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

In some embodiments, the dopant is a complex having the formula Ir (L1) _x (L2) _y (L3) _z , wherein
L1 is a monoanionic cyclic metalated bidentate ligand coordinated through carbon and nitrogen;
L2 is a monoanionic bidentate ligand that is not coordinated via carbon;
L3 is a monodentate ligand;
x is 1-3,
y and z are independently 0-2,
Further, x, y, and z are selected so that iridium is hexacoordinated and the complex is electrically neutral.
Some examples of this formula include Ir (L1) ₃ ; Ir (L1) ₂ (L2); and Ir (L1) ₂ (L3) (L3 ′) where L3 is an anion and L3 ′ Is non-ionic], but is not limited thereto.

  Examples of L1 ligands include phenyl pyridines, phenyl quinolines, phenyl pyrimidines, phenyl pyrazoles, thienyl pyridines, thienyl quinolines, thienyl pyrimidines, and their deuterated analogs. It is not limited to. The term “quinolines” as used herein includes “isoquinolines” unless otherwise specified. The fluorinated derivative may have one or more fluorine substituents. In some embodiments, 1 to 3 fluorine substituents are on the non-nitrogen ring of the ligand.

  L2, a monoanionic bidentate ligand, is well known in the art of metal coordination chemistry. In general, such ligands have N, O, P, or S as coordinating atoms and form a 5- or 6-membered ring when coordinated to iridium. Suitable coordinating groups include, but are not limited to, amino, imino, amide, alkoxide, carboxylate, phosphino, thiolate, and their deuterated analogs. Examples of suitable parent compounds for such ligands include β-dicarbonyls (β-enolate ligands) and their N and S analogs; aminocarboxylic acids (aminocarboxylate ligands); Acid (iminocarboxylate ligand); salicylic acid derivative (salicylate ligand); hydroxyquinolines (hydroxyquinolinate ligand) and their S analogs; phosphinoalkanols (phosphinoalkoxide ligand) And their deuterated analogs.

The monodentate ligand L3 may be anionic or nonionic. Anionic ligands include, but are not limited to, H ⁻ (“hydride”) and ligands having C, O, or S as a coordination atom. Coordinating groups include alkoxides, carboxylates, thiocarboxylates, dithiocarboxylates, sulfonates, thiolates, carbamates, dithiocarbamates, thiocarbazone anions, sulfonamide anions, and their deuterated analogs. It is not limited to. In some cases, the ligands listed above for L2, such as β-enolates and phosphinoalkoxides, can act as monodentate ligands. The monodentate ligand may be a coordinated anion such as halide, cyanide, isocyanide, nitrate, sulfate, hexahaloantimonate. These ligands are generally commercially available.

  The L3 monodentate ligand may be a nonionic ligand (such as CO), a monodentate phosphine ligand, or a deuterated monodentate phosphine ligand.

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

  Iridium complex dopants can be made, for example, using standard synthetic methods similar to those described in US Pat. No. 6,670,645 for non-deuterated analogs.

  In some embodiments, the electroluminescent material is a small organic compound. Examples of small molecule luminescent compounds include chrysene, pyrenes, perylenes, rubrenes, periflatenes, fluoranthenes, stilbenes, coumarins, anthracenes, thiadiazoles, their derivatives, their deuteration There are, but are not limited to, analogs and mixtures thereof.

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

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

  In some embodiments, the dopant is selected from the group consisting of spirobifluorene compounds and fluoranthene compounds that are not macromolecules.

  In some embodiments, the electroluminescent material is a compound having an arylamine group. In some embodiments, the electroluminescent material is selected from the following formula:

In the above formula,
A is an aromatic group which is the same or different at each occurrence and has 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 of 1 to 6.
In the above formula, the values of p and q can be limited by the available binding sites on the nuclear Q ′ group.

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

  In some embodiments of the above formula, at least one of A and Q 'in each formula has at least 3 fused rings. In some embodiments, p and q are equal to 1.

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

  In some embodiments, Q 'is an aromatic group having at least two fused 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, Selected from the group consisting of 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 following structure:

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

In the above formula,
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 are joined to form a 5- or 6-membered aliphatic ring You may;
Ar is the same or different and is selected from the group consisting of aryl groups;
Here, 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 at any site on the Q ′ group of the nucleus.

  In some embodiments, the electroluminescent material has the following formula:

In the above formula,
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 electroluminescence is an aryl acene or a deuterated analog thereof. In some embodiments, the electroluminescent material is an asymmetric aryl acene or a deuterated analog thereof.

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

上式において、
Ｒ²は、それぞれの出現箇所で同一または異なっていて、Ｄ、アルキル、アルコキシおよびアリールよりなる群から選択され、ここで、隣接したＲ²基は結合して５員または６員の脂肪族環を形成してよく；
Ａｒ³〜Ａｒ⁶は、同一または異なっていて、アリール基および重水素化アリール基よりなる群から選択され；
ｈは、それぞれの出現箇所で同一または異なっていて、０〜４の整数であり；
ここで、少なくとも１個のＤがある。

In the above formula,
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 are joined to form a 5- or 6-membered aliphatic ring May form;
Ar ^{3 to} Ar ⁶ are the same or different and are selected from the group consisting of an aryl group and a deuterated aryl group;
h is the same or different at each occurrence and is an integer of 0 to 4;
Here, there is at least one D.

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

In the above formula,
R ³ is the same or different at each occurrence, and consists of D, alkyl, alkoxyaryl, fluoro, cyano, nitro, —SO ₂ R ⁴ [wherein R ⁴ is alkyl or perfluoroalkyl]. Selected from the group, wherein adjacent R ³ groups may combine 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 i is the same or different at each occurrence and is an integer of 0 to 5;
Here, there is at least one D.

  In some embodiments of Formulas IV and V, substituents on the aryl ring are deuterated. An aryl group having a deuterated substituent may be an anthracene nucleus group of formula IV or a chrysene nucleus group of formula V; or an aryl on nitrogen; or an aryl group of a substituent. In some embodiments, the deuterated substituent on the aryl ring is selected from alkyl, aryl, alkoxy, and aryloxy. In some embodiments, the substituents are at least 10% deuterated, in some embodiments, at least 20% are deuterated, and in some embodiments, at least 30% are deuterated. , In some embodiments, at least 40% is deuterated, in some embodiments, at least 50% is deuterated, and in some embodiments, at least 60% is deuterated. In some embodiments, at least 70% is deuterated, in some embodiments, at least 80% is deuterated, and in some embodiments, at least 90% deuterated.

In some embodiments of Formulas IV and V, any one or more aryl groups Ar ^{3 to} Ar ⁶ are deuterated. 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 C of aryl in Ar ^{3 to} Ar ⁶ is substituted with D. In some embodiments, each aryl ring will have some D. In some embodiments, some, but not all, of the aryl ring has D. In some embodiments, Ar ^{3 to} Ar ⁶ are at least 20% deuterated, in some embodiments, at least 30% deuterated, and in some embodiments, at least 40% is deuterium. And in some embodiments, at least 50% is deuterated, in some embodiments, at least 60% is deuterated, and in some embodiments, at least 70% is deuterated. And in some embodiments, at least 80% is deuterated, and in some embodiments, at least 90% is deuterated.

In some embodiments of formula IV and V, both the substituent (R ² or R ³ ) and the aryl group are deuterated. In some embodiments, the compounds of Formulas IV and V are at least 10% deuterated, in some embodiments at least 20% deuterated, and in some embodiments at least 30% deuterated. Hydrogenated, in some embodiments at least 40% deuterated, in some embodiments at least 50% deuterated, and in some embodiments at least 60% deuterated. And in some embodiments, at least 70% is deuterated, in some embodiments, at least 80% is deuterated, and in some embodiments, at least 90% is deuterated. And in some embodiments, 100% is deuterated.

In some embodiments of Formula IV and V, the compound is symmetric about the amino group. In this case, Ar ³ = Ar ⁵ and 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 symmetrical about the amino group. In this case, Ar ³ is different from both Ar ⁵ and Ar ⁶ . Ar ³ may be different be the same as Ar ^4, Ar ⁴ may be different and the same as each of Ar ⁵ and Ar ^6.

  In some embodiments of Formula IV, both h are 0.

In some embodiments of Formula IV, at least one h is greater than zero. In some embodiments, at least one R ² is a 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, both h are equal to 4 and R ² is D.

In Formula V, the bond to (R ³ ) _i is intended to indicate that the R ³ group can be at any one or more sites on the two fused rings.

  In some embodiments of Formula V, both i are equal to 0.

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

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

In some embodiments, at least one of Ar ^{3 to} Ar ⁶ has the formula a or b shown 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 perdeuterated except for one or more alkyl groups on the terminal aryl.

Some non-limiting examples of deuterated electroluminescent materials are shown below as E1-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 a host material. Examples of non-deuteration of host compounds are disclosed, for example, in US Pat. No. 7,362,796 and US Patent Application Publication No. 2006-0115676.

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

  In some embodiments, the host material is an anthracene, chrysene, pyrene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinolines, isoquinolines, quinoxalines, phenylpyridines, dibenzofurans, diene Comprising difuranobenzenes, metal quinolinate complexes, indolocarbazoles, benzimidazoles, triazolopyridines, diheteroarylphenyls, substituted derivatives thereof, deuterated analogs thereof, and combinations thereof Selected from the group. In some embodiments, the aforementioned host compound has a substituent selected from the group consisting of aryl, alkyl, and deuterated analogs thereof. In some embodiments, the heteroaryl group is pyridine, pyrazine, pyrimidine, pyridazine, triazines, tetrazines, quinazoline, quinoxaline, naphthylpyridines, their heterobiaryl analogs, their heterotriaryl analogs, and their Selected from the group consisting of deuterated analogs.

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

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

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

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

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

  In some embodiments, the host material has the formula VI:

In the above formula,
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; and n is an integer from 0 to 6.
It will be understood that n can take values from 0 to 6, but for some Q groups the value of n is constrained 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 joined to form a ring such as carbazole. In Formula VI, “adjacent” means that their Ar groups are attached to the same N.

In some embodiments, Ar ⁷ is independently selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, naphthylphenyl, phenanthrylphenyl, and deuterated analogs thereof. More analogs with 5-10 phenyl rings than quaterphenyl can also be used.

In some embodiments, at least one of Ar ⁷ has at least one substituent. Substituents can 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 substituent increases the solubility of the host material and / or increases its Tg. In some embodiments, the substituent is 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 3-5 fused aromatic rings. In some embodiments, Q is anthracene, chrysene, pyrene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, dibenzofuran, difurano Selected from the group consisting of benzenes, indolocarbazoles, substituted derivatives thereof, and deuterated analogs thereof.

  In some embodiments, the host compound has Formula VII:

In the above formula,
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; and Ar ¹⁰ and Ar ¹¹ are the same or different and are selected from the group consisting of H, D, and aryl groups;
Here, there is at least one D.

  In some embodiments of Formula VII, at least one D is on an aryl ring substituent. In some embodiments, the substituent is 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 3 are D; in some embodiments, at least 4 are D; in some embodiments, at least 5 are D; in some embodiments, at least 6 are D; In some cases, at least 7 are D. In some embodiments, all of R ^{4 to} R ¹¹ are D.

In some embodiments, R ^{4 to} 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 six 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, five of R ^{4 to} R ¹¹ are D and three are H. In some embodiments, six of R ^{4 to} R ¹¹ are D and two are H. In some embodiments, seven of R ^{4 to} R ¹¹ are D and one is H. In some embodiments, eight 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 remainder of R ^{4 to} R ¹¹ is 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 that is at least 10% deuterated. In some embodiments, R ⁵ is from deuterated aryl that is at least 20% deuterated, in some embodiments, from at least 30% deuterated, in some embodiments, at least 40%. % From deuterated, in some embodiments from at least 50% deuterated, in some embodiments from at least 60% deuterated, depending on the embodiment. Selected from at least 70% deuterated, in some embodiments from at least 80% deuterated, and in some embodiments from at least 90% deuterated. Is done. In some embodiments, R ² is selected from deuterated aryls that are 100% deuterated.

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 aryls.

In some embodiments of Formula VII, Ar ⁸ -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, and in some embodiments at least 40% Is deuterated, in some embodiments at least 50% deuterated, in some embodiments at least 60% deuterated, and in some embodiments at least 70% deuterated. Hydrogenated, in some embodiments at least 80% deuterated, in some embodiments at least 90% deuterated, and in some embodiments 100% deuterated. ing.

  In some embodiments, the compound of Formula VII is at least 10% deuterated, in some embodiments at least 20% deuterated, and in some embodiments at least 30% deuterated. And in some embodiments, at least 40% is deuterated, in some embodiments, at least 50% is deuterated, and in some embodiments, at least 60% is deuterated. And in some embodiments, at least 70% is deuterated, in some embodiments, at least 80% is deuterated, and in some embodiments, at least 90% is 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 their deuterated analogs.

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

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, the heteroaryl group is at least 10% deuterated, in some embodiments at least 20% deuterated, and in some embodiments at least 30% deuterated. And in some embodiments, at least 40% is deuterated, in some embodiments, at least 50% is deuterated, and in some embodiments, at least 60% is deuterated. In some embodiments, at least 70% is deuterated, in some embodiments, at least 80% is deuterated, and in some embodiments, at least 90% is 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 -R ¹¹ is D and at least one of Ar ⁸ -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, and in some embodiments, at least 40% deuterated; In some embodiments, at least 50% is deuterated, in some embodiments, at least 60% is deuterated, and in some embodiments, at least 70% is deuterated, In some embodiments, at least 80% is deuterated, and in some embodiments, at least 90% is deuterated. In some embodiments, the compound is 100% deuterated.

  In some embodiments, the host compound has Formula VIII.

In the above formula,
R ¹² is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, silyl, and siloxane, or an adjacent R ¹² group bonded to form a 5- or 6-membered group. May form an aliphatic ring,
Ar ¹² and Ar ¹³ are the same or different and are aryl groups;
j is an integer from 0 to 6;
k is an integer from 0 to 2; and l is an integer from 0 to 3;
Here, there is at least one D.

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, the branched alkyl group is a 2-propyl group, a t-butyl group, or a deuterated analog thereof.

In some embodiments, Ar ¹² and Ar ¹³ are phenyl groups having a substituent 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, their deuterated analogs, and the formula a or Selected from the group consisting of groups having the formula b.

  In some embodiments, the host compound has Formula IX.

In the above formula,
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;
In addition, one of the following conditions is met:
(I) R ¹⁴ = R ¹⁵ and H, D, phenyl, biphenyl, naphthyl, naphthylphenyl, arylanthracenyl, phenanthryl, triphenylamino, carbazolylphenyl, and their deuteration Is selected from the group consisting of analogs;
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, there is at least one D.

In some embodiments, the phenanthroline compound is symmetric and both R ¹³ are the same and R ¹⁴ = R ¹⁵ . In some embodiments, R ¹³ = R ¹⁴ = R ¹⁵ . In some embodiments, the phenanthroline compound is asymmetric and the 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 is 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.

In the above formula,
R ¹⁶ is the same or different at each occurrence, and is selected from hydrogen, deuterium, phenyl, biphenyl, naphthyl, naphthylphenyl, phenanthryl, triphenylamino, carbazolyl, carbazolylphenyl, and their deuterated derivatives. Selected from the group consisting of:
R ¹⁷ is H or D; and Q ′ ″ is an aryl group;
Here, there is at least one D.

  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 their deuteration. Selected from the group consisting of derivatives.

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

In the above formula,
Ar ¹⁴ is an aromatic electron transport group;
Ar ¹⁵ is selected from the group consisting of an aryl group and an aromatic electron transport group; and 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;
Here, the compound has at least one D.

  In some embodiments of Formula XII and Formula XIII, deuterium is present in a moiety selected from the group consisting of an indolocarbazole nucleus, an aryl ring, a substituent on the aryl ring, 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 perform electron transport include the following, but are not limited thereto.

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; and r is an integer of 0-6.
The group can bind to nitrogen on the nucleus at any of the positions indicated by the wavy line.

In some embodiments, two or more of the same or different electron withdrawing substituents are combined to form an oligomer substituent. 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 the aromatic electron transport group described above. In some embodiments, Ar ¹⁵ is selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthylene, naphthylphenylene, deuterated derivatives thereof, and groups having formula a or formula b as described above.

  In some embodiments, the host material is a deuterated diarylanthracene, a deuterated aminochrysene, a deuterated diarylchrysene, a deuterated diarylpyrene, a deuterated indolocarbazole, a deuterated phenanthroline. , And combinations thereof.

Among the non-limiting examples of deuterated host compounds are the following compounds H1-H17.
Compound H1:

[Wherein, x + y + z + n = 1 to 26]
Compound H5:

[Wherein, x + y + z + p + n + q = 1 to 34]
Compound H8:

Compound H9:

Compound H13:

Compound H14:

Compound H15:

Compound H16:

[Where Σ (af) = 1-25]
Compound H17:

[Where Σ (af) = 1 to 28]

5. Electron Transport Layer The electron transport layer 150 contains an electron transport material. The term “electron transport” when referring to a layer, material, member, or structure refers to a relatively efficient, low charge loss, negative charge, by such layer, material, member, or structure. It is intended to mean that movement through such a layer, material, member, or thick part of the structure is facilitated. Although the luminescent material may also have some electron transport properties, the term “electron transport layer, material, member, or structure” includes a layer, material, member, or structure whose primary function is luminescence. Not intended.

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

  In some embodiments, the electron transport layer includes a deuterated material. In some embodiments, the electron transport material is at least 10% deuterated, in some embodiments at least 20% deuterated, and in some embodiments at least 30% deuterated. And in some embodiments, at least 40% is deuterated, in some embodiments, at least 50% is deuterated, and in some embodiments, at least 60% is deuterated. , In some embodiments, at least 70% is deuterated, in some embodiments, at least 80% is deuterated, and in some embodiments, at least 90% is deuterated. In some forms, 100% is deuterated.

  In some embodiments, the electron transport layer 150 includes a deuterated phenanthroline derivative having the Formula IX, Formula X, or Formula XI described above. In some embodiments, the electron transport layer 150 consists essentially of a deuterated phenanthroline derivative having the formula IX, formula X, or formula XI.

  In some embodiments, the electron transport layer 150 includes a deuterated indolocarbazole derivative having the above Formula XII or Formula XIII. In some embodiments, the electron transport layer 150 consists essentially of a deuterated indolocarbazole derivative having the formula XII or formula XIII.

  In some embodiments, the electron transport layer comprises a material selected from the group consisting of deuterated benzimidazoles, deuterated triazolopyridines, and deuterated diheteroarylphenyls.

  In some embodiments, the electron transport layer 150 includes a deuterated metal chelated oxinoid compound. Examples of such materials are deuterated tris (8-hydroxyquinolato) aluminum (d-AlQ), deuterated bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum (d- There are deuterated metal quinolate derivatives such as 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 phenanthrolines, deuterated indolocarbazoles, deuterated benzimidazoles, deuterated triazolopyridines, deuterated diheteroarylphenyls, deuterium. And an electron transport material selected from the group consisting of metal quinolates and combinations thereof. In some embodiments, the electron transport layer comprises deuterated phenanthrolines, deuterated indolocarbazoles, deuterated benzimidazoles, deuterated triazolopyridines, deuterated diheteroarylphenyls, deuterium. Consisting essentially of an electron transport material selected from the group consisting of metal quinolates and combinations thereof.

Examples of other electron transport materials that can be used for the electron transport layer 150 include 2- (4-biphenylyl) -5- (4-tert-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 ( Azole compounds such as 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 Group 2 metal salts (such as LiF, CsF, and Cs ₂ CO ₃ ); Group 1 and Group 2 metal organic compounds (such as Li quinolate); And molecular n-dopants (such as leuco dyes), metal complexes (W ₂ (hpp) ₄ [where hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido- [1,2- a] -pyrimidine] and cobaltcene), tetrathianaphthacene, bis (ethylenedithio) tetrathiafulvalene, heterocyclic groups or heterocyclic diradicals, and heterocyclic groups or heterocyclic groups There are, but are not limited to, dimers, oligomers, polymers, dispiro compounds and polycycles of groups. The n-dopant may also be deuterated.

Among the non-limiting examples of deuterated electron transport compounds are the following compounds ET1-ET4.
ET1:

ET2:

Here, Σ (x + y + z) = 1 to 54
ET3:

ET4:

6). Chemical containment To create a full color image display, each display pixel is divided into three sub-pixels, each emitting one of the three main display colors (red, green, and blue). To do. When applying different colors with liquid deposition techniques, it is necessary to prevent diffusion of liquid coloring material (ie, ink) and color mixing from subpixel to subpixel.

  One way to prevent color mixing is to provide a chemical confinement layer before applying the colored ink. The term “chemical confinement layer” is intended to mean a patterned layer that suppresses or limits the diffusion of a liquid material by surface energy effects rather than physical barrier structures. The term “confinement” when referring to a layer is intended to mean that the layer does not diffuse significantly beyond the area where the layer is deposited. The term “surface energy” is the energy required to create a unit area surface from a material. A characteristic of surface energy is that a liquid material with a given surface energy will not wet a surface with a smaller surface energy.

  In some embodiments, the chemical confinement layer includes a deuterated material. In some embodiments, the chemical containment material is at least 10% deuterated, in some embodiments at least 20% deuterated, and in some embodiments, at least 30% deuterated. And in some embodiments, at least 40% is deuterated, in some embodiments, at least 50% is deuterated, and in some embodiments, at least 60% is deuterated. And in some embodiments, at least 70% is deuterated, in some embodiments, at least 80% is deuterated, and in some embodiments, at least 90% is deuterated; In some embodiments, 100% is deuterated.

  In some embodiments, for devices initially made from the anode side, a chemical confinement layer is applied over the hole injection layer to confine both the hole transport layer and the electroluminescent layer. In some embodiments, a chemical confinement layer is applied over the hole transport layer to confine the electroluminescent layer. For devices initially made from the cathode side, the chemical confinement layer can be applied over the electron injection layer or the electron transport layer.

  In some embodiments, the chemical confinement layer is formed on the first layer using a primer layer, the primer layer having a surface energy that is significantly different from the surface energy of the first layer. The undercoat layer is applied to the entire first layer. The subbing layer is then exposed to radiation in a pattern so that exposed and unexposed areas occur. The primer layer is then developed to effectively remove the primer layer from exposed or unexposed areas. As a result, a patterned undercoat layer is formed on the first layer. The patterned subbing layer is a chemical confinement layer. The terms “effectively remove” and “effectively remove” mean that the primer layer is essentially completely removed in either the exposed or unexposed areas. The subbing layer may be partially removed in other regions. As a result, the remaining pattern of the primer layer may be thinner than the original primer layer.

  In some embodiments, the pattern of the primer layer has a surface energy that is greater than the surface energy of the first layer. The second layer is formed by attaching a liquid so as to cover the pattern of the undercoat layer on the first layer.

  In some embodiments, the pattern of the primer layer has a surface energy that is less than the surface energy of the first layer. The second layer is formed by attaching a liquid so as to cover the first layer in the region where the undercoat layer has been removed. This method and non-deuterated materials are described in US Patent Application Publication No. 2007/0205409.

  One way to determine the relative surface energy is for a given liquid contact angle with the first organic layer and an undercoat layer (hereinafter referred to as a “development subbing layer”) after exposure and development. It is to compare the contact angle of the same liquid. The contact angle increases as the surface energy decreases. Various manufacturers make devices that can measure contact angles.

  In some embodiments, the surface energy of the first layer is lower than the surface energy of the primer layer. In some embodiments, the first layer has a contact angle with anisole 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 developed subbing layer has a contact angle with anisole of less than 30 °; in some embodiments, less than 20 °; in some embodiments, less than 10 °. In some embodiments, the contact angle with the developed primer layer is at least 20 ° less than the contact angle with the first layer in a given solvent; in some embodiments, the contact angle with the developed subbing layer is developed in the given solvent. The contact angle with the subbing layer is at least 30 ° less than the contact angle with the first layer, and in some embodiments, the contact angle with the developed subbing layer in a given solvent is the contact angle with the first layer. Is at least 40 ° smaller.

  The primer layer comprises a composition that reacts when exposed to radiation to yield a material that is more or less likely to be removed from the underlying first layer as compared to the unexposed primer material. This change must be sufficient to allow physical differences between exposed and unexposed areas as well as development.

  In one embodiment, the primer layer comprises a radiation curable composition. In this case, when exposed to radiation, the subbing layer becomes less soluble or dispersible in the liquid medium, less sticky, less soft, less fluid, less liftable, Or a decrease in absorbency can occur. Other physical properties can also be affected.

  In one embodiment, the subbing layer consists essentially of one or more radiation-sensitive materials. In one embodiment, the subbing layer hardens or is less soluble, less swellable, or less dispersible, or less sticky or absorbable when exposed to radiation. It consists essentially of the substance that occurs. In one embodiment, the subbing layer consists essentially of a material having radiation-polymerizable groups. Examples of such groups include, but are not limited to, olefins, acrylates, methacrylates and vinyl ethers. In one embodiment, the primer material has two or more polymerizable groups that can cause crosslinking.

  In one embodiment, the subbing layer consists essentially of at least one reactive material and at least one radiation sensitive material. When exposed to radiation, a radiation sensitive material produces an active species that initiates the reaction of the reactive material. Examples of radiation sensitive materials include, but are not limited to, materials that generate free radicals, acids, or combinations thereof.

  In one embodiment, the reactive material is polymerizable or crosslinkable. The material polymerization or crosslinking reaction is initiated or catalyzed by the 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 type of radiation-sensitive material that produces free radicals can be used. Examples of radiation-sensitive substances that generate free radicals include quinones, benzophenones, benzoin ethers, aryl ketones, peroxides, imidazoles, benzyl dimethyl ketal, hydroxylalkylphenyl acetophone, Dialkoxy acetophenone, trimethylbenzoylphosphine oxide derivative, aminoketone, benzoylcyclohexanol, methylthiophenylmorpholinoketone, morpholinophenylaminoketone, alpha halogenoacetophenone, oxysulfonylketone, sulfonylketone, oxysulfonylketone , Sulfonyl ketones, benzoyloxime esthetics S, thioxanthrones compound (thioxanthrones), camphor quinone, ketocoumarins, and there are Michler's ketone, and the like. Alternatively, the radiation sensitive substance may be a mixture of compounds, one of which produces free radicals (when caused by a sensitizer 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 subbing layer.

  In one embodiment, the reactive material is one where polymerization initiated by acid can occur and the radiation sensitive material yields acid. Examples of such reactive materials include, but are not limited to, epoxy compounds. Examples of radiation sensitive materials that produce acid include, but are not limited to, sulfonium salts and iodonium salts (such as diphenyliodonium hexafluorophosphate).

  In one embodiment, the subbing layer comprises a radiation softening composition. In this case, when exposed to radiation, the subbing layer will have increased solubility or dispersibility in the liquid medium, increased tackiness, increased softness, increased fluidity, increased peelability, or absorbable properties. An increase can occur. Other physical properties can also be affected.

  In one embodiment, the subbing layer softens when exposed to radiation, or exhibits increased solubility, increased swellability, or increased dispersibility, or is tacky or absorbed when exposed to radiation. It consists essentially of substances that cause increased sex.

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

  In one example of a radiation softening composition, the subbing layer consists essentially of at least one polymer that undergoes skeletal degradation when exposed to deep ultraviolet light having a wavelength in the range of 200-300 nm. Examples of polymers where such degradation occurs 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 primer layer reacts with the underlying region when exposed to radiation. The exact mechanism of this reaction will depend on the material used. After exposure to radiation, the subbing layer is effectively removed in the unexposed areas by a suitable development process. In some embodiments, the primer layer is removed only in the unexposed areas. In some embodiments, the primer layer is partially removed even in the exposed areas, leaving a thin layer in those areas. In some embodiments, the primer layer remaining in the exposed area is less than 50 mm thick. In some embodiments, the primer layer remaining in the exposed area is essentially a monolayer in thickness.

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

  The subbing layer can be applied by any known deposition method. In one embodiment, the subbing layer is applied without being added to the solvent. In one embodiment, the primer layer is applied by vapor deposition.

  In one embodiment, the primer layer is applied by a setting method. When applying the primer layer by condensation from the vapor phase, if the surface layer temperature is too high during vapor condensation, the primer layer may enter pores or free volumes on the surface of the organic substrate. 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 placing the first layer on a surface cooled by a flowing liquid or gas).

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

  Applying the primer layer can be accomplished using either a continuous or batch process. For example, in a batch process, one or more devices will be coated simultaneously with a subbing layer and then simultaneously exposed to a radiation source. In a continuous process, a device transported on a belt or other conveyor device passes through a station where the device is continuously coated with a subbing layer and then leaves the station where the device is continuously exposed to a radiation source. Will pass. Some parts of the process may be continuous, while other parts of the process may be batch.

  In one embodiment, the primer material is a liquid at room temperature and is applied by liquid deposition over the first layer. The liquid primer material may form a film or may be absorbed or adsorbed on the surface of the first layer. In one embodiment, the liquid primer material is cooled to a temperature below its melting point to form the second layer over the first layer. In one embodiment, the primer material is not 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 cover the first layer. Let it form. For liquid deposition, any of the methods described above may be used.

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

  After forming the subbing layer, it is exposed to radiation. The type of radiation used will depend on the sensitivity of the primer layer described above. Exposure is done in a pattern. The term “patterned” as used herein indicates that only a selected portion of a substance or layer is exposed. Patterned exposure can be achieved using any well-known imaging technique. In one embodiment, the pattern is obtained by exposing through a mask. In one embodiment, the pattern is obtained by exposing only selected portions with a rastered laser. The exposure time can range from a few seconds to a few minutes depending on the specific chemistry of the primer layer used. When using a laser, depending on the power of the laser, the exposure time used for each individual area is much shorter. The exposure step can be performed in air or in an inert atmosphere, depending on the sensitivity of the material.

In one embodiment, the radiation is from the group consisting of ultraviolet light (10-390 nm), visible light (390-770 nm), infrared light (770-10 ⁶ nm), and combinations thereof (including simultaneous and sequential processing). Selected. In one embodiment, the radiation is selected from visible light and ultraviolet radiation. In one embodiment, the radiation has a wavelength in the range of 300-450 nm. In one embodiment, the radiation is deep ultraviolet (200-300 nm). In another embodiment, the ultraviolet radiation has a wavelength between 300 and 400 nm. In another embodiment, the radiation has a wavelength in the range of 400-450 nm. In one embodiment, the radiation is thermal radiation. In one embodiment, exposure to radiation is performed by heating. The temperature and duration of the heating step is such that it changes at least one physical property of the subbing layer 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 pattern exposure to radiation, the subbing layer is developed. Development can be accomplished by any known technique. Such techniques have been widely used in the photoresist and printing arts. Examples of development techniques include, but are not limited to, heating (evaporation), treatment with a liquid medium (cleaning), treatment with an absorbent material (blotting), and treatment with an adhesive material. The development step effectively removes the subbing layer in either the exposed or unexposed areas. The subbing layer then remains in either the unexposed area or the exposed area, respectively. The subbing layer may be partially removed in the unexposed area or in the exposed area, but must remain sufficient to ensure that there is a wettability difference between the exposed and unexposed areas . For example, the primer layer may be effectively removed in the unexposed areas and a portion of the thickness may be removed in the exposed areas. In some embodiments, the developing step effectively removes the subbing layer in the unexposed areas.

  In one embodiment, exposure of the primer layer to radiation changes the solubility or dispersibility of the primer layer in the solvent. In this case, the development can be performed by a wet development treatment. This treatment usually involves washing with a solvent that results in dissolution, dispersion, or stripping of one type of area. In one embodiment, patterned exposure to radiation insolubilizes the exposed areas of the primer layer and treatment with a solvent removes unexposed areas of the primer layer.

  In one embodiment, exposure of the primer layer to radiation causes a reaction that changes the volatility of the primer layer in the exposed area. In this case, development can be performed by heat development processing. This treatment involves heating to a temperature above the volatilization or sublimation temperature of the more volatile material and below the temperature at which the material thermally reacts. For example, in the case of a polymerizable monomer, the material will be heated at a temperature above the sublimation temperature and below the thermal polymerization temperature. It will be appreciated that a primer material having a thermal reaction temperature close to or below the volatilization temperature may not be developed in this manner.

  In one embodiment, exposing the primer layer to radiation changes the temperature at which the material melts, softens or flows. In this case, the development can be performed by a dry development treatment. Dry development processing may involve bringing the outermost surface of the element into contact with the adsorbent surface to absorb or blot softer portions. This dry development can be carried out at elevated temperatures as long as it does not further affect the properties of the remaining areas.

  The development step produces an area where the undercoat layer remains and an area where the underlying first layer is exposed.

  In some embodiments, the primer layer includes a hole transport material. In some embodiments, the subbing layer comprises a material selected from the group consisting of triarylamines, carbazoles, fluorenes, their polymers, their copolymers, their deuterated analogs, and combinations thereof. Including. In some embodiments, the subbing layer comprises polymeric triarylamines, polycarbazoles, polyfluorenes, polymeric triarylamines having a conjugated moiety bonded in a non-planar configuration, fluorenes and triarylamines A material selected from the group consisting of: a copolymer of: a deuterated analog thereof; and combinations thereof. In some embodiments, the polymeric material is crosslinkable. In some embodiments, the subbing layer includes an electron transport material. In some embodiments, the subbing layer includes a metal chelated oxinoid compound. In some embodiments, the subbing layer includes a metal quinolate derivative. In some embodiments, the subbing layer comprises tris (8-hydroxyquinolato) aluminum, bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum, tetrakis- (8-hydroxyquinolato) hafnium, And a substance selected from the group consisting of tetrakis- (8-hydroxyquinolato) zirconium. In some embodiments, the subbing 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 subbing layer consists essentially of a hole transport material. In some embodiments, the hole transport material is a 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 primer material is a polymeric triarylamine having a conjugated moiety bonded in a non-planar configuration, a compound having at least one fluorene moiety and at least two triarylamine moieties, and their weights. Selected from the group consisting of hydrogenated analogs. In some embodiments, the polymeric triarylamines have the above Formula I, Formula II, or Formula III.

  Among the exemplary compounds that can be used as the subbing layer are deuterated fluorene, deuterated polyfluorene, deuterated polyvinyl carbazole, compounds HT1-HT12, ET3 and ET4.

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

  The anode 110 is an electrode that is particularly efficient for injecting positive charge carriers. It can be made, for example, of a metal-containing material, mixed metal, alloy, metal oxide or mixed metal oxide, or it can be a conductive polymer, or a mixture thereof. . Suitable metals include Group 11 metals, Group 4-6 metals, and Group 8-10 transition metals. When making the anode light transmissive, mixed metal oxides (such as indium-tin-oxide) of Group 12, Group 13 and Group 14 metals are generally used. The anode 110 is “Flexible light-emitting diodes made from a solid conducting polymer,” Nature vol. 357, pp 477-479 (11 June 1992), and can also contain organic substances such as polyaniline. At least one of the anode and the cathode is desirably at least partially transparent so that the generated light can be seen.

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

  It is known to provide another layer in an organic electronic device. For example, a layer between the anode 110 and the hole injection layer 120 to control the amount of positive charge injected and / or to match the band gap of the layer or to function as a protective layer (see FIG. (Not shown). Layers known in the art can be used, including ultrathin layers of copper phthalocyanine, silicon oxynitride, fluorocarbons, silanes, or metals (such as Pt). Alternatively, part or all of the anode layer 110, the active layers 120, 130, 140, and 150, or the cathode layer 160 can be surface treated to increase charge carrier transport efficiency. The choice of material for each component layer is preferably determined by balancing positive and negative charges so that the device has high electroluminescence efficiency. Any or all of these layers can include a deuterated material.

  It is understood that each functional layer can be composed of a plurality of layers.

  Devices can be made by a variety of techniques, including the sequential deposition of individual layers on a suitable substrate. Substrates such as glass, plastic, and metal can be used. Conventional vapor deposition techniques such as thermal evaporation and chemical vapor deposition can be used. Alternatively, using conventional coating techniques or printing techniques such as but not limited to spin coating, dip coating, roll-to-roll techniques, inkjet printing, screen printing, gravure printing, The organic layer can be applied from a dispersion or solution of a suitable solvent.

In some embodiments, the method for manufacturing an organic light emitting device is:
Providing a substrate having a patterned anode thereon;
Forming an electrically active layer by depositing a first liquid composition comprising (a) a deuterated deuterated electroactive material and (b) a liquid medium;
Forming the entire cathode.

  The term “liquid composition” means a liquid medium in which one or more substances are dissolved to form a solution, a liquid medium in which one or more substances are dispersed to form a dispersion, or one or more kinds of liquid compositions. It is intended to include a liquid medium in which the substance is suspended into a suspension or emulsion.

  In some of the method embodiments described above, the deuterated electroactive material is a deuterated hole injection material. In some of the above method embodiments, the deuterated electroactive material is a deuterated hole transport material. In some of the method embodiments described above, the deuterated electroactive material is a deuterated electroluminescent material. In some of the above method embodiments, the deuterated electroactive material is a deuterated host material. In some of the above method embodiments, the deuterated electroactive material is a deuterated electron transport material. In some of the method embodiments described above, the deuterated electroactive material is a deuterated chemical confinement material.

In some embodiments, the method includes:
The method further includes forming a second electroactive layer by depositing a second liquid composition including a second deuterated electroactive material in the second liquid medium.

  In some embodiments, the second deuterated electroactive material is a deuterated hole injection material, a deuterated hole transport material, a deuterated electroluminescent material, a deuterated host material, a deuterated electron. Selected from the group consisting of transport materials and deuterated chemical confinement materials.

  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, ink jet 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. While nozzle printing can be viewed as a continuous technique, the pattern can be formed by placing the nozzles only over the desired areas where the layers are to be formed. For example, a continuous row pattern can be formed.

Suitable liquid media for the particular composition to be deposited can be readily determined by one skilled in the art. Depending on the application, it may be desirable to dissolve the compound in a non-aqueous solvent. Such non-aqueous solvents can be relatively polar (such as C ₁ -C ₂₀ alcohols, ethers, and acid esters), or can be relatively non-polar (C ₁ -C ₁₂ alkanes or aromatics). Compounds (toluene, xylene, trifluorotoluene, etc.). Chlorinated hydrocarbons (such as methylene chloride, chloroform, chlorobenzene, etc.) as other liquids suitable for making liquid compositions containing new compounds (either as solutions or dispersions described herein) , Aromatic hydrocarbons (such as substituted or unsubstituted toluene or xylene, including trifluorotoluene), polar solvents (such as tetrahydrofuran (THF), N-methylpyrrolidone (NMP)), esters (such as ethyl acetate), alcohols (Such as isopropanol), ketones (such as cyclopentatone), or any mixture thereof, but are not limited thereto. Examples of solvent mixtures for electroluminescent materials are described, for example, in US Patent Application Publication No. 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 a hole injection layer, a hole transport layer, and an electrically active layer, and evaporation of the anode, electron transport layer, electron injection layer, and cathode.

8). Synthesis of Deuterated Materials Non-deuterated analogs of the compounds described herein can be prepared by well-known coupling and substitution reactions. The new deuterium compound then uses a deuterated precursor material, or more commonly a Lewis acid H / D exchange catalyst (such as aluminum trichloride or ethyl aluminum chloride), or It can be prepared in a similar manner by treating a non-deuterium compound with a deuterated solvent (such as d6-benzene) in the presence of an acid (such as CF ₃ COOD, DCl). Exemplary preparations are shown in the examples. The level of deuteration can be determined by NMR analysis and mass spectrometry (such as atmospheric pressure solid analysis probe mass spectrometry (ASAP-MS)).

  Starting materials for perdeuterated or partially deuterated aromatics or alkyl compounds can be purchased from product suppliers or obtained using well-known methods. Some examples of such methods are: a) “Efficient H / D Exchange Reactions of Alkyl-Substituted Benzen Derivatives by Means of the Pd / C-H2-D2O System”. , Tomohiro Maegawa, Yasunari Monguchi, and Hironao Sajiki Chem. Eur. J. et al. 2007, 13, 4052-4063; b) “Aromatic H / D Exchange Reaction Catalyzed by Groups 5 and 6 Metal Chords,” GUO, Qiao-Xia, SHEN, BaO-Jian; GUH, QIA-Xia, SHEN, Bao-Jian; , 2005, 23, 341-344; c) “A novel deuterium effect on dual charge-transfer and ligand-field emission of the cis-dichlorobis (2,2′-bipyridine) (R)”. . Watts, Shlomo Efrima, and Horia Metiu J. et al. Am. Chem. Soc. , 1979, 101 (10), 2742-2743; d) "Efficient HD Exchange of Aromatic Compounds in Near-Critical D20 Catalyzed by a Polymer-Supreme E) US 3849458; f) "Efficient C-H / C-D Exchange Reaction on the Alky Side Chain of Aromatic Compounds Using Heterogeneous Pd / C in D2O". onao Sajiki, Fumiyo Aoki, Hiroyoshi Esaki, Tomohiro Maegawa, and Kosaku Hirota Org. Lett. 2004, 6 (9), 1485-1487.

  The compounds described herein can be made into films using liquid deposition techniques. Surprisingly, these compounds unexpectedly have significantly improved properties compared to similar non-deuterium compounds. Electronic devices that include active layers having the compounds described herein have significantly improved lifetime. In addition, the lifetime has been increased with high quantum efficiency and good saturation. In addition, the deuterium compounds described herein have greater air tolerance than non-deuterated analogs. Therefore, processing tolerance in both preparation and purification of the material can be increased, and electronic devices using the material can be formed.

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

Example 1 of synthesis
This example illustrates the preparation of D-HIJ-1, a deuterated hole injection material.

a. Heavy water and (D ₂ O) Preparation tetrafluoroethylene dispersion containing Juutero HFAP in ( "TFE") and perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid ( "PSEPVE") The copolymer was deuterated and colloidally dispersed in D ₂ O as follows. Initially, poly (TFE-PSEPVE) with one proton of sulfonic acid per 987 grams (weight of copolymer per acidic site) was measured according to US Pat. No. 6, except that the temperature was approximately 270 ° C. An aqueous dispersion was made using a procedure similar to that of Part 2 of Example 1 of the 150,426 specification. The non-deuterated poly (TFE-PSEPVE) dispersion was converted to poly (TFE-PSEPVE) free-flowing solid flakes on a tray having a liquid depth of 5/8 "or less. First, the aqueous dispersion was frozen at less than 0 ° C. Once frozen, a partial vacuum pressure of 1 mmHg or less was applied until most of the water was removed, then the partially dried solid was about 30 ° C. under vacuum pressure. The water was completely removed without coalescence of the polymer.

21 g of solid flakes non-deuterated poly (TFE-PSEPVE) (pre-dried in a vacuum oven to remove water) was placed in a metal cylinder tube (pre-cleaned with nitrogen). . Cambridge Isotop Lab, Inc. 150 g of D ₂ O purchased from was immediately added to the tube containing poly (TFE-PSEPVE). In a pressure laboratory, the tube is capped and heated to about 270 ° C. and then cooled to room temperature so that the solid flakes are a colloidal dispersion containing poly (TFE-PSEPVE) in D ₂ O. did. Furthermore, the deuteration of poly (TFE-PSEPVE) was completed by replacing the protons in poly (TFE-PSEPVE), which is overwhelmingly higher than deuterium, with deuterium. A dispersion containing deuterated poly (TFE-PSEPVE) in D ₂ O (“D-poly (TFE-PSEPVE)”) was further treated to remove large particles. The weight% of D-poly (TFE-PSEPVE) in the D ₂ O dispersion was 11.34% by weight based on the total weight of the dispersion as measured by the gravimetric method.

b. Deutero HFAP and a direct method of making a dispersion comprising deutero HFAP in heavy water (D ₂ O).

A copolymer of tetrafluoroethylene (“TFE”) and perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid (“PSEPVE”) is deuterated as follows in D ₂ O The liquid can be colloidally dispersed in the liquid. Poly (TFE-PSEPVE) resin with one proton of sulfonic acid per 987 grams (weight of copolymer per acidic site), except that the temperature is approximately 270 ° C. and D ₂ O is used Can be made into a D2O dispersion using a procedure similar to that of Part 2 of Example 1 of US Pat. No. 6,150,426.

c. Preparation of Deuterated Conducting 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 the structure.

Polymerization of D ₅ -Py in the D-poly (TFE-PSEPVE) / D ₂ O dispersion was carried out as follows. 70.2 g of D-poly (TFE-PSEPVE) / D ₂ O prepared in Example 1 was weighed and 500 mL of the resin reaction kettle was initially charged, followed by an additional 14 g of D ₂ O. The amount of D-poly (TFE-PSEPVE) / D ₂ O corresponds to 8.14 mmol of acid. The reaction kettle was capped with a glass with an overhead stirrer. While stirring D-poly (TFE-PSEPVE) / D ₂ O, 0.135 g (0.26 mmol) ferric sulfate and 0.62 g (2.6 mmol) Na ₂ S ₂ O ₈ (pre- In 10 mL) was added to D-poly (TFE-PSEPVE) / D ₂ O. Immediately thereafter, 0.175 g (2.43 mmol) of D ₅ -Py (predissolved in 7 mL of D ₂ O) was added to the mixture within 1 minute. As soon as D ₅ -Py was added, polymerization started. The polymerization was allowed to proceed for 10 minutes. Component addition and polymerization were carried out under nitrogen. At the end of 10 minutes, Dowex M-43 resin was added to the resin reaction kettle and mixed for approximately 5 minutes. After vacuum filtration through 417 filter paper, Dowex M-31 Na ⁺ resin was added to the mixture and mixed for 5 minutes. The resulting material was vacuum filtered once more using 417 filter paper. A D ₂ O dispersion of deuterated polypyrrole doped with D-poly (TFE-PSEPVE) (“Poly (D ₅ -Py) / D-Poly (TFE-PSEPVE)”) again with ion-exchanged resin. Upon processing, the dispersion was further purified. The dispersion only contained 1.79 ppm sulfate and 0.79 ppm chloride. The% solids in the dispersion was measured to be 4.3% and the pH measured to 5.2. The measured electrical conductivity of the cast film baked at 275 ° C. for 30 minutes in the dry box was ˜1 × 10 ⁻⁶ S / cm at room temperature.

Example 2 of synthesis
This example illustrates a method for producing a deuterated hole transport material (HT5). This is shown below, where R ¹ = n-propyl, R ² = n-octyl, y = 0 and x = 42:

This compound is made according to the following scheme.

Synthesis of intermediate compound Y1:
Under a nitrogen atmosphere, AlCl ₃ (0.17 g, 1.29 mmol) was added to 2,2′-dioctyl-4,4′-dibromo-1,1′-binaphthylene (2.328 g, 3.66 mmol). C ₆ D ₆ (100 mL) was added to the solution. The resulting mixture was stirred at room temperature for 30 minutes, after which D ₂ O (50 mL) was added. The layers were separated and the aqueous layer was washed with CH ₂ Cl ₂ (2 × 30 mL). The combined organic layers were dried over magnesium sulfate and volatiles were removed by rotary evaporation. 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 made from compound Y1 using a procedure similar to the method for preparing intermediate compound C1 described above. Compound Y2 is purified using chromatography.

Synthesis of intermediate compound Y3:

  Under nitrogen, a 100 mL round bottom flask was charged with compound Y2 (2.100 g, 2.410 mmol) and dichloromethane (30 mL). It was allowed to stir for 5 minutes, after which trifluoroacetic acid (1.793 mL) was added and the reaction was left stirring overnight. When the reaction was complete, it was quenched with saturated sodium carbonate solution. Water was removed, washed with CH2Cl2, and the combined organic layers were evaporated to dryness. The residue was dissolved in diethyl ether. The product was washed with sodium carbonate, brine and water and dried with magnesium sulfate. Compound Y3 was purified using chromatography to obtain 1.037 g.

The structure of the compound was confirmed by ¹ H NMR as shown in FIG.

Synthesis of intermediate compound Y4:

A solution of 4-bromo-4′-propylbiphenyl (5.10 g, 18.53 mmol) in C6D6 (20 mL) was washed with nitrogen for 30 minutes. A 1.0 M solution containing ethylaluminum dichloride solution in hexane (4.0 mL, 4.0 mmol) was added dropwise via syringe and the reaction mixture was heated at reflux under a nitrogen atmosphere for 1.75 hours. After cooling to room temperature under a nitrogen atmosphere, heavy water (20 mL) is added and the mixture is shaken before the layers are separated. The aqueous layer was extracted with benzene (3 × 10 mL) and the combined organic phases were dried over magnesium sulfate, filtered and concentrated by rotary evaporation. The product thus obtained was repeatedly subjected to the above reaction conditions twice more. After the third treatment, the crude product is recrystallized from ethanol (20 mL) to give compound Y4 (1.01 g) as a white solid. Mp 110.1-111.6 ° C. Purity (UPLC): 100%. The ¹ H NM spectrum of Y4 was consistent with an average of 7.64 when 8 aromatic protons were replaced with 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-butylphosphine (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 was stirred at room temperature for 40 hours. 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 then added, and The reaction mixture was warmed to 50 ° C. After an additional 72 hours, the reaction mixture was filtered through a pad of celite and washed with CH2Cl2 (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% gradient methylene chloride / hexane) to give 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'-positional isomers. 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 washed with nitrogen for 30 minutes. A 1.0 M solution of ethylaluminum dichloride solution in hexane (4.0 mL, 4.0 mmol) was added dropwise with a syringe and the reaction mixture was heated at reflux under nitrogen atmosphere for 50 minutes. After cooling to room temperature under a nitrogen atmosphere, heavy water (20 mL) is added and the mixture is shaken before the layers are separated. The organic phase is dried over magnesium sulfate, filtered and concentrated by rotary evaporation. The product thus obtained was repeatedly exposed to the above reaction conditions four more times. After the fifth treatment, the crude product was recrystallized from ethanol (20 mL) to give the title compound of Step 1 (2.26 g) as a white solid. Mp 92.8-94.1 ° C. Purity (UPLC): 98.14%. The mass spectrum showed that 6-9 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 minutes. 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 recrystallized with EtOH / EtOAc (1/1) to give Y6 (1.31 g) as a white solid. Mp 179.0-181.3C. Purity (UPLC): 100%. The mass spectrum showed that an average of 6-7 deuterium atoms were incorporated.

Synthesis of intermediate compound Y7:

In a nitrogen-washed glove box, a three-necked round bottom flask equipped with a magnetic stirrer, thermometer and reflux condenser (with a gas inlet adapter at the top in the closed position) in a Y5 (986 mg, 0.92 mmol), Y6 (1.30 g, 3.55 mmol), tris (dibenzylideneacetone) dipalladium (0) (124 mg, 14.8 mol%), bis (diphenylphosphonoferrocene (bis) (Diphenylphosphinoferrocene)) (151 mg, 29.6 mol%) and toluene (20 mL) were charged from the open neck Sodium t-butoxide (0.30 g, 3.12 mmol) was added to the opening. The lid was removed and the reactor was removed from the glove box. A gas bubble adapter hose was attached to the gas injection adapter and the stopcock was turned to an open position under slightly positive nitrogen.The reaction was heated while refluxing.After 21 hours, the reaction was completed by UPLC analysis of aliquots. The reaction was cooled to room temperature, the reaction mixture was filtered through a pad of celite and washed with CH 2 Cl 2. The filtrate was concentrated by rotary evaporation, the crude product was dried under high vacuum, Purification by medium pressure liquid chromatography on silica gel (0-40% gradient methylene chloride / hexane) gave a white solid of 1.21 that was triturated with boiling methanol for 2 hours to give 0.975 g of solid. the Y7 was obtained. ¹ H NMR analysis, that the structure of the intermediate compound Y7 is a mixture of 4,4'- and 4,5'- mixture of regioisomers And an average of 14 aromatic protons remained, confirming that 36 out of 50 aromatic hydrogens were replaced by deuterium. Mass spectrum parent ion (m / z 1550.3), purity (UPLC):> 99%.

Synthesis of compound of hole transport compound HT5:
The polymerization of intermediate compound Y7 was carried out as described for comparative A. The polymer was obtained as a white solid in 68% yield (0.285 g). 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.

Example 3 of synthesis
This example illustrates the preparation of compound HT11 (where Σ (x) = 18) which is a deuterated hole transport material.

Synthesis of compound 2

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

Synthesis of compound 3

A 250 mL 3-neck round bottom flask equipped with a condenser and dropping funnel was washed 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 of 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% aqueous Na ₂ S ₂ O ₃ was added and the reaction mixture was stirred for 1 hour. The organic layer was extracted and the aqueous layer was washed 3 times with 100 mL dichloromethane. The combined organic layers were dried over Na ₂ SO ₄ , filtered and concentrated to dryness. When acetone was added to the resulting oil, a white precipitate formed. Filtration and drying gave a white powder (13.3 g, 52.2%). NMR analysis showed that the material was Compound 3 having the structure shown above.

Synthesis of compound 4

Under a nitrogen atmosphere, in a 250 mL round bottom, 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. The reaction mixture was stirred for 10 minutes, after which NaO ^t Bu (3.68 g, 38.33 mmol) was added and the reaction mixture was stirred at room temperature for 1 day. The resulting reaction mixture was diluted with 3 L of toluene and filtered through a plug of silica and celite. Once the volatiles were evaporated, the resulting dark brown oil was purified by flash column chromatography on silica gel using a 1:10 mixture of ethyl acetate: hexane as eluent. 50.2% (6.8 g) of product was obtained as a pale yellow powder. NMR analysis showed that the material was Compound 4 having the structure shown above.

Synthesis of compound 5

In a 250 mL three-necked round bottom flask equipped with a condenser, 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 minutes. 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 toluene and 1 L THF and passed through a plug of silica and celite to remove insoluble salts. Once the volatiles were evaporated, the resulting brown oil was purified by flash column chromatography on silica gel using a 1:10 mixture of dichloromethane: hexane as eluent. A yellow powder was obtained after drying (4.8 g, 84.8%). NMR analysis showed that the material was Compound 5 having the structure shown above.

Synthesis of compound 6

Under a nitrogen atmosphere, 1 g of compound 5 was dissolved in C ₆ D ₆ (20 mL), and CF ₃ OSO ₂ D (1.4 mL) was added dropwise thereto. The reaction mixture so as to be stirred at room temperature overnight and then quenched with saturated Na2CO ₃ / D ₂ O. The organic layer was separated and dried over MgSO ₄ . The product was purified using silica chromatography (20% CH2Cl2: hexanes) to give 0.688 g of material. The MS spectrum of the separated material confirmed its structure with 18 aromatic Ds.

Polymerization of compound 6:
All operations were performed in a nitrogen-cleaned glove box unless otherwise noted. Compound 6 (0.652 g, 0.50 mmol) was added to a scintillation vial and dissolved in 16 mL toluene. A clean and dry 50 mL Schlenk tube was charged with bis (1,5-cyclooctadiene) nickel (0) (0.344 g, 1.252 mmol). 2,2′-dipyridyl (0.195 g, 1.252 mmol) and 1,5-cyclooctadiene (0.135 g, 1.252 mmol) are weighed into a scintillation vial and 3.79 g of N, N Dissolved in '-dimethylformamide. The solution was added to the Schlenk tube. The Schlenk tube was inserted into an aluminum block and the block was heated and stirred with a hot plate / stirrer at a set point where the internal temperature was 60 ° C. The catalyst system was held at 60 ° C for 45 minutes and then raised to 65 ° C. A monomer toluene solution was added to the Schlenk tube and the tube was sealed. The polymerization mixture was stirred by 1 at 65 ° C. while adjusting the viscosity by adding toluene (8 mL). The reaction mixture was cooled to room temperature and 20 mL of concentrated HCL was added. The mixture was left stirring for 45 minutes. The polymer was collected by vacuum filtration, washed with additional methanol and dried under high vacuum. The polymer was purified by continuous precipitation from toluene to acetone and MeOH. White fibrous polymer (0.437 g, 79% yield) was obtained. 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 that the structure was compound HT11, which is a polymer.

Example 4 of synthesis
This example illustrates a method for producing the deuterated electroluminescent material E4 shown below.

0.45 g 2,6-di-t-butyl-9,10-dibromoanthracene (1 mM) (Muller, U .; Adam, M .; Mullen, K. Chem. Ber. 1994, 127, 437-444) Was placed in a round bottom flask in a glove box filled with nitrogen and 0.38 g (2.2 mM) di (peruterophenyl) amine and 0.2 g sodium tert-butoxide (2 mM) in 40 mL. Added with toluene. 0.15 g Pd ₂ DBA ₃ (0.15 mM) and 0.07 g P (t-Bu) 3 (0.3 mM) were dissolved in 10 mL toluene and added to the first solution with stirring. When all materials are mixed, the solution slowly exotherms and becomes tan. The solution was stirred and heated in a glove box at 80 C for 1 hour under nitrogen. The solution is immediately dark purple in color, but when it reaches ˜80 C, it is dark yellow-green with eye-catching green luminescence. After cooling to room temperature, the solution is removed from the glove box, filtered through a short plug of basic alumina and eluted with toluene to obtain a bright yellow-green band. The solvent was evaporated and the material was recrystallized with toluene / methanol. Yield: 0.55g. The structure was confirmed by ¹ H NMR.

Example 5 of synthesis
This example illustrates the preparation of deuterated host compound H14.

  A non-deuterated analog compound (Comparative Compound A) was first made.

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 contained 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] undec-7-ene (“DBU”) was added via a dropping funnel over 1.5 hours. It was. The solution turned orange, became opaque and then turned crimson. To the still cold solution, 58 ml (345.0 mmol) of triflic anhydride was added with a syringe over about 1.5 hours while keeping the temperature of the solution below 5 ° C. The reaction was allowed to proceed for 3 hours at room temperature, after which additional 1 mL of triflic anhydride was added and stirring at room temperature was continued for 30 minutes. When 500 mL of water was added slowly, the layers separated. The aqueous layer was extracted with 3 × 200 mL of dichloromethane (“DCM”) and the combined organic layers were dried over magnesium sulfate, filtered and concentrated by rotary evaporation to give a red oil. Column chromatography on silica gel followed by crystallization with hexane yielded 43.1 g (43%) of a tan powder.

Synthesis of Compound 3 A 200 mL Kjeldahl reaction flask equipped with a magnetic stir bar in a nitrogen filled glove box was charged with anthracen-9-yl trifluoromethanesulfonate (6.0 g, 18.40 mmol), Naphthalen-2-yl. Boronic acid (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) were added. After removal from the dry box, the reaction mixture was flushed with nitrogen and degassed water (50 mL) was added via syringe. A condenser was then attached and the reaction was refluxed overnight. The reaction was monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature. The organic layer was separated and the aqueous layer was extracted with DCM. The organic portions 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 hexane and filtered. Purification by column chromatography on silica gel gave 4.03 g (72%) of the product as a pale yellow crystalline material.

Synthesis of compound 4:
9- (Naphthalen-2-yl) anthracene (11.17 g (36.7 mmol)) was suspended in 100 mL DCM. 6.86 g (38.5 mmol) of N-bromosuccinimide was added and the mixture was stirred while lighting a 100 W lamp. A yellow clear solution was formed, followed by precipitation. The reaction was monitored by TLC. After 1.5 hours, the reaction mixture was partially concentrated to remove methylene chloride and then crystallized with acetonitrile to give 12.2 g of pale yellow crystals (87%).

Synthesis of compound 7:
A 500 mL round bottom flask equipped with a stir bar in a glove box filled with nitrogen was charged with naphthalen-1-yl-1-boronic acid (14.2 g, 82.6 mmol), 1-bromo-2-iodo. Benzene (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). added. After removal from the dry box, the reaction mixture was flushed with nitrogen and degassed water (120 mL) was added via syringe. The reaction flask was then fitted with a condenser and the reaction 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 portions were combined and the solvent was removed under reduced pressure to give a yellow oil. Purification by column chromatography using silica gel yielded 13.6 g of a clear oil (58%).

Synthesis of compound 6:
To a 1 liter flask equipped with a magnetic stir bar, reflux condenser (connected to a nitrogen line) and an oil bath was added 4-bromophenyl-1-naphthalene (28.4 g, 10.0 mmol), bis. (Pinacolate) diboron (40.8 g, 16.0 mmol), Pd (dppf) ₂ Cl ₂ (1.64 g, 2.0 mmol), potassium acetate (19.7 g, 200 mmol), and DMSO ( 350 mL) was added. The mixture was bubbled with nitrogen for 15 minutes before Pd (dppf) ₂ Cl ₂ (1.64 g, 0.002 mol) was added. During this process, the mixture gradually turned dark brown. The reaction was stirred at 120 ° C. (oil bath) under nitrogen for 18 hours. After cooling, the mixture was poured into ice water and extracted with chloroform (3x). The organic layer was washed with water (3x) and saturated brine (1x) and dried over MgSO4. After filtration and removal of the solvent, the residue was purified by chromatography on a silica gel column. The parts containing the product were combined and the solvent was removed by rotary evaporation. The resulting white solid was crystallized with hexane / chloroform and dried in a vacuum oven at 40 ° C. to give the product as white crystalline flakes (15.0 g, 45% yield). 1H and 13C-NMR spectra are consistent with the expected structure.

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

  The product was further purified as described in U.S. Patent Application Publication No. 2008-0138655 to achieve a HPLC purity of at least 99.9% and an impurity absorbance of 0.01 or less.

The ¹ H NMR spectrum of Compound A is shown in FIG.

  Deuterated host compound H14 was made from Comparative Compound A.

Under a nitrogen atmosphere, AlCl ₃ (0.48 g, 3.6 mmol) was added to Comparative Compound A of Comparative Example A (5 g, 9.87 mmol) perdeuterobenzene or benzene-D6 (C ₆ D ₆ ) (100 mL) was added to the solution. The resulting mixture was stirred at room temperature for 6 hours, after which D ₂ O (50 mL) was added. The layers were separated and the aqueous layer was washed with CH ₂ Cl ₂ (2 × 30 mL). The combined organic layers were dried over magnesium sulfate and volatiles were removed by rotary evaporation. The crude product was purified by column chromatography. The 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 U.S. Patent Application Publication No. 2008-0138655, to a purity of at least 99.9% on HPLC and an impurity absorbance of 0.01 or lower. From the above, the material was found to be the same level of purity as Comparative Compound A.

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

In the above equation, “D / H” indicates that H or D is at this atomic position with approximately equal probability. The structure was confirmed by ¹ H NMR, ¹³ C NMR, ² D NMR, and ¹ H- ¹³ C HSQC (heteronuclear single quantum coherence method).

Example 6 of synthesis
This example illustrates a method for producing a deuterated electron transport material (ET2).

  a) Using the procedure of Yamada et al Bull Chem Soc Jpn, 63, 2710, 1990, trimethylene-bridged bathophenanthroline was prepared as follows: 2 g of bathophenanthroline was placed in 20 g of 1,3-dibromopropane, Refluxed under air. After about 30 minutes, the dark orange slurry was cooled. Methanol was added to dissolve the solid, then acetone was added to precipitate a bright orange solid. This was filtered and washed with toluene and dichloromethane (“DCM”), resulting in an orange powder in a yield of 2.8 g.

  b) 2.8 g of the above product was dissolved in 12 mL of water and added dropwise over about 30 minutes to an ice cold solution containing 21 g of potassium ferricyanide and 10 g of sodium hydroxide in 30 mL of water, followed by stirring for 90 minutes . This was cooled again with ice and neutralized with 60 mL of 4M HCl to a pH of about 8. A pale tan / yellow solid was filtered off and sucked dry. The filtered solid was placed in a Soxhlet and the brown solution was extracted by extraction with chloroform. This was evaporated to a brownish oily solid and then washed with a small amount of methanol to give a light brown solid (˜1.0 g, 47%). The product may be recrystallized from chloroform / methanol as gold platelets by evaporating chloroform from the mixture. The structure was identified by NMR as the following diketone.

c) The combined diketone parts of step (b) above (total 5.5 g (13.6 mM)) were suspended in 39 mL POCl ₃ and 5.4 g PCl ₅ was added. . This was degassed and refluxed under nitrogen for 8 hours. Excess POCl3 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 under vacuum, and the mother liquor was extracted with methylene chloride. All brown materials were combined and evaporated to a brown gum and methanol was added. After shaking and stirring, a pale yellow solid separated and was recrystallized from CHCl3 and methanol (1:10) as off-white needles. Analysis by NMR showed that the structure was 2,9-dichloro-4,7-diphenyl-1,10-phenanthroline shown below.

  d) Non-deuterated analog compounds were prepared using the Suzuki coupling of 2,9-dichloro-4,7-diphenyl-1,10-phenanthroline and boronate ester shown below.

1.0 g dichloro-phen (2.5 mM) is placed in the glove box and 3.12 g (6 mM) boronic ester is added. Add 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), all of which Dissolve in 30 mL dioxane and 15 mL water. Mix and heat for 1 hour at 100C in the mantle in the glove box, then gently warm overnight under nitrogen (minimum setting of the rectifier). The solution is then dark purple immediately, but when it reaches ˜80 ° C., it is a tan brown slurry, which slowly becomes clear brown when a dense precipitate occurs. As the solution refluxes (air condenser), a brown gum is formed. Cool out by removing it from the glove box and then add water. Extract into DCM and dry over magnesium sulfate. Chromatographic separation on a silica / florisil plug, eluting with DCM and then DCM / methanol (2: 1). The evaporated pale yellow solution is collected and methanol is added to precipitate a white / pale yellow solid. The structure was confirmed to be the following compound by NMR analysis.

  e) Compound ET2 was made from a non-deuterated analog compound.

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

Synthesis Example 7
This example illustrates a method for producing a deuterated electron transport material (ET4).

Synthesis of D _{6-8-hydroxyquinoline} is a ligand

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. , Heated to 180 C for 16 hours. The resulting mixture was added to diethyl ether (200 mL), the layers were separated, and the organic layer was filtered through celite. After the volatiles were evaporated, the resulting solid was purified using chromatography (20% DCM / hexanes), the D _{6-8-hydroxyquinoline} The product of 2.4 g (77% yield) Obtained.

Zirconium chloride synthesis 1.0g of ET4 (IV) was mixed with dry methanol 10 mL, was added to the stirred solution containing D _{6-8-hydroxyquinoline} 3.2g in dry methanol 10 mL. This was stirred and refluxed under nitrogen for 30 minutes. The Zr reaction immediately formed a dark yellow precipitate, which was stirred and heated to reflux for 30 minutes. To this was added 4.8 g of tri-n-butylamine and reflux was continued for 15 minutes. The dark yellow precipitate was filtered and washed with methanol and ammonia (1N). After drying it, it was extracted with methylene chloride as a pale yellow solution and reprecipitated with methanol. The structure was confirmed by ¹ H NMR.

Example 8 of synthesis
This example illustrates the preparation of deuterated electroluminescent compound E13.

  a) The compounds shown below were prepared according to Yan et. al. , J .; Mater. Chem. 2004, 14, 2295-3000.

  b) Non-deuterium compounds were prepared according to the following scheme.

Place 1.0 g of bromostilbene (2.3 mM) in the glove box and add 0.74 g (2.3 mM) of the indicated secondary amine and 0.24 g of t-BuONa (2.4 mM) to 10 mL. Add with toluene. Add 40 mg P (t-Bu) ₃ , 100 mg Pd ₂ DBA ₃ dissolved in toluene. Mix and heat for 1 hour at 80 C in a mantle under nitrogen in a glove box. The solution is then dark purple immediately, but when it reaches ˜80 C, it is dark yellow with significant blue luminescence. The material is cooled, removed from the glove box, purified by chromatography and eluted with toluene. Blue luminescent material dissolves very well and elutes as a pale yellow solution. The solution is evaporated to reduce the volume and methanol is added to precipitate a pale yellow solid with a bright blue photoluminescence. The structure was confirmed by NMR analysis.

  c) Compound E13 was prepared by deuterating the compound from step (b) above using a procedure similar to that of Synthesis Example 6.

Examples 1 to 6 of the device
The following non-deuterated materials were used.

  HIJ-A and HIJ-B are aqueous dispersions of conductive polymers and polymeric fluorinated sulfonic acids. Such materials include, for example, U.S. Patent Application Publication No. 2004/0102577, U.S. Patent Application Publication No. 2004/0127637, U.S. Patent Application Publication No. 2005/0205860, and published PCT applications. In International Publication No. 2009/018009.

Polymer Pol-A is a non-crosslinked arylamine polymer (20 nm).
ELM-A and ELM-B are electroluminescent bis (diarylamino) chrysene compounds that emit blue light.

  Host A is a diarylanthracene compound.

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

In Example 1 of the device, 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 Example 5 of the device, the deuterated material was present in the electron transport layer. The electron transport layer was ET2 from Synthesis Example 6.

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

  In 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 anode thickness was 50 nm, and 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, and in Example 5, the thickness of the electron injection was 0.7 nm. The other layer materials and thicknesses are summarized in Table 1 below.

  The OLED device was made by using a combination of solution processing and thermal evaporation techniques. A glass substrate (from Thin Film Devices, Inc.) coated with patterned indium tin oxide (ITO) was used. Such an ITO substrate is based on Corning 1737 glass coated with ITO having a sheet resistance of 30 ohms / square and a light transmission of 80%. The patterned ITO substrate was cleaned using ultrasonic waves in a cleaning solution and rinsed with distilled water. The patterned ITO was then cleaned using ultrasound in acetone, rinsed with isopropanol, and dried with a stream of nitrogen.

  Just prior to device fabrication, the cleaned patterned ITO substrate was treated with ultraviolet ozone for 10 minutes. Immediately after cooling, an aqueous dispersion of the hole injection material was spin-coated so as to cover the ITO surface and heated to remove the solvent. After cooling, the substrate was then spin coated with a solution of hole transport material and then heated to remove the solvent. After cooling, the substrate was spin coated with the electroluminescent layer solution and heated to remove the solvent. The substrate was masked and placed in a vacuum chamber. The electron transport layer was deposited by thermal evaporation, and then the CsF layer was deposited as an electron injection layer. Next, the mask was changed in vacuum, and the Al layer was deposited by thermal evaporation to form a cathode. The chamber was degassed and the device was encapsulated with a glass lid, desiccant, and UV curable epoxy.

  OLED samples were characterized by measuring (1) current-voltage (IV) curves, (2) electroluminescence brightness vs. voltage, and (3) electroluminescence spectrum vs. voltage. All three types of measurements were performed and controlled simultaneously on a computer. The current efficiency of the device at a certain voltage is determined by dividing the electroluminescence brightness of the LED by the current required to operate the device. The unit is cd / A. Power efficiency is the current efficiency multiplied by pi and divided by the operating voltage. The unit is lm / W. Device data are shown in Tables 2 and 3.

  In this example, the time to reach 70% brightness was determined instead of the half-life. However, the calculated half-life will be much longer than the calculated time to reach 70% brightness. Thus, the half-life at 1000 nits is clearly longer than 10,000 hours.

Example 7 of device
This example illustrates an electronic device having a deuterated subbing layer formed by liquid deposition. Here, 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)
Undercoat layer: HT11 (20 nm)
Hole transport layer = Pol-A (20 nm)
Electroluminescent layer = host H14: dopant ELM-B is in a 13: 1 weight ratio (40 nm)
Electron transport layer = ET-A (10 nm)
Cathode = CsF / Al (1/100 nm)

  The OLED device was made by using a combination of solution processing and thermal evaporation techniques. A glass substrate (from Thin Film Devices, Inc.) coated with patterned indium tin oxide (ITO) was used. The ITO substrate is based on Corning 1737 glass coated with ITO having a sheet resistance of 30 ohms / square and a light transmission of 80%. The patterned ITO substrate was cleaned using ultrasonic waves in a cleaning solution and rinsed with distilled water. The patterned ITO was then cleaned using ultrasound in acetone, rinsed with isopropanol, and dried with a stream of nitrogen.

Just prior to device fabrication, the cleaned patterned ITO substrate was treated with ultraviolet ozone for 10 minutes. Immediately after cooling, an aqueous dispersion of HIJ-B was spin-coated so as to cover the ITO surface, and heated to remove the solvent. After cooling, an undercoat layer was formed by spin coating a toluene solution of HT11 on the hole injection layer. The subbing layer was exposed imagewise at 248 nm using a radiation dose of 100 mJ / cm ² . After exposure, the subbing layer was developed by spraying anisole while spinning at 2000 rpm for 60 seconds, spinning for 30 seconds and drying. 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 from the methyl benzoate solution by spin coating and then heated to remove the solvent. After cooling, the substrate was masked and placed in a vacuum chamber. The electron transport material was then deposited by thermal evaporation, followed by the CsF layer. The mask was then changed in vacuum and the Al layer was deposited by thermal evaporation. The chamber was degassed and the device was encapsulated with a glass lid, desiccant, and UV curable epoxy.

  The OLED sample had the characteristics as described above.

  The obtained device data is shown in Table 4.

Example 8 of device
This example illustrates 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)
Electroluminescence layer = host H14: dopant E13 is in a weight ratio of 86:14 (40 nm)
Electron transport layer = ET-A (10 nm)
Cathode = CsF / Al (0.7 / 100 nm)

  The OLED device was made as described in Device Example 1. The results are shown in Table 5.

  As shown by the data in the table, the device with at least one layer containing deuterated material had a calculated half-life of greater than 5000 hours. In device Example 3, the calculated half-life was greater than 50,000 hours.

  Not all of the tasks described above in the overview and examples are necessary, some of the specific tasks may not be necessary, and one or more additional tasks in addition to those described Note that can be performed. Still further, the order of operations listed is not necessarily the order in which they are performed.

  In the foregoing specification, each concept has 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. The specification and drawings are accordingly to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

  In the above, benefits, other advantages, and solutions to problems have been described with reference to specific embodiments. However, benefits, benefits, solutions to problems, and any features that may provide or make any benefit, advantage, or solution an important feature of any or all claims, essential It should not be interpreted as a feature or a basic feature.

  It should be understood that the specific features described herein in the context of separate embodiments may be combined in one embodiment for clarity. Conversely, various features that are described in the context of one embodiment for the sake of brevity may be provided separately or in any subcombination.

  Where numbers within the various ranges specified herein are used, they are shown as approximations, which are “about” to both the minimum and maximum values within the indicated range. It seems that the word is attached. Thus, slight change values above and below the indicated range can be used to obtain substantially the same results as values within that range. Also, such disclosed ranges include all values between the minimum and maximum average values (including fractional values that can occur when some of the components of one value are combined with the components of another value). It is intended to be a continuous range including. Further, where a wide range and a narrow range are disclosed, combining the minimum value of one range with the maximum value of another range and vice versa is also contemplated in the present invention.

Claims (17)

  An organic light emitting diode comprising an anode and a cathode and an organic active layer therebetween, wherein the organic active layer comprises a deuterium compound and the calculated half-life at 1000 nits of the device is at least 5000 hours Light emitting diode.   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 hole transporting deuterium compound having at least two diarylamino moieties per molecular formula unit.   The organic active layer is a deuterated polymer triarylamine, a deuterated polycarbazole, a deuterated polyfluorene, a deuterated polymer triarylamine having a conjugated portion bonded in a non-planar configuration. The organic light emitting diode of claim 1 comprising a material selected from the group consisting of: a class, a deuterated copolymer of fluorene and triarylamine, and combinations thereof.   The organic active layer comprises deuterated chrysenes, deuterated pyrenes, deuterated perylenes, deuterated rubrenes, deuterated perifuranthenes, deuterated fluoranthenes, deuterated stilbenes, deuterium. Comprising an electroluminescent compound selected from the group consisting of deuterated coumarins, deuterated anthracenes, deuterated thiadiazoles, deuterated spirobifluorenes, derivatives thereof, and mixtures thereof. The organic light emitting diode as described. The organic active layer has the following formula:

[Where:
A is an aromatic group which is the same or different at each occurrence and has 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, and the like Selected from the group consisting of substituted derivatives of and deuterated analogs thereof,
p and q are the same or different and each is an integer of 1 to 6]
An electroluminescent compound having one of
The organic light-emitting diode according to claim 1, wherein at least 10% of the compound is deuterated.   Electroluminescence wherein the organic active layer is selected from the group consisting of deuterated aminoanthracenes, deuterated aminocricenes, deuterated aminostilbenes, deuterated metal quinolate complexes, and deuterated iridium complexes The organic light emitting diode according to claim 1, comprising a compound.   The organic active layer comprises (a) deuterated anthracenes, deuterated chrysenes, deuterated pyrenes, deuterated phenanthrenes, deuterated triphenylenes, deuterated phenanthrolines, deuterated naphthalenes. Deuterated quinolines, deuterated isoquinolines, deuterated quinoxalines, deuterated deuterated phenylpyridines, deuterated dibenzofurans, deuterated difuranobenzenes, deuterated metal quinolinate complexes, At least one selected from the group consisting of deuterated indolocarbazoles, deuterated benzimidazoles, deuterated triazolopyridines, deuterated diheteroarylphenyls, substituted derivatives thereof, and combinations thereof A seed host material and (b) an electroluminescence having an emission maximum between 380 and 750 nm And at least one dopant capable, organic light emitting diode according to claim 1.   The host material is a deuterated diarylanthracene, a deuterated aminochrysene, a deuterated diarylchrysene, a deuterated diarylpyrene, a deuterated indolocarbazole, a deuterated phenanthroline, and their The organic light emitting diode according to claim 8, which is selected from the group consisting of combinations.   The organic active layer is composed of deuterated phenanthrolines, deuterated indolocarbazoles, deuterated benzimidazoles, deuterated triazolopyridines, deuterated diheteroarylphenyls, deuterated metal quinolates. The organic light-emitting diode according to claim 1, comprising an electron transport material selected from the group consisting of:   The active layer is a chemical confinement layer formed using an undercoat layer, and the undercoat layer comprises deuterated polymer triarylamines, deuterated polycarbazoles, deuterated polyfluorene. , Deuterated polymeric triarylamines having conjugated moieties attached in a non-planar configuration, deuterated copolymers of fluorene and triarylamine, deuterated metal quinolate derivatives, and combinations thereof The organic light emitting diode according to claim 1, comprising a material selected from:   The organic light emitting diode according to claim 1, further comprising a second active layer, wherein the second active layer includes a deuterium compound.   The organic light emitting diode of claim 1, wherein the calculated half-life at 1000 nits is at least 10,000 hours.   2. The organic light emitting diode according to 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 organic light emitting diode comprising an anode and a cathode and an organic layer therebetween, wherein the organic layer is a hole injection layer, a hole transport layer, an electroluminescence layer, an electron transport layer, and a cathode; An organic light emitting diode, wherein at least two of the organic layers consist essentially of deuterated materials.   The organic light emitting diode of claim 16, wherein all of the organic layer consists essentially of deuterated material.

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