KR20210147899A - Organic light emitting device - Google Patents

Abstract

The present invention relates to an organic light emitting diode including at least one light emitting material layer including a host in which an anthracene core is substituted with deuterium and a boron-based dopant, at least one electron blocking layer including an amine-based compound substituted with at least one spiro aryl group, and at least one hole blocking layer including an azine-based or benzimidazole-based compound as needed, and an organic light emitting device. According to the present invention, by applying an organic compound to the light emitting device, the luminescence efficiency of the element can be improved, and the luminescence lifespan can be drastically increased.

Description

Organic light emitting device {ORGANIC LIGHT EMITTING DEVICE}

The present invention relates to an organic light emitting device, and more particularly, to an organic light emitting device having significantly improved luminous efficiency and a light emitting lifetime of a device.

As one of the currently widely used flat panel display devices, an organic light emitting diode is attracting attention as a display device that quickly replaces a liquid crystal display device. Organic light emitting diodes (OLEDs) are formed of a thin organic thin film within 2000 Å, and images can be implemented in a single direction or in both directions depending on the configuration of an electrode used. In addition, since the organic light emitting display device can form an element on a flexible transparent substrate such as plastic, it is easy to implement a flexible or foldable display device. In addition, the organic light emitting display device can be driven at a low voltage and has excellent color purity, which has great advantages compared to the liquid crystal display device.

Conventional general fluorescent materials have low luminous efficiency because only singlet excitons participate in light emission. A phosphorescent material that also participates in light emission of triplet excitons has higher luminous efficiency than a fluorescent material. However, a metal complex, which is a typical phosphorescent material, has a short luminescence lifetime, so there is a limit to commercialization. In particular, the blue light emitting material is not satisfactory in terms of luminous lifespan and luminous efficiency as compared with other color luminescent materials. Therefore, there is a need to develop a compound or device structure with improved luminous efficiency and luminous lifetime.

SUMMARY OF THE INVENTION It is an object of the present invention to provide an organic light emitting diode having significantly improved luminous efficiency and luminous lifetime, and an organic light emitting device including the same.

The present invention is a substrate; and a first electrode, a second electrode facing the first electrode, at least one light emitting material layer positioned between the first electrode and the second electrode, and the first electrode and the at least one light emitting material a light emitting layer including at least one electron blocking layer positioned between the layers, wherein the at least one light emitting material layer includes a first host that is an anthracene-based compound and a first dopant that is a boron-based compound, wherein the first The anthracene core of the host is substituted with deuterium, the first dopant has a structure of the following formula (3), and the at least one electron blocking layer includes an organic light emitting diode including an amine-based compound having a structure of the following formula (5) An organic light emitting device is provided.

[Formula 3]

In Formula 3, _{each of R 11} to R _{14 ,} each of R ₂₁ to R _{24 ,} each of R ₃₁ to R _{35 , and} each of R ₄₁ to R ₄₅ are independently hydrogen, deuterium, C ₁ -C ₁₀ alkyl, C ₆ -C ₃₀ selected from the group consisting of aryl, C ₆ -C ₃₀ arylamino and C ₅ -C _{30 heteroaryl, R 11} to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₅ are each other may be the same or different, and the C ₆ -C ₃₀ aryl may each independently be unsubstituted or substituted with C ₁ -C ₁₀ alkyl; R ₅₁ is selected from the group consisting of hydrogen, deuterium, C ₁ -C ₁₀ alkyl and C ₃ -C _{15 cycloalkyl.}

[Formula 5]

In Formula 5, L ₂ is a C ₆ ~ C ₃₀ arylene group; c is 0 or 1; R ₆₁ to R ₆₄ are each independently C ₆ ~ C ₃₀ aryl or C ₅ ~ C ₃₀ heteroaryl, C ₆ ~ C ₃₀ aryl C ₅ ~ C ₃₀ and heteroaryl are each independently unsubstituted or C ₁ -C ₁₀ May be substituted with at least one of an alkyl group and C ₆ -C _{30 aryl.}

For example, the first host may include an anthracene-based compound having the structure of Formula 1 below.

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, L ₁ is C ₆ -C ₃₀ arylene, a is an integer of 0 or 1, b is an integer from 1 to 8;

In the organic light emitting device of the present invention, the light emitting layer may further include an electron transport layer or at least one hole blocking layer including an azine-based compound and/or a benzimidazole-based compound.

In the organic light emitting device of the present invention, the light emitting layer may consist of a single light emitting unit or may have a tandem structure including a plurality of light emitting units.

For example, in the organic light emitting device of the present invention, the light emitting layer is positioned between the first electrode and the second electrode, and between the first light emitting material layer and the first electrode and the first light emitting material layer. A first light emitting unit including a first electron blocking window positioned, a second light emitting unit positioned between the first light emitting unit and the second electrode, and including a second light emitting material layer, and the first light emitting unit and a first charge generation layer positioned between the second light emitting unit, wherein at least one of the first light emitting material layer and the second light emitting material layer includes the first host and the first dopant have. The organic light emitting diode having a tandem structure may emit light in blue (B) or selectively emit light in white (W).

In the organic light emitting device of the present invention, a red pixel, a green pixel and a blue pixel are defined on the substrate, and the organic light emitting diode corresponds to the red pixel, the green pixel and the blue pixel, respectively, the red pixel and the green color A color conversion layer may further include a color conversion layer disposed between the substrate and the organic light emitting diode or on the organic light emitting diode corresponding to the pixel.

In the organic light emitting device of the present invention, a red pixel, a green pixel and a blue pixel are defined on the substrate, and the organic light emitting diode corresponds to the red pixel, the green pixel and the blue pixel, respectively, the red pixel and the green color The display device may further include a color filter layer disposed between the substrate and the organic light emitting diode or on the organic light emitting diode corresponding to the pixel and the blue pixel.

The organic light emitting diode according to the present invention comprises at least one light emitting material layer including a first host, which is an anthracene-based compound, in which only an anthracene core is substituted with deuterium, and a boron-based dopant, and at least one amine-based compound substituted with an aryl group with a spiro. It has at least one electron blocking layer including, and at least one hole blocking layer, optionally including an azine-based and/or benzimidazole-based compound.

In a light emitting device that implements blue (B) light emission, which has been considered a weakness in conventional organic light emitting devices, while minimizing an increase in manufacturing cost by introducing a compound in which only the anthracene core is substituted with deuterium as the first host used in the light emitting material layer The luminous efficiency and luminous lifetime are improved. Optionally, by substituting a dopant, which is a boron compound, with deuterium, it is possible to implement an organic light emitting diode and an organic light emitting device that maximizes luminous efficiency and light emitting lifetime while emitting blue light.

1 is a schematic circuit diagram of an organic light emitting diode display according to an exemplary embodiment of the present invention.
2 is a cross-sectional view schematically illustrating an organic light emitting display device as an example of an organic light emitting diode having an organic light emitting diode according to the first exemplary embodiment of the present invention.
3 is a cross-sectional view schematically illustrating an organic light emitting diode used in an organic light emitting diode display according to the first exemplary embodiment of the present invention, and having a single organic light emitting layer.
4 is a cross-sectional view schematically illustrating an organic light emitting diode having a double stack structure as an organic light emitting diode used in the organic light emitting diode display according to the first exemplary embodiment of the present invention.
5 is a cross-sectional view schematically illustrating an organic light emitting display device according to a second exemplary embodiment of the present invention.
6 is a cross-sectional view schematically illustrating an organic light emitting diode having a double stack structure as an organic light emitting diode used in an organic light emitting diode display according to a second exemplary embodiment of the present invention.
7 is a cross-sectional view schematically illustrating an organic light emitting diode having a triple stack structure as an organic light emitting diode used in an organic light emitting diode display according to a second exemplary embodiment of the present invention.
8 is a cross-sectional view schematically illustrating an organic light emitting display device according to another exemplary embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings, if necessary.

According to the present invention, by applying a predetermined series of organic compounds to at least one light emitting unit constituting the light emitting device, it is possible to improve the luminous efficiency and light emitting lifetime of the light emitting device. The light emitting device according to the present invention can be applied to an organic light emitting device such as an organic light emitting display device or a lighting device to which an organic light emitting diode is applied. As an example, a display device to which an organic light emitting diode according to the present invention is applied will be described.

1 is a schematic circuit diagram of an organic light emitting diode display according to an exemplary embodiment of the present invention. As shown in FIG. 1 , in the organic light emitting display device, a gate line GL that crosses each other to define a pixel region P, a data line DL and a power line PL are formed, and the pixel region P is formed. ), a switching thin film transistor (Ts), a driving thin film transistor (Td), a storage capacitor (Cst), and an organic light emitting diode (D) are formed. The pixel region P may include a red (R) pixel region, a green (G) pixel region, and a blue (B) pixel region.

The switching thin film transistor Ts is connected to the gate line GL and the data line DL, and the driving thin film transistor Td and the storage capacitor Cst are connected between the switching thin film transistor Ts and the power line PL. do. The organic light emitting diode D is connected to the driving thin film transistor Td. In such an organic light emitting display device, when the switching thin film transistor Ts is turned on according to the gate signal applied to the gate line GL, the data signal applied to the data line DL is applied to the switching thin film transistor It is applied to the gate electrode of the driving thin film transistor Td and one electrode of the storage capacitor Cst through Ts.

The driving thin film transistor Td is turned on according to the data signal applied to the gate electrode, and as a result, a current proportional to the data signal is transmitted from the power line PL through the driving thin film transistor Td to the organic light emitting diode D , and the organic light emitting diode D emits light with a luminance proportional to the current flowing through the driving thin film transistor Td. At this time, the storage capacitor Cst is charged with a voltage proportional to the data signal so that the voltage of the gate electrode of the driving thin film transistor Td is constantly maintained for one frame. Accordingly, the organic light emitting display device can display a desired image.

2 is a cross-sectional view schematically illustrating an organic light emitting display device according to a first exemplary embodiment of the present invention. As shown in FIG. 2 , the organic light emitting diode display 100 includes a thin film transistor Tr and an organic light emitting diode D connected to the thin film transistor Tr. For example, a red pixel, a green pixel, and a blue pixel are defined on the substrate 102 , and the organic light emitting diode D is positioned for each pixel. That is, the organic light emitting diodes D emitting red, green, and blue light, respectively, are provided in the red pixel, the green pixel, and the blue pixel, respectively.

The substrate 102 may be a glass substrate, a thin flexible substrate, or a polymer plastic substrate. For example, the substrate 102 may include polyimide (PI), polyethersulfone (PES), polyethylenenaphthalate (PEN), polyethylene terephthalate (PET), and polycarbonate; PC) may be formed. The thin film transistor Tr and the substrate 102 on which the organic light emitting diode 200 is positioned form an array substrate.

A buffer layer 106 is formed on the substrate 102 , and a thin film transistor Tr is formed on the buffer layer 106 . The buffer layer 106 may be omitted.

The semiconductor layer 110 is formed on the buffer layer 106 . For example, the semiconductor layer 110 may be formed of an oxide semiconductor material. When the semiconductor layer 110 is made of an oxide semiconductor material, a light blocking pattern (not shown) may be formed under the semiconductor layer 110 . The light blocking pattern (not shown) prevents light from being incident on the semiconductor layer 110 and prevents the semiconductor layer 110 from being deteriorated by the light. Alternatively, the semiconductor layer 110 may be made of polycrystalline silicon, and in this case, both edges of the semiconductor layer 110 may be doped with impurities.

A gate insulating layer 120 made of an insulating material is formed on the entire surface of the substrate 102 on the semiconductor layer 110 . The gate insulating layer 120 may be made of an inorganic insulating material such as _{silicon oxide (SiO 2 ) or silicon nitride (SiNx).}

A gate electrode 130 made of a conductive material such as metal is formed on the gate insulating layer 120 to correspond to the center of the semiconductor layer 110 . Although the gate insulating layer 120 is formed on the entire surface of the substrate 102 in FIG. 2 , the gate insulating layer 120 may be patterned to have the same shape as the gate electrode 130 .

An interlayer insulating film 140 made of an insulating material is formed on the entire surface of the substrate 102 on the gate electrode 130 . The interlayer insulating layer 140 _{may be formed of an inorganic insulating material such as silicon oxide (SiO 2} ) or silicon nitride (SiNx), or an organic insulating material such as benzocyclobutene or photo-acryl. have.

The interlayer insulating layer 140 has first and second semiconductor layer contact holes 142 and 144 exposing upper surfaces of both sides of the semiconductor layer 110 . The first and second semiconductor layer contact holes 142 and 144 are positioned at both sides of the gate electrode 130 to be spaced apart from the gate electrode 130 . In FIG. 2 , it is shown that the first and second semiconductor layer contact holes 142 and 144 are also formed in the gate insulating layer 120 . In contrast, when the gate insulating layer 120 is patterned to have the same shape as the gate electrode 130 , the first and second semiconductor layer contact holes 142 and 144 are formed only in the interlayer insulating layer 140 .

A source electrode 152 and a drain electrode 154 made of a conductive material such as metal are formed on the interlayer insulating layer 140 . The source electrode 152 and the drain electrode 154 are positioned to be spaced apart from the center of the gate electrode 130 , respectively, to both sides of the semiconductor layer 110 through the first and second semiconductor layer contact holes 142 and 144 , respectively. contact

The semiconductor layer 110 , the gate electrode 130 , the source electrode 152 , and the drain electrode 154 form a thin film transistor Tr, and the thin film transistor Tr functions as a driving element. The thin film transistor Tr illustrated in FIG. 2 has a coplanar structure in which the gate electrode 130 , the source electrode 152 , and the drain electrode 154 are positioned on the semiconductor layer 110 . Alternatively, the thin film transistor Tr may have an inverted staggered structure in which a gate electrode is positioned under a semiconductor layer and a source electrode and a drain electrode are positioned above the semiconductor layer. In this case, the semiconductor layer may be made of amorphous silicon.

Although not shown in FIG. 2 , the gate line and the data line cross each other to define a pixel area, and a switching element connected to the gate line and the data line is further formed. The switching element is connected to a thin film transistor Tr as a driving element. In addition, the power wiring is formed to be spaced apart from the data wiring or the data wiring in parallel, and a storage capacitor is further configured to keep the voltage of the gate electrode of the thin film transistor Tr as the driving element constant during one frame. can

A protective layer 160 is formed on the source electrode 152 and the drain electrode 154 over the entire surface of the substrate 102 to cover the thin film transistor Tr. The protective layer 160 has a flat top surface and has a drain contact hole 162 exposing the drain electrode 154 of the thin film transistor Tr. Here, the drain contact hole 162 is illustrated as being formed directly on the second semiconductor layer contact hole 144 , but may be formed to be spaced apart from the second semiconductor layer contact hole 144 .

The organic light emitting diode (D) is positioned on the protective layer 160 and is sequentially stacked on the first electrode 210 connected to the drain electrode 154 of the thin film transistor Tr, and the first electrode 210 . It includes an organic light emitting layer 230 and a second electrode 220 .

One electrode 210 is formed separately for each pixel area. The first electrode 210 may be an anode, and may be made of a conductive material having a relatively large work function value. For example, the first electrode 210 may be formed of a transparent conductive oxide (TCO). Specifically, the first electrode 210 is indium-tin-oxide (ITO), indium-zinc-oxide (IZO), indium-tin-zinc-oxide (indium-) It may be made of tin-zinc oxide (ITZO), tin oxide (SnO), zinc oxide (ZnO), indium-copper-oxide (ICO), and aluminum:zinc oxide (Al:ZnO; AZO). .

Meanwhile, when the organic light emitting diode display 100 of the present invention is a top-emission type, a reflective electrode or a reflective layer may be further formed under the first electrode 210 . For example, the reflective electrode or the reflective layer may be made of an aluminum-palladium-copper (APC) alloy.

In addition, a bank layer 164 covering an edge of the first electrode 210 is formed on the passivation layer 160 . The bank layer 164 exposes the center of the first electrode 210 corresponding to the pixel area.

An organic light emitting layer 230 is formed on the first electrode 210 . In one exemplary embodiment, as shown in FIGS. 3 and 4 , the organic light emitting layer 230 includes a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer ( electron blocking layer (EBL), emitting material layer (EML), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL) and and/or a charge generation layer (CGL). The organic light emitting layer 230 may be formed of a single light emitting unit, and two or more light emitting units may form a tandem structure.

The organic light emitting layer 230 may include at least one light emitting material layer including an anthracene-based host and boron-based dopant, and at least one electron blocking layer including a spiroaryl amine-based compound. Optionally, the organic emission layer 230 includes at least one hole blocking layer including an azine-based compound and/or a benzimidazole-based compound. By introducing the organic light-emitting layer 230 , the light-emitting efficiency and light-emitting lifetime of the organic light-emitting diode D and the organic light-emitting display device 100 can be greatly improved, which will be described later.

The second electrode 220 is formed on the substrate 102 on which the organic emission layer 230 is formed. The second electrode 220 may be positioned on the entire surface of the display area and may be a conductive material having a relatively small work function value and may be a cathode for injecting electrons. For example, the second electrode 220 may include aluminum (Al), magnesium (Mg), calcium (ca), silver (Ag), or an alloy or combination thereof (eg, aluminum-magnesium alloy (AlMg)) and It may be made of a material having the same reflective properties.

On the second electrode 220, an encapsulation film 170 is formed in order to prevent external moisture from penetrating into the organic light emitting diode (D). The encapsulation film 170 may have a stacked structure of the first inorganic insulating layer 172 , the organic insulating layer 174 , and the second inorganic insulating layer 176 , but is not limited thereto. The encapsulation film 170 may be omitted.

A polarizing plate (not shown) for reducing reflection of external light may be attached on the encapsulation film 170 . For example, the polarizing plate (not shown) may be a circular polarizing plate. In addition, a cover window (not shown) may be attached to the encapsulation film 170 or a polarizing plate (not shown). In this case, since the substrate 102 and the cover window (not shown) have flexible characteristics, a flexible display device may be configured.

As described above, by introducing a specific series of organic compounds into the organic light emitting layer 230, an organic light emitting diode having improved light emitting efficiency and light emitting lifetime can be implemented. An organic light emitting diode according to the present invention will be described. 3 is a cross-sectional view schematically illustrating an organic light emitting diode having one light emitting unit according to an exemplary embodiment of the present invention.

As shown in FIG. 3 , the organic light emitting diode D1 according to the exemplary embodiment of the present invention has a first electrode 210 and a second electrode 220 facing each other, and the first and second electrodes 210 and 220 . ) and an organic light emitting layer 230 positioned between them. In the exemplary embodiment, the organic light emitting layer 230 includes an emitting material layer (EML) 340 positioned between the first and second electrodes 210 and 220 , the first electrode 210 and the light emitting material An electron blocking layer (EBL) 330 which is a first exciton blocking layer positioned between the layers 340 and a second exciton blocking layer positioned between the light emitting material layer 340 and the second electrode 220 . It may include a hole blocking layer (HBL, 350).

In addition, the organic light emitting layer 230 includes a hole injection layer (HIL) 310 positioned between the first electrode 210 and the electron blocking layer 330, a hole injection layer 310 and an electron blocking layer ( 330) may include a hole transfer layer (HTL, 320) located between. In addition, the organic emission layer 230 includes an electron injection layer (EIL) 360 positioned between the hole blocking layer 320 and the second electrode 220 . In an optional embodiment, the organic emission layer 230 may further include an electron transfer layer (ETL) positioned between the hole blocking layer 350 and the electron injection layer 360 .

The first electrode 210 may be an anode for supplying holes to the light emitting material layer 360 . The first electrode 210 is preferably formed of a conductive material having a relatively high work function value, for example, a transparent conductive oxide (TCO). For example, the first electrode 210 may include indium-tin-oxide (ITO), indium-zinc-oxide (IZO), or indium-tin-zinc-oxide (indium). -tin-zinc oxide (ITZO), tin oxide (SnO), zinc oxide (ZnO), indium-copper-oxide (ICO) and aluminum:zinc oxide (Al:ZnO; AZO) have.

The second electrode 220 may be a cathode for supplying electrons to the light emitting material layer 340 . The second electrode 220 has a reflective characteristic such as a conductive material having a relatively small work function value, for example, aluminum (Al), magnesium (Mg), calcium (Ca), silver (Ag), or an alloy or combination thereof. It can be made of good material. For example, the first electrode 210 and the second electrode 320 may be stacked to a thickness of 30 to 300 nm, respectively.

The light emitting material layer 340 includes a first host 342 that is an anthracene-based compound and a first dopant 344 that is a boron-based compound, and emits blue light. In this case, the anthracene core constituting the anthracene-based compound serving as the first host 342 is substituted with deuterium. In addition, in the boron-based compound serving as the first dopant 344 , some or all of hydrogen may be substituted with deuterium. In other words, the anthracene core of the first host 342 may be substituted with deuterium, and the first dopant 344 may not be substituted with deuterium, or some or all of hydrogen may be substituted with deuterium. For example, the first host 342, which is an anthracene-based compound in which an anthracene core is substituted with deuterium, may have the structure of Formula 1 below.

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, L ₁ is C ₆ -C ₃₀ arylene, a is an integer of 0 or 1, b is an integer from 1 to 8;

That is, in the anthracene-based compound constituting the first host 342 , at least one of the remaining hydrogens except for the substituents of the anthracene moiety constituting the core is substituted with deuterium (D), and the substituents (R ₁ , R ₂ , L _{1 )} ) is not substituted with deuterium. For example, in Formula 1, R ₁ and R ₂ are each independently phenyl, naphthyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, It may be selected from phenanthrenyl, carbazolyl, and carbolinyl, and preferably phenyl or naphthyl (eg, 1-naphthyl or 2-naphthyl). Meanwhile, L ₁ may be phenylene or naphthylene, and b may be 8.

In an exemplary embodiment, the first host 342 may be any one compound having the structure of Formula 2 below.

[Formula 2]

Meanwhile, the first dopant 344 , which is a boron-based compound emitting blue light, may have a structure of Formula 3 below.

[Formula 3]

In Formula 3, _{each of R 11} to R _{14 ,} each of R ₂₁ to R _{24 ,} each of R ₃₁ to R _{35 , and} each of R ₄₁ to R ₄₅ are independently hydrogen, deuterium, C ₁ -C ₁₀ alkyl, C ₆ -C ₃₀ selected from the group consisting of aryl, C ₆ -C ₃₀ arylamino and C ₅ -C _{30 heteroaryl, R 11} to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₅ are each other may be the same or different, and the C ₆ -C ₃₀ aryl may each independently be unsubstituted or substituted with C ₁ -C ₁₀ alkyl; R ₅₁ is selected from the group consisting of hydrogen, deuterium, C ₁ -C ₁₀ alkyl and C ₃ -C _{15 cycloalkyl.}

When _{aryl or arylamino which may be R 11} to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₅ is substituted, the substituent is C ₁ -C ₁₀ alkyl, for example tert- It may be a _{C 1} -C ₅ alkyl such as butyl.

_{At least one of deuterium, C 1} -C ₁₀ alkyl, C ₆ -C ₃₀ aryl and C ₆ -C ₃₀ arylamino in a benzene ring connected to boron and two nitrogens in the boron-based compound as the first dopant 344 is substituted, and the light emitting characteristic of the organic light emitting diode D1 is improved.

More specifically, _{the arylamino which may be R 11} to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₅ may be diphenylamine or phenyl-naphthylamine, and R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₅ aryl which may be unsubstituted or substituted with at least 1, for example 1-2 C ₁ -C ₁₀ alkyl groups, phenyl or may be naphthyl. Alkyl which may be R ₁₁ to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R _{45 is C 1} such as methyl, ethyl, propyl, butyl (eg tert-butyl), pentyl -C ₅ alkyl. In this case, arylamino, aryl and alkyl constituting each substituent may be further substituted with deuterium.

In addition, R ₅₁ may be selected from the group consisting of hydrogen, deuterium, C ₁ -C ₁₀ alkyl (eg, methyl, methyl, ethyl, propyl, butyl, pentyl) and adamantanyl.

In one exemplary embodiment, one of R ₁₁ -R ₁₄ , one of R ₂₁ - R ₂₄ , one of R ₃₁ - R ₃₅ , one of R ₄₁ - R ₄₅ can each be tert-butyl, and R ₁₁ The remainder of to R14, the remainder of R ₂₁ to R ₂₄ , the remainder of R ₃₁ to R ₃₅ , and the remainder of R ₄₁ to R ₄₅ may be hydrogen or deuterium, and R ₅₁ may be hydrogen, deuterium, or methyl.

In another exemplary embodiment, one of R ₁₁ -R ₁₄ , R ₂₁ - R ₂₄ , one of R ₃₁ - R ₃₅ , one of R ₄₁ - R ₄₅ is tert-butyl and the other of R ₃₁ - R ₃₅ one is tert-butylphenyl _{, the remainder of R 11} to R ₁₄ , the remainder of R ₂₁ to R24, the remainder of R ₃₁ to R ₃₅ , the remainder of R ₄₁ to R ₄₅ is hydrogen or deuterium, R ₅₁ is hydrogen, deuterium or methyl.

For example, the first dopant 344, which is a boron-based compound, may include any one compound having the structure of Chemical Formula 4 below.

[Formula 4]

For example, the first dopant 344, which is a boron-based compound, may be doped in the light emitting material layer 340 at a ratio of 1 to 50 wt%, preferably 1 to 30 wt%. The light emitting material layer 340 may be formed to a thickness of 10 to 200 nm, preferably 20 to 100 nm, more preferably 20 to 50 nm, but the present invention is not limited thereto.

The hole injection layer 310 is positioned between the first electrode 210 and the hole transport layer 320 , and improves the interface characteristics between the inorganic first electrode 210 and the organic hole transport layer 320 . In one exemplary embodiment, the hole injection layer 310 may include 4,4',4"-tris(3-methylphenylamino)triphenylamine (4,4',4"-Tris(3-methylphenylamino)triphenylamine; MTDATA), 4,4',4"-tris(N,N-diphenyl-amino)triphenylamine (4,4',4"-Tris(N,N-diphenyl-amino)triphenylamine; NATA), 4 ,4′,4″-Tris(N-(naphthalene-1-yl)-N-phenyl-amino)triphenylamine(4,4′,4″-Tris(N-(naphthalene-1-yl)-N -phenyl-amino)triphenylamine; 1T-NATA), 4,4',4"-tris(N-(naphthalen-2-yl)-N-phenyl-amino)triphenylamine (4,4',4"- Tris(N-(naphthalene-2-yl)-N-phenyl-amino)triphenylamine; 2T-NATA), Copper phthalocyanine (CuPc), Tris(4-carbazolyl-9yl-phenyl)amine (Tris( 4-carbazoyl-9-yl-phenyl)amine; TCTA), N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine (N,N'-Diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine; NPB; NPD), 1,4,5,8,9,11 -Hexaazatriphenylenehexacarbonitrile (1,4,5,8,9,11-Hexaazatriphenylenehexacarbonitrile, Dipyrazino[2,3-f:2'3'-h]quinoxaline-2,3,6,7,10 ,11-hexacarbonitrile; HAT-CN), 1,3,5-tris[4-(diphenylamino)phenyl]benzene (1,3,5-tris[4-(diphenylamino)phenyl]benzene; TDAPB), poly (3,4-ethylenedioxythiophene)polystyrene sulfonate (poly(3,4-ethylenedioxythiphene)polystyrene sulfonate; PEDOT/PSS), N-(biphenyl-4-yl)-9,9- Dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine(N-(biphenyl-4-yl)-9,9-dimethyl-N -(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine) and/or a compound having a structure of Formula 12 below, but is not limited thereto.

[Formula 12]

In an alternative embodiment, the hole injection layer 310 may be formed by doping a hole transport material to be described later with the hole injection material described above. In this case, the hole injection material may be doped in a proportion of approximately 1 to 50% by weight, preferably 1 to 30% by weight. Depending on the characteristics of the organic light emitting diode D1, the hole injection layer 310 may be omitted.

The hole transport layer 320 is positioned between the first electrode 210 and the electron blocking layer 330 and adjacent to the electron blocking layer 330 . In one exemplary embodiment, the hole transport layer 320 is N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (N ,N'-Diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine; TPD), NPB(NPD), 4,4'-bis(N-carba) Zolyl)-1,1'-biphenyl (4,4'-bis(N-carbazolyl)-1,1'-biphenyl; CBP), poly[N,N'-bis(4-butylphenyl)-N, N'-bis(phenyl)-benzidine](Poly[N,N'-bis(4-butylpnehyl)-N,N'-bis(phenyl)-benzidine]; Poly-TPD), poly[(9,9- Dioxylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))](Poly[(9,9-dioctylfluorenyl-2, 7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], TFB), di-[4-(N,N-di-p-tolyl-amino)phenyl ]cyclohexane (Di-[4-(N,N-di-p-tolyl-amino)-phenyl]cyclohexane; TAPC), 3,5-di(9H-carbazol-9-yl)-N,N- Diphenylaniline (3,5-Di(9H-carbazol-9-yl)-N,N-diphenylaniline; DCDPA), N-(biphenyl-4-yl)-9,9-dimethyl-N-(4- (9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine (N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9- phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine), N-(biphenyl]-4-yl)-N-(4-(9-phenyl-9H-carbazole-3 -yl) phenyl) biphenyl) -4-amine (N- (biphenyl-4-yl) -N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) biphenyl-4-amine), N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene -2-amine (N -([1,1'-Biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine ), N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine (N4,N4, N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine) and/or a compound having the structure of Formula 11 may be included, but is not limited thereto.

[Formula 11]

In an exemplary embodiment, the hole injection layer 310 and the hole transport layer 320 may be laminated to a thickness of 5 nm to 200 nm, preferably 5 nm to 100 nm, respectively, but the present invention is not limited thereto.

The electron blocking layer 330 prevents electrons from moving to the first electrode 210 through the light emitting material layer 340 . The electron blocking layer 330 may include a spiroaryl amine-based compound having a structure of the following Chemical Formula 5.

[Formula 5]

In Formula 5, L ₂ is a C ₆ ~ C ₃₀ arylene group; c is 0 or 1; R ₆₁ and R ₆₂ are each independently C ₆ ~ C ₃₀ aryl or C ₅ ~ C ₃₀ heteroaryl, C ₆ ~ C ₃₀ aryl C ₅ ~ C ₃₀ and hetero aryl are each independently unsubstituted or C ₁ -C ₁₀ May be substituted with at least one of an alkyl group and C ₆ -C _{30 aryl.}

For example, in Formula 5, L ₂ may be a phenylene group, R ₆₁ and R ₆₂ are each independently unsubstituted, or a C ₁ ~ C ₁₀ alkyl group and a C ₆ ~ C ₃₀ aryl group (eg, a phenyl group) It may be a phenyl group, a biphenyl group, a fluorenyl group, a carbazolyl group, a phenylcarbazolyl group, a carbazolylphenyl group, a dibenzofuranyl group, or a dibenzothiophenyl group, which may be substituted with at least one of them.

For example, the electron blocking layer 330 may include any one of the spiroaryl amine-based compound having the structure of the following Chemical Formula 6.

[Formula 6]

Optionally, the organic light emitting diode D1 may include a hole blocking layer 350 to prevent holes from moving to the second electrode 220 through the light emitting material layer 340 . For example, the hole blocking layer 350 may include an azine-based compound having a structure of Chemical Formula 7 and/or a benzimidazole-based compound having a structure of Chemical Formula 9 below.

[Formula 7]

In Formula 7, Y ₁ to Y ₅ are each independently CR ₇₁ or nitrogen (N), 1 to 3 of which are nitrogen, and R ₇₁ is C ₆ -C ₃₀ aryl; L ₃ is a C ₆ -C ₃₀ arylene group; R ₇₂ is C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, C ₆ -C ₃₀ aryl is unsubstituted, substituted with another C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, or may form a spiro structure with a C ₁₀ -C ₃₀ fused aryl ring or a C ₁₀ -C ₃₀ fused heteroaryl ring, wherein the other C ₆ -C ₃₀ aryl is unsubstituted, another C ₆ -C ₃₀ aryl or may be substituted with another C ₅ -C ₃₀ heteroaryl, or form a spiro structure with a _{C 10} -C _{30 condensed aryl ring;} R ₇₃ is hydrogen or adjacent groups combine to form a fused aromatic ring; f is 0 or 1, g is 1 or 2, and h is an integer from 0 to 4.

[Formula 9]

In Formula 9, Ar is a C ₁₀ -C ₃₀ arylene group; R ₈₁ is C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, C ₆ -C ₃₀ aryl and C ₅ -C ₃₀ heteroaryl may each be unsubstituted or substituted with C ₁ -C ₁₀ alkyl; R ₈₂ and R ₈₃ are each independently hydrogen, C ₁ -C ₁₀ alkyl or C ₆ -C ₃₀ aryl.

For example, in Formula 7, _{the aromatic substituent constituting R 72} is unsubstituted, substituted with another C ₆ -C ₃₀ aryl group or C ₅ -C ₃₀ heteroaryl group, or another condensed aryl ring or condensed heteroaryl ring and Spies can form structures. For example, the aromatic functional group that may be substituted for _{R 72 may be a C 10} ~ C ₃₀ condensed aryl group or a condensed heteroaryl group. In Formula 7, R ₇₃ may be condensed to form a naphthyl group.

For example, the hole blocking layer 350 may include any one azine-based compound having a structure of the following Chemical Formula 8.

[Formula 8]

Meanwhile, in Formula 9, Ar may be a naphthylene group or an anthracenylene group, R ₈₁ may be a phenyl group or a benzimidazolyl group, R ₈₂ may be a methyl group, an ethyl group, or a phenyl group, and R ₈₃ is hydrogen, a methyl group, or It may be a phenyl group. For example, the benzimidazole-based compound applicable to the hole blocking layer 350 may include any one benzimidazole-based compound having a structure of the following Chemical Formula 10.

[Formula 10]

In an exemplary embodiment, the electron blocking layer 330 and the hole blocking layer 350 may be laminated to a thickness of 5 nm to 200 nm, preferably 5 nm to 100 nm, respectively, but the present invention is not limited thereto. .

The azine-based and/or benzimidazole-based compounds represented by Chemical Formulas 7 to 10 have excellent hole blocking ability as well as excellent electron transport properties. In this case, the hole blocking layer 350 may function as a hole blocking layer and an electron transport layer.

In an optional embodiment, the organic light emitting diode D1 may include an electron transport layer (not shown) between the hole blocking layer 350 and the electron injection layer 360 . Electron transport layer (not shown) is oxadiazole-base, triazole-base, phenanthroline-base, benzoxazole-based, benzothiazole-base ), benzimidazole-based (benzimidazole-base), and may include derivatives such as triazine-base.

For example, the electron transport layer (not shown) is tris (8-hydroxyquinoline) aluminum (tris- (8-hydroxyquinoline aluminum; Alq ₃ ), 2-biphenyl-4-yl-5- (4-tertiary- Butylphenyl)-1,3,4-oxadiazole (2-biphenyl-4-yl-5-(4-t-butylphenyl)-1,3,4-oxadiazole; PBD), spiro-PBD, lithium quinol Lithium quinolate (Liq), 1,3,5-tris (N-phenylbenzimidazol-2-yl)benzene (1,3,5-Tris (N-phenylbenzimidazol-2-yl)benzene; TPBi), Bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-biphenyl-4-olato)aluminum (Bis(2-methyl-8-quinolinolato-N1,O8)-( 1,1'-biphenyl-4-olato)aluminum; BAlq), 4,7-diphenyl-1,10-phenanthroline (4,7-diphenyl-1,10-phenanthroline; Bphen), 2,9- bis(naphthalen-2-yl)4,7-diphenyl-1,10-phenanthroline (2,9-Bis(naphthalene-2-yl)4,7-diphenyl-1,10-phenanthroline; NBphen); 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-Dimethyl-4,7-diphenyl-1,10-phenathroline; BCP), 3-(4-biphenyl) -4-phenyl-5-tert-butylphenyl-1,2,4-triazole (3- (4-Biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole; TAZ), 4-(Naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (4-(Naphthalen-1-yl)-3,5-diphenyl-4H-1,2, 4-triazole; NTAZ), 1,3,5-tri(p-pyrid-3-yl-phenyl)benzene (1,3,5-Tri(p-pyrid-3-yl-phenyl)benzene; TpPyPB) , 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)1,3,5-triazine (2,4,6-Tris(3'-(p yridin-3-yl)biphenyl-3-yl)1,3,5-triazine; TmPPPyTz), poly[(9,9-bis(3′-((N,N-dimethyl)-N-ethylammonium)-propyl)-2,7-fluorene)-alt-2,7-(9, 9-dioctylfluorene)](Poly[9,9-bis(3'-((N,N-dimethyl)-N-ethylammonium)-propyl)-2,7-fluorene]-alt-2,7- (9,9-dioctylfluorene)]; PFNBr), tris(phenylquinoxaline) (tris(phenylquinoxaline; TPQ), diphenyl-4-triphenylsilyl-phenylphosphine oxide; TSPO1 ), 2-[4-(9,10-di-naphthalen-2-yl-anthracen-2-yl)phenyl)]-1-phenyl-1H-benzimidazole (2-[4-(9,10- Di-2-naphthalen2-yl-2-anthracen-2-yl)phenyl]-1-phenyl-1H-benzimidazole; ZADN), 1,3-bis(9-phenyl-1,10-phenanthroline-2- yl)benzene (1,3-bis(9-phenyl-1,10-phenathrolin-2-yl)benzene), 1,4-bis(2-phenyl-1,10-phenanthrolin-4-yl)benzene (1,4-bis(2-phenyl-1,10-phenanthrolin-4-yl)benzene; p-bPPhenB) and/or 1,3-bis(2-phenyl-1,10-phenanthroline)-4 It may include an electron transport material such as -yl)benzene (1,3-bis(2-phenyl-1,10-phenanthrolin-4-yl)benzene; m-bPPhenB), but the present invention is not limited thereto.

The electron injection layer 360 is positioned between the hole blocking layer 350 and the second electrode 220 , and by improving the characteristics of the second electrode 220 , the lifespan of the device may be improved. In an exemplary embodiment, the electron injection layer 360 is _{an alkali halide-based material such as LiF, CsF, NaF, BaF 2} , and/or Liq (lithium quinolate), lithium benzoate, sodium stearate. ) and the like may be used, but the present invention is not limited thereto.

In an alternative embodiment, the electron injection layer 360 may be an organic layer doped with an alkali metal such as Li, Na, K, Cs and/or an alkaline earth metal such as Mg, Sr, Ba, Ra. The organic host used for the electron injection layer 360 may be the aforementioned electron transport material, and may be doped with an alkali metal or alkaline earth metal in an amount of about 1 to 30 wt%.

For example, the electron transport layer (not shown) and the electron injection layer 360 may each be stacked to a thickness of 10 to 200 nm, preferably 10 to 100 nm, but the present invention is not limited thereto.

A first host 342, which is an anthracene-based compound having a structure of Formulas 1 to 2, and a first dopant 344, which is a boron-based compound having a structure of Formulas 3 to 4, are applied to the light emitting material layer 340, and , a spiroaryl amine compound having a structure of Chemical Formulas 5 to 6 is applied to the electron blocking layer 330, and optionally an azine compound having a structure of Chemical Formulas 7 to 8 and/or Chemical Formulas 9 to 10 By applying the benzimidazole-based compound having a structure to the hole blocking layer 350 , the luminous efficiency of the organic light emitting diode D1 can be improved and the luminous lifespan can be greatly improved.

3 illustrates an organic light emitting diode including one light emitting unit, the organic light emitting diode according to the present invention may have a tandem structure including a plurality of light emitting units. 4 is a cross-sectional view schematically illustrating an organic light emitting diode according to an exemplary embodiment of the present invention.

As shown in FIG. 4 , the organic light emitting diode D2 according to the exemplary embodiment of the present invention has a first electrode 210 and a second electrode 220 facing each other, and a first electrode 210 and a second An organic light emitting layer 230A positioned between the electrodes 220 is included. The organic light emitting layer 230A is a first light emitting unit 400 positioned between the first electrode 210 and the second electrode 220 , and a first light emitting unit 400 positioned between the first light emitting unit 400 and the second electrode 220 . It includes a second light emitting unit 500 and a charge generation layer 470 positioned between the first and second light emitting units 400 and 500 .

The first electrode 210 is an anode for injecting holes, and may be made of a conductive material having a high work function, for example, ITO, IZO, ITZO, SnO, ZnO, ICO, and/or AZO. The second electrode 220 is a cathode for injecting electrons, and may be formed of a conductive material having a low work function, for example, Al, Mg, Ca, Ag, an alloy or combination thereof.

The first light emitting unit 400 includes a first light emitting material layer 440 , and a first electron blocking layer 430 positioned between the first electrode 210 and the first light emitting material layer 440 ; A first hole blocking layer 450 positioned between the first light emitting material layer 440 and the first charge generating layer 470 may be further included. In addition, the first light emitting unit 400 includes a hole injection layer 410 positioned between the first electrode 210 and the first electron blocking layer 430, the hole injection layer 410 and the first electron blocking layer ( A first hole transport layer 420 positioned between the 430 may be further included.

Meanwhile, the second light emitting unit 500 includes a second light emitting material layer 540 , and a second electron blocking layer 530 positioned between the first charge generating layer 470 and the second light emitting material layer 540 . ) and a second hole blocking layer 550 positioned between the second light emitting material layer 540 and the second electrode 220 . In addition, the second light emitting unit 500 includes a second hole transport layer 520 positioned between the first charge generation layer 470 and the second electron blocking layer 530 , the second hole blocking layer 550 and the second electron blocking layer 530 . An electron injection layer 560 positioned between the two electrodes 220 may be further included.

For example, the first light-emitting material layer 430 and the second light-emitting material layer 530 may include first hosts 442 and 542 that are anthracene-based compounds having structures of Chemical Formulas 1 to 2, respectively, and Chemical Formulas 3 to 4 The first dopants 444 and 544 that are boron-based compounds having a structure of may be included. The anthracene core of the anthracene-based compound serving as the first host (442, 542) is substituted with deuterium, but the boron-based compound serving as the first dopant (444, 544) is not substituted with deuterium, or some or all of hydrogen is substituted with deuterium. can At this time, the organic light emitting diode D2 emits blue light. The host 442 of the first light emitting material layer 440 and the host 542 of the second light emitting material layer 540 may be the same or different, and the dopant 444 of the first light emitting material layer 440 is The dopants 544 of the two light emitting material layers 540 may be the same or different.

The hole injection layer 410 is positioned between the first electrode 210 and the first hole transport layer 420 to improve the interface characteristics between the first electrode 210 and the first hole transport layer 420 . For example, the hole injection layer 410 is MTDATA, NATA, 1T-NATA, 2T-NATA, CuPc, TCTA, NPB (NPD), HAT-CN, TDAPB, PEDOT / PS), N- (biphenyl-4- yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine and/or a compound having a structure of formula 12, etc. It may be made of a hole injection material consisting of. Optionally, the hole injection layer 410 may be formed by doping a hole transport material with a hole injection material. The hole injection layer 410 may be omitted depending on the characteristics of the organic light emitting diode D2.

The first and second hole transport layers 420 and 520 are TPD, NPB, CBP, Poly-TPD, TFB, TAPC, DCDPA, N-(biphenyl-4-yl)-9,9-dimethyl-N-( 4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine, N-(biphenyl-4-yl)-N-(4-(9-phenyl-9H) -carbazol-3-yl)phenyl)biphenyl)-4-amine, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-) Phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine, N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)- [1,1'-biphenyl]-4,4'-diamine and/or a compound selected from the group consisting of a compound having a structure of Formula 11 and the like may be included, but the present invention is not limited thereto. The hole injection layer 410 and the first and second hole transport layers 420 and 520 may be laminated to a thickness of 5 nm to 200 nm, preferably 5 nm to 100 nm, respectively, but the present invention is not limited thereto. .

In the first and second electron blocking layers 430 and 530 , electrons pass through the first and second light emitting material layers 440 and 540 , respectively, and move to the first electrode 210 and the first charge generation layer 470 . to prevent For example, the first and second electron blocking layers 430 and 530 may each include a spiroaryl amine-based compound having a structure of Chemical Formulas 5 to 6, respectively.

In the first and second hole blocking layers 450 and 550 , holes move to the first charge generating layer 470 and the second electrode 220 through the first and second light emitting material layers 440 and 540 , respectively. to prevent For example, the first and second hole blocking layers 450 and 550 may each include an azine-based compound having a structure of Chemical Formulas 7 to 8 and/or a benzimidazole-based compound having a structure of Chemical Formulas 9 to 10. . The first and second electron blocking layers 430 and 530 and the first and second hole blocking layers 450 and 550 may be laminated to a thickness of 5 nm to 200 nm, preferably 5 nm to 100 nm, respectively. , the present invention is not limited thereto.

As described above, since the compounds having the structures of Chemical Formulas 7 to 10 have excellent electron transport properties as well as hole blocking ability, the first and second hole blocking layers 450 and 550 are formed from the hole blocking layer and the hole blocking layer, respectively. It can function as an electron transport layer.

In an optional embodiment, the first light emitting unit 400 may include a first electron transport layer (not shown) positioned between the first hole blocking layer 450 and the first charge generation layer 470, The second light emitting unit 500 may include a second electron transport layer (not shown) positioned between the second hole blocking layer 550 and the electron injection layer 560 . The first and second electron transport layers (not shown) are oxadiazole-base, triazole-base, phenanthroline-base, benzoxazole-based, benzoxazole, respectively. It may include derivatives such as thiazole-based (benzothiazole-base), benzimidazole-based (benzimidazole-base), and triazine-base.

For example, the first and second electron transport _{layers (not shown) are Alq 3} , PBD, spiro-PBD, Liq, TPB), BAlq, Bphen, NBphen, BCP, TAZ, NTAZ, TpPyPB, TmPPPyTz, PFNBr, TPQ , TSPO1, ZADN, 1,3-bis(9-phenyl-1,10-phenanthrolin-2-yl)benzene, p-bPPhenB and/or m-bPPhenB. The invention is not limited thereto.

The electron injection layer 560 is positioned between the second hole blocking layer 550 and the second electrode 220 . The electron injection layer 560 is an alkali halide-based material such as LiF, CsF, NaF, BaF ₂ , and/or an organometallic material such as lithium quinolate (Liq), lithium benzoate, and sodium stearate. may be used, but the present invention is not limited thereto.

In an alternative embodiment, the electron injection layer 560 may be an organic layer doped with an alkali metal such as Li, Na, K, Cs and/or an alkaline earth metal such as Mg, Sr, Ba, Ra. The organic host used for the electron injection layer 560 may be the aforementioned electron transport material, and may be doped with an alkali metal or alkaline earth metal in an amount of about 1 to 30 wt%. For example, the first and second electron transport layers (not shown) and the electron injection layer 560 may each be stacked to a thickness of 10 to 200 nm, preferably 10 to 100 nm, but the present invention is limited thereto. doesn't happen

A charge generation layer (CGL) 470 is positioned between the first light emitting unit 400 and the second light emitting unit 500 . The charge generation layer 470 includes an N-type charge generation layer (N-CGL) 480 positioned adjacent to the first light-emitting unit 400 and a P-type charge generation layer (N-CGL) 480 positioned adjacent to the second light-emitting unit 500 . P-CGL, 490). The N-type charge generation layer 480 injects electrons into the first light-emitting unit 400 , and the P-type charge generation layer 490 injects holes into the second light-emitting unit 500 .

The N-type charge generation layer 480 may be an organic layer doped with an alkali metal such as Li, Na, K, or Cs and/or an alkaline earth metal such as Mg, Sr, Ba or Ra. For example, the host organic material used in the N-type charge generation layer 480 includes 4,7-diphenyl-1,10-phenanthroline (4,7-dipheny-1,10-phenanthroline; Bphen), MTDATA and It may be the same material, and the alkali metal or alkaline earth metal may be doped in an amount of about 0.01 to 30% by weight.

Meanwhile, the P-type charge generation layer 490 is selected from the group consisting of tungsten oxide (WOx), molybdenum oxide (MoOx), beryllium oxide (Be ₂ O ₃ ), vanadium oxide (V ₂ O ₅ ), and combinations thereof. inorganic substances and/or NPD, HAT-CN, F4TCNQ, TPD, N,N,N',N'-tetranaphthalenyl-benzidine (TNB), TCTA, N,N'-dioctyl-3,4,9 , 10-perylenedicarboximide (N,N'-dioctyl-3,4,9,10-perylenedicarboximide; PTCDI-C8) and a combination thereof may be formed of an organic material selected from the group consisting of.

The organic light emitting diode (D2) according to an exemplary embodiment of the present invention comprises the first hosts 442 and 542, which are anthracene-based compounds, in which the anthracene core is substituted with deuterium, and the first dopants 444 and 544, which are boron-based compounds. The first and second light-emitting material layers 440 and 540 are applied, and the spiroaryl amine-based compound is applied to the first and second electron blocking layers 430 and 530, and optionally azine-based and/or benzimi. The dazole-based compound is applied to the first and second hole blocking layers 450 and 550 to improve luminous efficiency and luminous lifetime. In particular, by stacking the two light emitting units 400 and 500 that emit blue (B) in a double stack structure, an image of high color purity can be realized in the organic light emitting display device 100 (refer to FIG. 1 ). .

Meanwhile, in FIG. 4 , an organic light emitting diode in which two light emitting units form a tandem structure has been described. Alternatively, the organic light emitting diode may include three light emitting units forming a second charge generating layer and a third light emitting unit on the second light emitting unit 500 except for the electron injection layer 560 (see FIG. 7 ). .

Meanwhile, in the above-described embodiment, an organic light emitting diode display and an organic light emitting diode for realizing blue (B) light emission have been described. Alternatively, a full-color display including white (W) light emission can also be implemented, which will be described. 5 is a cross-sectional view schematically illustrating an organic light emitting display device as an example of an organic light emitting device according to a second exemplary embodiment of the present invention.

As shown in FIG. 5 , in the organic light emitting diode display 600 according to the second exemplary embodiment of the present invention, a first substrate 602 in which a red pixel RP, a green pixel GP, and a blue pixel BP are defined, respectively. ), a second substrate 604 facing the first substrate 602, and an organic light emitting diode 700 positioned between the first substrate 602 and the second substrate 604 and emitting white light; The color filter layer 680 is positioned between the organic light emitting diode 700 and the second substrate 602 .

The first substrate 602 and the second substrate 604 may each be a glass substrate, a flexible substrate, or a polymer plastic substrate. For example, each of the first and second substrates 602 and 604 may be formed of any one of PI, PES, PEN, PET, and PC.

A buffer layer 606 is formed on the first substrate 602 , and a thin film transistor Tr is formed on the buffer layer 606 to correspond to each of the red pixel RP, the green pixel GP, and the blue pixel BP. . The buffer layer 606 may be omitted.

A semiconductor layer 610 is formed on the buffer layer 606 . For example, the semiconductor layer 610 may be made of an oxide semiconductor material or polycrystalline silicon.

An insulating material, for example, a _{gate insulating layer 620 made of an inorganic insulating material such as silicon oxide (SiO 2} ) or silicon nitride (SiNx) is formed on the semiconductor layer 610 .

A gate electrode 630 made of a conductive material such as metal is formed on the gate insulating layer 620 to correspond to the center of the semiconductor layer 610 . On the upper portion of the gate electrode 630 _{, an insulating material, an interlayer insulating film made of an inorganic insulating material such as silicon oxide (SiO 2} ) or silicon nitride (SiNx), or an organic insulating material such as benzocyclobutene or photo-acryl (photo-acryl) 640) is formed.

The interlayer insulating layer 640 has first and second semiconductor layer contact holes 142 and 144 exposing upper surfaces of both sides of the semiconductor layer 610 . The first and second semiconductor layer contact holes 142 and 144 are positioned at both sides of the gate electrode 130 to be spaced apart from the gate electrode 130 .

A source electrode 652 and a drain electrode 654 made of a conductive material such as metal are formed on the interlayer insulating layer 640 . The source electrode 652 and the drain electrode 654 are positioned to be spaced apart from the center of the gate electrode 630 , respectively, on both sides of the semiconductor layer 610 through the first and second semiconductor layer contact holes 642 and 644 , respectively. contact

The semiconductor layer 110 , the gate electrode 130 , the source electrode 152 , and the drain electrode 154 form a thin film transistor Tr, and the thin film transistor Tr functions as a driving element.

Although not shown in FIG. 5 , the gate line and the data line cross each other to define a pixel area, and a switching element connected to the gate line and the data line is further formed. The switching element is connected to a thin film transistor Tr as a driving element. In addition, the power wiring is formed to be spaced apart from the data wiring or the data wiring in parallel, and a storage capacitor is further configured to keep the voltage of the gate electrode of the thin film transistor Tr as the driving element constant during one frame. can

A protective layer 660 is formed on the source electrode 652 and the drain electrode 654 over the entire surface of the first substrate 602 to cover the thin film transistor Tr. The passivation layer 660 has a drain contact hole 662 exposing the drain electrode 654 of the thin film transistor Tr.

The organic light emitting diode D is positioned on the protective layer 660 . The organic light emitting diode D includes a first electrode 710 connected to the drain electrode 652 of the thin film transistor Tr, a second electrode 720 facing the first electrode 710, and first and first An organic light emitting layer 730 positioned between the two electrodes 710 and 720 is included.

The first electrode 710 formed for each pixel area may be an anode, and may be made of a conductive material having a relatively large work function value. For example, the first electrode 710 may be formed of ITO, IZO, ITZO, SnO, ZnO, ICO, AZO, or the like. A reflective electrode or a reflective layer may be further formed under the first electrode 710 . For example, the reflective electrode or the reflective layer may be made of an APC alloy.

A bank layer 664 covering an edge of the first electrode 710 is formed on the passivation layer 660 . The bank layer 664 exposes the center of the first electrode 710 in correspondence with the pixels RP, GP, and BP. The bank layer 664 may be omitted.

An organic light emitting layer 730 including a light emitting unit is formed on the first electrode 710 . 6 and 7, the organic light emitting layer 730 may include a plurality of light emitting units 800, 900, 1000, 1100, 1200 and one or more charge generating layers 870, 1070, 1170. have. Each light emitting unit includes a light emitting material layer, and may further include a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and/or an electron injection layer.

A second electrode 720 is formed on the first substrate 602 on which the organic emission layer 730 is formed. The second electrode 720 is positioned on the front surface of the display area, and is made of a material having a relatively small work function value, and may be a cathode for injecting electrons. For example, the second electrode 720 may include aluminum (Al), magnesium (Mg), calcium (ca), silver (Ag), or an alloy or combination thereof (eg, aluminum-magnesium alloy (AlMg)) and It may be made of a material having the same reflective properties.

Meanwhile, in the organic light emitting display device 600 according to the second exemplary embodiment of the present invention, since light emitted from the organic light emitting layer 730 is incident on the color filter layer 680 through the second electrode 720 , the second The electrode 720 has a thin thickness to allow light to pass therethrough.

The color filter layer 680 is positioned on the organic light emitting diode D, and includes a red color filter 682 and a green color filter corresponding to each of the red pixel RP, the green pixel GP, and the blue pixel BP. 684 ) and a blue color filter 686 . Although not shown, the color filter layer 680 may be attached to the organic light emitting diode D by an adhesive layer. Alternatively, the color filter layer 680 may be formed directly on the organic light emitting diode (D).

Although not shown, in order to prevent external moisture from penetrating into the organic light emitting diode (D), an encapsulation film may be formed. For example, the encapsulation film may have a laminated structure of a first inorganic insulating layer, an organic insulating layer, and a second inorganic insulating layer, but is not limited thereto (see 170 of FIG. 1 ). In addition, a polarizing plate for reducing reflection of external light may be attached to the outer surface of the second substrate 604 . For example, the polarizing plate may be a circular polarizing plate.

In FIG. 5 , light from the organic light emitting diode (D) passes through the second electrode 720 , and the color filter layer 680 is disposed on the organic light emitting diode (D). Alternatively, light from the organic light emitting diode D may pass through the first electrode 710 , and the color filter layer 680 may be disposed between the organic light emitting diode D and the first substrate 602 . In addition, a color conversion layer (not shown) may be provided between the organic light emitting diode D and the color filter layer 680 . The color conversion layer includes a red color conversion layer, a green color conversion layer, and a blue color conversion layer corresponding to each pixel, and may convert white light emitted from the organic light emitting diode D into red, green, and blue, respectively.

As described above, the white light from the organic light emitting diode D is a red color filter 682 and a green color filter 684 corresponding to each of the red pixel RP, the green pixel GP, and the blue pixel BP. , by passing through the blue color filter 686 , red, green, and blue light are displayed in the red pixel RP, the green pixel GP, and the blue pixel BP.

An organic light emitting diode applicable to an organic light emitting diode display according to the second embodiment of the present invention will be described in detail with reference to FIGS. 6 and 7 . 6 is a cross-sectional view schematically illustrating a double stack organic light emitting diode used in an organic light emitting diode display according to an exemplary embodiment of the present invention.

Referring to FIG. 6 , an organic light emitting diode D3 according to an exemplary embodiment of the present invention includes first and second electrodes 710 and 720 facing each other, and a first electrode 710 and a second electrode 720 . ) and an organic light emitting layer 730 positioned between them. The organic light emitting layer 730 includes a first light emitting unit 800 positioned between the first and second electrodes 720 , and a second light emitting unit positioned between the first light emitting unit 800 and the second electrode 720 . and a charge generation layer 870 positioned between 900 and the first and second light emitting units 800 and 900 .

The first light emitting unit 800 includes a first light emitting material layer 840 . In addition, the first light emitting unit 800 includes a first electron blocking layer 830 positioned between the first electrode 710 and the first light emitting material layer 840 , the first light emitting material layer 840 and the first A first hole blocking layer 850 positioned between the charge generation layers 870 may be further included. In addition, the first light emitting unit 800 includes a hole injection layer 810 positioned between the first electrode 710 and the first electron blocking layer 830, the hole injection layer 810 and the first electron blocking layer ( A first hole transport layer 820 positioned between the 830 may be further included.

In this case, the first light emitting material layer 840 includes a first host 842 that is an anthracene-based compound and a first dopant 844 that is a boron-based compound. The anthracene core of the anthracene-based compound serving as the first host 842 may be substituted with deuterium, but the boron-based compound serving as the first dopant 844 may not be substituted with deuterium, or some or all of hydrogen may be substituted with deuterium. The first light emitting material layer 840 emits blue light.

The first electron blocking layer 830 may include a spiroaryl amine compound having a structure of Chemical Formulas 5 to 6. The first hole blocking layer 850 may include an azine-based compound having a structure of Chemical Formulas 7 to 8 and/or a benzimidazole-based compound having a structure of Chemical Formulas 9 to 10. As described above, since the compounds having the structures of Chemical Formulas 7 to 10 have excellent electron transport properties as well as hole blocking ability, the first hole blocking layer 850 functions as a hole blocking layer and an electron transport layer, respectively. can

In an optional embodiment, the first light emitting unit 800 may include a first electron transport layer (not shown) positioned between the first hole blocking layer 850 and the first charge generation layer 870 .

Meanwhile, the second light emitting unit 900 includes a second light emitting material layer 940 . In addition, the second light emitting unit 900 includes a second hole transport layer 920 positioned between the charge generating layer 870 and the second light emitting material layer 940 , the second light emitting material layer 940 and the second electrode. An electron transport layer (a second electron transport layer, not shown) positioned between the 720 may be included. Also, the second light emitting unit 900 includes a second electron blocking layer 930, a second light emitting material layer 940 and a second hole transport layer 920 and a second light emitting material layer 940 positioned between the second light emitting material layer 940 and the second light emitting material layer 940 . A second hole blocking layer 950 positioned between the electron transport layer (not shown), and an electron injection layer 960 positioned between the second electron transport layer and the second electrode 720 may be further included.

In one exemplary embodiment, the second light-emitting material layer 940 may emit red-green (RG) light. In this case, the second light emitting material layer 940 may include a second host 942 , a second dopant 944 that is a green dopant, and a third dopant 946 that is a red dopant. For example, the second dopant 944 and the third dopant 946 may each be a fluorescent compound, a phosphorescent compound, and/or a delayed fluorescent compound.

For example, the second host 942 included in the second collapsing material layer 940 is 9,9'-diphenyl-9H,9'H-3,3'-bicarbazole (9,9'-) Diphenyl-9H,9'H-3,3'-bicarbazole; BCzPh), CBP, 1,3,5-tris(carbazol-9-yl)benzene (1,3,5-Tris(carbazole-9-yl) )benzene; TCP), TCTA, 4,4'-bis(carbazole-9-yl)-2,2'-dimethylbiphenyl(4,4'-Bis(carbazole-9-yl)-2,2'-dimethylbipheyl; CDBP), 2,7-bis(carbazole-9-yl)-9,9-dimethylfluorene (2,7-Bis(carbazole-9-yl)-9,9-dimethylfluorene (DMFL-CBP) ), 2,2',7,7'-tetrakis (carbazol-9-yl)-9,9-spirofluorene (2,2',7,7'-Tetrakis (carbazole-9-yl) -9,9-spiorofluorene; Spior-CBP), DPEPO, 4'-(9H-carbazol-9-yl)biphenyl-3,5-dicarbonitrile (4'-(9H-carbazol-9-yl) biphenyl-3,5-dicarbonitrile; PCzB-2CN), 3'-(9H-carbazol-9-yl)biphenyl-3,5-dicarbonitrile (3'-(9H-carbazol-9-yl)biphenyl -3,5-dicarbonitrile; mCzB-2CN), 3,6-bis(carbazol-9-yl)-9-(2-ethyl-hexyl)-9H-carbazole (3,6-Bis(carbazole-9) -yl)-9-(2-ethyl-hexyl)-9H-carbazole; TCz1), bis(2-(2-hydroxyphenyl)-pyridine)beryllium; Bepp ₂ ), bis (10-hydroxylbenzo [h] quinolinato) beryllium (Bis (10-hydroxylbenzo [h] quinolinato) beryllium; Bebq ₂ ), 1,3,5-tris (1-pyrenyl) benzene (1 ,3,5-Tris(1-pyrenyl)benzene; TPB3) and the like, but the present invention is not limited thereto.

On the other hand, the second dopant 944, which may be a green dopant, is [bis(2-phenylpyridine)](pyridyl-2-benzofuro[2,3-b]pyridine)iridium ([Bis(2-phenylpyridine) ](pyridyl-2-benzofuro[2,3-b]pyridine)iridium), fac-Tris(2-phenylpyridine)iridium(III); fac-Ir( ppy) ₃ ), bis(2-phenylpyridine)(acetylacetonate)iridium(III)(Bis(2-phenylpyridine)(acetylacetonate)iridium(III); Ir(ppy) ₂ (acac)), tris[2- (p-tolyl) pyridine] iridium (III) (Tris [2- (p-tolyl) pyridine] iridium (III); Ir (mppy) ₃ ), bis (2-naphthalen-2-yl) pyridine) (acetylaceto nate) iridium (III) (Bis (2- (naphthalene-2-yl) pyridine) (acetylacetonate) iridium (III); Ir (npy) ₂ acac), tris (2-phenyl-3-methyl-pyridine) iridium ( Tris(2-phenyl-3-methyl-pyridine)iidium; Ir(3mppy) ₃ ), pac-tris(2-(3-p-xylyl)phenyl)pyridine iridium(III)(fac-Tris(2-( 3-p-xylyl)phenyl)pyridine iridium(III); TEG), and the like, but the present invention is not limited thereto.

A third dopant 946 that may be used as the red dopant is [bis(2-(4,6-dimethyl)phenylquinoline)](2,2,6,6-tetramethylheptene-3,5-dionate)iridium (III)([Bis(2-(4,6-dimethyl)phenylquinoline)](2,2,6,6-tetramethylheptane-3,5-dionate)iridium(III), bis[2-(4-n- Hexylphenyl)quinoline](acetylacetonate)iridium(III)(Bis[2-(4-n-hexylphenyl)quinoline](acetylacetonate)iridium(III); Hex-Ir(phq) ₂ (acac)), tris[ 2- (4-n-hexylphenyl) quinoline] iridium (III) (Tris [2- (4-n-hexylphenyl) quinoline] iridium (III), Hex-Ir (phq) ₃ ), tris [2-phenyl- 4-methylquinoline] iridium (III) (Tris [2-phenyl-4-methylquinoline] iridium (III), Ir (Mphq) ₃ ), bis (2-phenylquinoline) (2,2,6,6-tetramethyl Heptene-3,5-dionate) iridium (III) (Bis (2-phenylquinoline) (2,2,6,6-tetramethylheptene-3,5-dionate) iridium (III), Ir (dpm) PQ ₂ ), Bis(phenylisoquinoline)(2,2,6,6-tetramethylheptene-3,5-dionate)iridium(III)(Bis(phenylisoquinoline)(2,2,6,6-tetramethylheptene-3,5- dionate)iridium(III), Ir(dpm)(piq) ₂ ), bis[(4-n-hexylphenyl)isoquinoline](acetylacetonate)iridium(III)(Bis[(4-n-hexylphenyl)isoquinoline ](acetylacetonate)iridium(III); Hex-Ir(piq) ₂ (acac)), tris[2-(4-n-hexylphenyl)quinoline]iridium(III)(Tris[2-(4-n-hexylphenyl) ) quinoline] iridium (III), Hex-Ir (piq) ₃ ), tris (2- (3-methylphenyl) -7-methyl-quinolato) iridium (Tris (2- (3-methy) lphenyl)-7-methyl-quinolato)iridium; Ir(dmpq) ₃ ), bis[2-(2-methylphenyl)-7-methyl-quinoline](acetylacetonate)iridium(III)(Bis[2-(2-methylphenyl)-7-methyl-quinoline]( acetylacetonate)iridium(III);Ir(dmpq) ₂ (acac)),bis[2-(3,5-dimethylphenyl)-4-methyl-quinoline](acetylacetonate)iridium(III)(Bis[2- (3,5-dimethylphenyl)-4-methyl-quinoline](acetylacetonate)iridium(III); Ir(mphmq) ₂ (acac)) and the like.

In an alternative embodiment, the second light-emitting material layer 940 may emit yellow-green (YG) light. In this case, the second light emitting material layer 940 may include a second host 942 , a second dopant 944 that is a green dopant, and a third dopant 946 that is a yellow dopant.

The second host 942 for yellow-green (YG) emission may be the same as that used for the above-described red-green (RG) emission, and the second dopant 946 as a green dopant is the green dopant described in yellow-green (YG) emission. can be the same as The third dopant 946, which is a yellow dopant, is 5,6,11,12-tetraphenylnaphthalene (5,6,11,12-Tetraphenylnaphthalene; Rubrene), 2,8-di-tert-butyl-5,11-bis (4-tert-butylphenyl)-6,12-diphenyltetracene (2,8-Di-tert-butyl-5,11-bis(4-tert-butylphenyl)-6,12-diphenyltetracene; TBRb); Bis(2-phenylbenzothiazolato)(acetylacetonate)iridium(III)(Bis(2-phenylbenzothiazolato)(acetylacetonate)irdium(III); Ir(BT) ₂ (acac)), bis(2-(9) ,9-diethyl-fluoren-2-yl)-1-phenyl-1H-benzo[d]imidazolato)(acetylacetonate)iridium(III)(Bis(2-(9,9-diethytl-) fluoren-2-yl)-1-phenyl-1H-benzo[d]imdiazolato)(acetylacetonate)iridium(III); Ir(fbi) ₂ (acac)), bis(2-phenylpyridine)(3-(pyridine- 2-yl)-2H-chromen-2-onate)iridium(III)(Bis(2-phenylpyridine)(3-(pyridine-2-yl)-2H-chromen-2-onate)iridium(III); fac-Ir(ppy) ₂ Pc), bis(2-(2,4-difluorophenyl)quinoline)(picolinate)iridium(III)(Bis(2-(2,4-difluorophenyl)quinoline)( picolinate)iridium(III); FPQIrpic), and the like, but the present invention is not limited thereto.

When the second light-emitting material layer 940 emits red-green (RG) or yellow-green (YG) light, the second dopant 944 and the third dopant 946 are formed from 1 to 50 in the second light-emitting material layer 940 . It may be doped in a proportion of 1 to 30% by weight, preferably 1 to 30% by weight.

In this embodiment, the second electron blocking layer 930 is TCTA, tris [4- (diethylamino) phenyl] amine (tris [4- (diethylamino) phenyl] amine), N- (biphenyl-4-yl) )-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine, TAPC, MTDATA, 1,3-bis(carba Zol-9-yl) benzene (1,3-Bis (carbazol-9-yl) benzene; mCP), 3,3-di (9H-carbazol-9-yl) biphenyl (3,3-Di (9H) -carbazol-9-yl)biphenyl; mCBP), CuPC, N,N'-bis[4-[bis(3-methylphenyl)amino]phenyl]-N,N'-diphenyl-[1,1'-bi Phenyl]-4,4'-diamine (N,N'-bis[4-[bis(3-methylphenyl)amino]phenyl]-N,N'-diphenyl-[1,1'-biphenyl]-4,4 '-diamine; DNTPD), TDAPB, DCDPA and/or 2,8-bis(9-phenyl-9H-carbazol-3-yl)dibenzo[b,d]thiophene (2,8-bis(9- phenyl-9H-carbazol-3-yl)dibenzo[b,d]thiophene), but the present invention is not limited thereto.

For the second hole blocking layer 950 , derivatives such as oxadiazole-based, triazole-based, phenanthroline-based, benzoxazole-based, benzothiazole-based, benzimidazole-based, and triazine-based derivatives may be used. For example, the second hole blocking layer 950 may include BCP, BAlq, Alq3, PBD, Spiro-PBD, Liq, bis-, which has a lower HOMO energy level compared to the material used for the second light emitting material layer 940 . 4,6-(3,5-di-3-pyridylphenyl)-2-methylpyrimidine (bis-4,6-(3,5-di-3-pyridylphenyl)-2-methylpyrimidine; B3PYMPM), bis [2-(diphenylphosphino)phenyl]etheroxide (Bis[2-(diphenylphosphino)phenyl]teeth oxide; DPEPO), 9-(6-(9H-carbazol-9-yl)pyridin-3-yl) It may consist of a compound selected from the group consisting of -9H-3,9'-bicarbazole, TSPO1, and combinations thereof.

The charge generation layer 870 is positioned between the first light emitting unit 800 and the second light emitting unit 900 . The charge generation layer 870 may be a PN junction charge generation layer in which the N-type charge generation layer 880 and the P-type charge generation layer 890 are joined. The charge generation layer 870 includes an N-type charge generation layer 880 positioned adjacent to the first light emitting unit 800 and a P-type charge generation layer 890 positioned adjacent to the second light emitting unit 900 . include

In the organic light emitting diode (D3) according to the third embodiment of the present invention, a first host 842, which is an anthracene-based compound, and a first dopant 844, which is a boron-based compound, are applied to the first light-emitting material layer 840, , Spiroarylamine-based compound is applied to the first electron blocking layer 830, and optionally an azine-based and/or benzimidazole-based compound is applied to the first hole blocking layer 850, and a second light-emitting material layer In 940, red-green or yellow-green is emitted to improve luminous efficiency and luminous lifetime. In particular, the first light emitting unit 800 emitting light in blue (B) and the second light emitting unit 900 emitting light in red green (RG) or yellow green (YG) are laminated in a double stack structure, The light emitting display device 600 (refer to FIG. 5 ) may emit white (W) light. Optionally, the first light-emitting material layer 840 positioned between the first electrode 710 and the charge generating layer 870 is a yellow-green or red-green light-emitting material layer, and the charge generating layer 870 and the second electrode 720 . ), the second light emitting material layer 940 may be a blue light emitting material layer including a first host that is an anthracene derivative and a first dopant that is a boron derivative.

Meanwhile, the organic light emitting diode may have a triple stack structure.

Referring to FIG. 7 , an organic light emitting diode D4 according to an exemplary embodiment of the present invention includes first and second electrodes 710 and 720 facing each other, and a first electrode 710 and a second electrode 720 . ) and an organic light emitting layer 730A positioned between them. The organic light emitting layer 730A includes a first light emitting unit 1000 positioned between the first and second electrodes 710 and 720 , and a second light emitting unit 1000 positioned between the first light emitting unit 1000 and the second electrode 720 . The light emitting unit 1100, the third light emitting unit 1200 positioned between the second light emitting unit 1100 and the second electrode 720, and the first and second light emitting units 1000 and 1100 positioned between It includes a first charge generation layer 1070 and a second charge generation layer 1170 positioned between the second and third light emitting units 1100 and 1200 .

At this time, at least one of the first to third light emitting units 1000 , 1000 , and 1200 emits blue (B) light, and at least one of the first to third light emitting units 1000 , 1100 and 1200 emits red green light. It can emit light in (RG) or yellow-green (YG). Hereinafter, a case in which the first and third light emitting units 1000 and 1200 emit light in blue (B) and the second light emitting unit 1100 emit light in red-green (RG) or yellow-green (YG) will be mainly described. .

The first electrode 710 is an anode for injecting holes, and may be made of a conductive material having a high work function, for example, ITO, IZO, ITZO, SnO, ZnO, ICO, and/or AZO. The second electrode 720 is a cathode for injecting electrons, and may be formed of a conductive material having a low work function, for example, Al, Mg, Ca, Ag, an alloy or a combination thereof.

The first light emitting unit 1000 includes a first light emitting material layer 1040, a first electron blocking layer 1030 positioned between the first electrode 710 and the first light emitting material layer 1040; A first hole blocking layer 1050 positioned between the first light emitting material layer 1040 and the first charge generating layer 1070 may be further included.

In addition, the first light emitting unit 1000 includes a hole injection layer 1010 positioned between the first electrode 710 and the first electron blocking layer 1030, a hole injection layer 1010 and a first electron blocking layer ( A first hole transport layer 1020 positioned between 1030 may be further included.

Meanwhile, the second light emitting unit 1100 includes a second light emitting material layer 1140 , and a second hole transport layer 1120 positioned between the first charge generating layer 1070 and the second light emitting material layer 1140 . and a second electron transport layer (not shown) positioned between the second light emitting material layer 1140 and the second charge generation layer 1170 . In addition, the second light emitting unit 1100 includes a second electron blocking layer 1130 positioned between the second hole transport layer 1120 and the second light emitting material layer 1140 , the second light emitting material layer 1140 and the second light emitting material layer 1140 . A second hole blocking layer 1150 positioned between the two electron transport layers (not shown) may be further included.

Meanwhile, the third light emitting unit 1200 includes a third light emitting material layer 1240 , and a third electron blocking layer 1230 positioned between the second charge generating layer 1170 and the third light emitting material layer 1240 . ) and a third hole blocking layer 1250 positioned between the third light emitting material layer 1240 and the second electrode 720 . In addition, the third light emitting unit 1200 includes a third hole transport layer 1220 positioned between the second charge generation layer 1170 and the third electron blocking layer 1230 , the third hole blocking layer 1250 and the second electron blocking layer 1230 . An electron injection layer 1260 positioned between the two electrodes 720 may be further included.

At this time, the first light-emitting material layer 1040 and the third light-emitting material layer 1240 are the first hosts 1042 and 1242, which are anthracene-based compounds having structures of Chemical Formulas 1 to 2, respectively, and Chemical Formulas 3 to 4, respectively. The first dopants 1044 and 1244 that are boron-based compounds having a structure may be included. At this time, the anthracene core of the anthracene-based compound serving as the first host (1042, 1242) is substituted with deuterium, but the boron-based compound serving as the first dopant (1044, 1244) is not substituted with deuterium, or some or all of hydrogen is replaced with deuterium may be substituted. The host 1042 of the first light emitting material layer 1040 and the host 1242 of the third light emitting material layer 1240 may be the same or different, and the dopant 1044 of the first light emitting material layer 1040 and the first 3 The dopant 1244 of the light emitting material layer 1240 may be the same or different. In this case, the first light-emitting material layer 1040 and the third light-emitting material layer 1240 emit blue light, respectively.

The first and third electron blocking layers 1030 and 1230 may each include a spiroaryl amine compound having a structure of Chemical Formulas 5 to 6, respectively.

The first and third hole blocking layers 1050 and 1250 may include an azine-based compound having a structure of Chemical Formulas 7 to 8 and/or a benzimidazole-based compound having a structure of Chemical Formulas 9 to 10, respectively.

As described above, since the compounds having the structures of Chemical Formulas 7 to 10 have excellent electron transport properties as well as hole blocking ability, the first and third hole blocking layers 1050 and 1250 are formed from the hole blocking layer and the hole blocking layer, respectively. It can function as an electron transport layer.

In an optional embodiment, the first light emitting unit 1000 may include a first electron transport layer (not shown) positioned between the first hole blocking layer 1050 and the first charge generation layer 1070, The third light emitting unit 1200 may include a third electron transport layer (not shown) positioned between the third hole blocking layer 1250 and the electron injection layer 1260 .

In one exemplary embodiment, the second light emitting material layer 1140 may emit red-green (RG) light. In this case, the second light emitting material layer 1140 may include a second host 1142 , a second dopant 1144 serving as a green dopant, and a third dopant 1146 serving as a red dopant.

In an optional embodiment, the second light-emitting material layer 1140 may emit yellow-green (YG) light. In this case, the second light emitting material layer 1140 may include a second host 1142 , a second dopant 1144 that is a green dopant, and a third dopant 1146 that is a yellow dopant. The second host 1142 , the second dopant 1144 , and the third dopant 1146 of the second light emitting material layer 1140 emitting yellow-green or red-green light may be the same as described with reference to FIG. 6 .

When the second light-emitting material layer 1140 emits red-green (RG) or yellow-green (YG) light, the second dopant 1144 and the third dopant 1146 are 1 to 50 in the second light-emitting material layer 1140 . It may be doped in a proportion of 1 to 30% by weight, preferably 1 to 30% by weight.

The second electron blocking layer 1130 is TCTA, tris [4- (diethylamino) phenyl] amine (tris [4- (diethylamino) phenyl] amine), N- (biphenyl-4-yl) -9,9 -Dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine, TAPC, MTDATA, 1,3-bis(carbazol-9-yl) ) Benzene (1,3-Bis(carbazol-9-yl)benzene; mCP), 3,3-di(9H-carbazol-9-yl)biphenyl (3,3-Di(9H-carbazol-9-) yl)biphenyl; mCBP), CuPC, N,N'-bis[4-[bis(3-methylphenyl)amino]phenyl]-N,N'-diphenyl-[1,1'-biphenyl]-4, 4'-diamine (N,N'-bis[4-[bis(3-methylphenyl)amino]phenyl]-N,N'-diphenyl-[1,1'-biphenyl]-4,4'-diamine; DNTPD ), TDAPB, DCDPA and/or 2,8-bis(9-phenyl-9H-carbazol-3-yl)dibenzo[b,d]thiophene (2,8-bis(9-phenyl-9H-carbazol) -3-yl)dibenzo[b,d]thiophene), but the present invention is not limited thereto.

For the second hole blocking layer 1150, an oxadiazole-based, triazole-based, phenanthroline-based, benzoxazole-based, benzothiazole-based, benzimidazole-based derivative, or a triazine-based derivative may be used.

The first charge generation layer 1070 is positioned between the first light emitting unit 1000 and the second light emitting unit 1100, and the second charge generation layer 1170 is formed between the second light emitting unit 1100 and the third light emitting unit ( 1200) is located between The first and second charge generation layers 1070 and 1170 are PNs in which the first and second N-type charge generation layers 1080 and 1180 and the second and second P-type charge generation layers 1090 and 1190 are bonded to each other, respectively. It may be a junction charge generating layer. The first and second charge generation layers 1070 and 1170 include first and second N-type charge generation layers 1080 and 1180 positioned adjacent to the first and second light emitting units 1000 and 1100, respectively; and first and second P-type charge generation layers 1090 and 1190 positioned adjacent to the second and third light emitting units 1100 and 1200 . The first and second N-type charge generation layers 1080 and 1180 inject electrons into the first and second light emitting units 1000 and 1100, respectively, and the first and second P-type charge generation layers 1090 , 1190 injects holes into the second and third light emitting units 1100 and 1200, respectively.

The organic light emitting diode D4 according to the third embodiment of the present invention includes first hosts 1042 and 1242 that are anthracene-based compounds and first dopants 1044 and 1244 that are boron-based compounds as first and third light-emitting materials. The layers 1040 and 1240 are applied, and the spiroaryl amine compound is applied to the first and third electron blocking layers 1030 and 1230, and optionally an azine-based and/or benzimidazole-based compound is applied to the first and It is applied to the third hole blocking layers 1050 and 1250 and the second light emitting material layer 1140 emits red-green or yellow-green color to improve luminous efficiency and luminous lifetime. In particular, the two light emitting units 1000 and 1200 that emit light in blue (B) and the light emitting unit 1100 that emit light in red-green (RG) or yellow-green (YG) are stacked in a triple stack structure to form an organic The light emitting display device 600 (refer to FIG. 5 ) may emit white (W) light.

Meanwhile, in FIG. 6 , an organic light emitting diode having a tandem structure in which three light emitting units are stacked has been described. Alternatively, the organic light emitting diode may further include an additional light emitting unit and a charge generating layer.

Meanwhile, the organic light emitting device according to the present invention may include a color conversion layer. 8 is a cross-sectional view schematically illustrating an organic light emitting display device as an example of an organic light emitting device according to a third exemplary embodiment of the present invention.

As shown in FIG. 8 , the organic light emitting diode display 1300 includes a first substrate 1302 in which a red pixel RP, a green pixel GP, and a blue pixel BP are defined, the first substrate 1302 and An organic light emitting diode (D) positioned between the facing second substrate 1304 and the first substrate 1302 and the second substrate 1304 and emitting blue light, the organic light emitting diode (D) and the second substrate and a color conversion layer 1380 positioned between 1304 . Although not shown, a color filter may be formed between each of the second substrate 1304 and the color conversion layer 1380 .

A thin film transistor Tr is provided on the first substrate 1302 to correspond to each of the red pixel RP, the green pixel GP, and the blue pixel BP, and one electrode constituting the thin film transistor Tr, for example For example, a protective layer 1360 having a drain contact hole exposing a drain electrode (not shown) is formed to cover the thin film transistor Tr.

An organic light emitting diode D including a first electrode 1410 , an organic light emitting layer 1430 , and a second electrode 1420 is formed on the passivation layer 1360 . In this case, the first electrode 1410 may be connected to a drain electrode (not shown) of the thin film transistor Tr through a drain contact hole. In addition, a bank layer 1164 covering the edge of the first electrode 1410 is formed at the boundary of each of the red pixel RP, the green pixel GP, and the blue pixel BP.

In this case, the organic light emitting diode (D) may have the structure of FIG. 3 or 4 and emit blue (B) light. That is, the organic light emitting diode D is provided in each of the red pixel RP, the green pixel GP, and the blue pixel BP to provide blue light.

The color conversion layer 1380 includes a first color conversion layer 1382 corresponding to the red pixel RP and a second color conversion layer 1384 corresponding to the green pixel BP. For example, the color conversion layer 1380 may be formed of an inorganic light emitting material such as quantum dots.

The blue light emitted from the organic light emitting diode D in the red pixel RP is converted into red light by the first color conversion layer 1382, and the blue light emitted from the organic light emitting diode D in the green pixel GP is blue. The light is converted into green light by the second color conversion layer 1384 . Accordingly, the organic light emitting display device 1300 may implement a color image.

On the other hand, when the light emitted from the organic light emitting diode D passes through the first substrate 1302 and is displayed, the color conversion layer 1380 may be provided between the organic light emitting diode D and the first substrate 1302 . may be

Hereinafter, the present invention will be described through exemplary embodiments, but the present invention is not limited to the technical ideas described in the following examples.

Synthesis Example 1: Synthesis of Host 1

(1) Intermediate H-1 synthesis

[Scheme 1-1]

Anhydrous cupric bromide (45 g, 0.202 mol) was added to _{CCl 4} solution of Anthracene-D10 (18.8 g, 0.10 mol) and reacted. The reaction _{was stirred under N 2} atmosphere with heating for 12 hours. After the reaction was completed, the white CuBr(I) material was removed with a filter, and the filtrate was purified by passing it through a 35-nm Alumina column. In a vacuum, the solvent was removed from the reaction solution first purified through a column to obtain a mixture containing the intermediate H-1 (9-bromoanthracene-D9). The mixture was a mixture containing the intermediate H-1, the reaction starter (anthracene-D10) and dibromo-byproduct, and the mixture was used as a reactant in the next reaction without further purification.

(2) intermediate H-2 synthesis

[Scheme 1-2]

Intermediate H-1 (2.66 g, 0.01 mol) and naphtalene-1-boronic acid (1.72 g, 0.01 mol) were added to a round-bottom flask, and toluene solution (30 mL) was added to make a mixed solution. While stirring the mixed solution under a nitrogen atmosphere, an aqueous solution of _{Na 2} CO _{3 dissolved in Na 2} CO ₃ (2.12 g) in distilled water (10 mL) was added. Then, a catalyst Pd(PPh ₃ ) ₄ (tetrakis(triphenylphosphine)palladium(0), 0.25 g, 0.025 mmol) was added and stirred. After completion of the reaction, the reaction solution was put into a methanol solution to precipitate a product, and the precipitate was filtered. In the reduced pressure filter, the precipitate was washed with water, aqueous hydrogen chloride solution (concentration of 10%), water, and methanol in this order. The precipitate was purified to obtain an intermediate H-2 as a white powder (2.6 g).

(3) intermediate H-3 synthesis

[Scheme 1-3]

Intermediate H-2 (2.8 g, 8.75 mmol) was dissolved in dichloromethane (50 mL), Br ₂ (1.4 g, 8.75 mmol) was added to the solution, and the mixture was stirred at room temperature (RT). After the reaction was completed, 2M Na ₂ S ₂ O ₃ (10 mL) aqueous solution was added to the reaction mixture and stirred. After separating the organic layer from the mixed layer, the organic layer was _{washed with 10% Na 2} CO ₃ (10 mL) aqueous solution and distilled water. After the organic layer was separated again, water in the organic layer was removed using _{MgSO 4 .} After concentrating the organic layer, an excess of methanol was poured to precipitate the product, followed by filtration to obtain an intermediate H-3 (3.3 g).

(4) Host 1 synthesis

[Scheme 1-4]

Intermediate H-3 (1.96 g, 0.05 mol) and naphtalene-2-boronic acid (1.02 g, 0.06 mol) were dissolved in toluene (30 mL). The mixed solution was stirred under _{N 2 conditions. Na 2} CO ₃ (1.90 g) in distilled water (8 mL) was _{dissolved in Na 2} CO ₃ aqueous solution (1 mL) was added to the mixed solution. Then, Pd(PPh ₃ ) ₄ (0.125 g, 0.0125 mmol) was added. The mixture was reacted in a nitrogen atmosphere while heating. After the reaction, the organic layer was separated, and methanol was added thereto to precipitate a white solid mixture. The solid mixture was purified by silica-gel column chromatography using chloroform:hexane (volume ratio = 1:3) as an eluent to obtain Host 1 (2.30 g).

Synthesis Example 2: Synthesis of Host 2

[Scheme 2]

Intermediate H-3 (1.96 g, 0.05 mol), 4-(naphthalene-2-yl)phenylboronic acid (1.49 g, 0.06 mol) was dissolved in toluene (30 mL). The mixed solution was stirred under _{N 2 conditions. Na 2} CO ₃ (1.90 g) in distilled water (8 mL) was _{dissolved in Na 2} CO ₃ aqueous solution (1 mL) was added to the mixed solution. Pd(PPh ₃ ) ₄ (0.125 g, 0.0125 mmol) was added. The mixture was reacted in a nitrogen atmosphere while heating. After the reaction, the organic layer was separated, and methanol was added thereto to precipitate a white solid mixture. The solid mixture was purified by silica-gel column chromatography using chloroform:hexane (volume ratio = 1:3) as an eluent to obtain Host 2 (2.30 g).

Synthesis Example 3: Synthesis of Dopant 11-2

(1) intermediate I-P synthesis

[Scheme 3-1]

Under nitrogen condition, 2,3-dichlorobromobenzene-D (22.0 g), compound IE (26.6 g), Pd(dba) ₂ (bis(dibenzylideneacetone)palladium(0), 2.68 g), NaOtBu (sodium tert-butoxide, 16.8) g), tBu ₃ PHBF ₄ (tri-t-butylphosphonium tetrafluoroborate, 2.70 g), and xylene (300 mL) were placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene and heptane (volume ratio = 1:1) as a developing solvent to obtain an intermediate IP (35.0 g).

(2) intermediate I-Q synthesis

[Scheme 3-2]

Under nitrogen condition, intermediate IP (15.0 g), intermediate IE (8.4 g), palladium catalyst Pd-132 (dichlorobis[(di-t-butyl(4-dimethylaminophenyl)phosphino)palladium], 0.21 g), NaOtBu (sodium) -t-butoxide, 4.3 g) and xylene (60 mL) were placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene as a developing solvent to obtain Intermediate I-Q (14.6 g).

(3) Synthesis of Dopant 11-2

[Scheme 3-3]

Under nitrogen, 0°C, 1.56 M t-butyllithium pentane solution (27.5 mL) was added dropwise to the flask containing the intermediate IQ (14.6 g) and t-butylbenzene (120 mL). After completion of the dropwise addition of t-butyllithium pentane solution, the temperature of the mixture was raised to 70° C. and stirred for 0.5 hour. The residue was cooled to -50 °C and boron tribromide (10.7 g) was added. The temperature of the mixture was raised to room temperature and stirred again for 0.5 hours. Then, the mixture was cooled to 0° C. again, and EtNiPr ₂ (N,N-diisopropylethylamine (5.5 g) was added. The mixture was stirred at room temperature until heat generation stopped. Then, the temperature of the mixture was increased to 100 The temperature was raised to ℃ and stirred for 1 hour The reaction solution was cooled to room temperature, cooled aqueous sodium acetate solution and ethyl acetate were added, and the mixture was partitioned. The organic layer was concentrated and toluene was used as a developing solvent. A crude product was obtained through silica-gel short pass column chromatography, and the crude product was reprecipitated with heptane to obtain Dopant 11-2 (0.5 g).

Synthesis Example 4: Synthesis of Dopant 11-3

(1) Intermediate I-F synthesis

[Scheme 4-1]

Under nitrogen condition, 2,3-dichlorobromobenzene (22.0 g), compound IE (26.6 g), Pd(dba) ₂ (2.68 g), NaOtBu (16.8 g), tBu ₃ PHBF ₄ (2.70 g), xylene (300 mL) ) was placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene and heptane (volume ratio = 1:1) as a developing solvent to obtain an intermediate IF (38.0 g).

(2) Intermediate I-G synthesis

[Scheme 4-2]

Under nitrogen condition, Intermediate IF (15.0 g), Intermediate IE (8.4 g), palladium catalyst Pd-132 (0.21 g), NaOtBu (4.3 g), xylene (60 mL) were placed in a flask and heated at 120°C for 1 hour. heated. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene as a developing solvent to obtain Intermediate I-G (15.0 g).

(3) Synthesis of Dopant 11-3

[Scheme 4-3]

Under nitrogen and 0 °C conditions, 1.56 M t-butyllithium pentane solution (27.5 ml) was added dropwise to the flask containing the intermediate IG (15.0 g) and t-butylbenzene (120 mL). After completion of the dropwise addition of t-butyllithium pentane solution, the temperature of the mixture was raised to 70° C. and stirred for 0.5 hour. The residue was cooled to -50 °C and boron tribromide (10.7 g) was added. The temperature of the mixture was raised to room temperature and stirred for 0.5 hour. Then the mixture was cooled back to 0° C. and EtNiPr ₂ (5.5 g) was added. The mixture was stirred at room temperature until heat generation ceased. Then, the temperature of the mixture was raised to 100° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, cooled aqueous sodium acetate solution and ethyl acetate were added, and the mixture was partitioned. The organic layer was concentrated and a crude product was obtained through silica-gel short pass column chromatography using toluene as a developing solvent. The crude product was reprecipitated with heptane to obtain Dopant 11-3 (6.5 g).

Synthesis Example 5: Synthesis of Dopant 11-4

(1) intermediate I-S synthesis

[Scheme 5-1]

Under nitrogen condition, 2,3-dichlorobromobenzene (22.0 g), compound IR (26.6 g), Pd(dba) ₂ (2.68 g), NaOtBu (16.8 g), tBu ₃ PHBF ₄ (2.70 g), xylene (300 mL) ) was placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene and heptane (volume ratio = 1:1) as a developing solvent to obtain an intermediate IS (38.0 g).

(2) intermediate I-T synthesis

[Scheme 5-2]

Under nitrogen condition, Intermediate IS (15.0 g), Intermediate IR (8.4 g), palladium catalyst Pd-132 (0.21 g), NaOtBu (4.3 g), and xylene (60 mL) were placed in a flask and heated at 120°C for 1 hour. heated. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene as a developing solvent to obtain an intermediate I-T (15.0 g).

(3) Synthesis of Dopant 11-4

[Scheme 5-3]

Under nitrogen and 0 °C conditions, 1.56 M t-butyllithium pentane solution (27.5 ml) was added dropwise to the flask containing the intermediate IT (15.0 g) and t-butylbenzene (120 mL). After completion of the dropwise addition of t-butyllithium pentane solution, the temperature of the mixture was raised to 70° C. and stirred for 0.5 hour. The residue was cooled to -50 °C and boron tribromide (10.7 g) was added. The temperature of the mixture was raised to room temperature and stirred for 0.5 hour. Then the mixture was cooled back to 0° C. and EtNiPr ₂ (5.5 g) was added. The mixture was stirred at room temperature until heat generation ceased. Then, the temperature of the mixture was raised to 100° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, cooled aqueous sodium acetate solution and ethyl acetate were added, and the mixture was partitioned. The organic layer was concentrated and a crude product was obtained through silica-gel short pass column chromatography using toluene as a developing solvent. The crude product was reprecipitated with heptane to obtain Dopant 11-4 (8.0 g).

Synthesis Example 6: Synthesis of Dopant 11-1

(1) Synthesis of Intermediate I-5

[Scheme 6-1]

Under nitrogen condition, 2,3-dichlorobromobenzene (22.0 g), bis(4-t-butylphenyl)amine (26.6 g), Pd(dba) ₂ (2.68 g), NaOtBu (16.8 g), tBu ₃ PHBF ₄ (2.70) g), xylene (300 mL) was placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene and heptane (volume ratio = 1:1) as a developing solvent to obtain Intermediate I-5 (38.0 g).

(2) Intermediate I-6 synthesis

[Scheme 6-2]

Under nitrogen condition, intermediate I-5 (15.0 g), bis(4-t-butylphenyl)amine (8.4 g), palladium catalyst Pd-132 (0.21 g), NaOtBu (4.3 g), xylene (60 mL) were prepared It was placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene as a developing solvent to obtain Intermediate I-6 (15.0 g).

(3) Synthesis of Dopant 11-1

[Scheme 6-3]

Under nitrogen and 0 °C conditions, 1.56 M t-butyllithium pentane solution (27.5 ml) was added dropwise to the flask containing Intermediate I-6 (15.0 g) and t-butylbenzene (120 mL). After completion of the dropwise addition of t-butyllithium pentane solution, the temperature of the mixture was raised to 70° C. and stirred for 0.5 hour. The residue was cooled to -50 °C and boron tribromide (10.7 g) was added. The temperature of the mixture was raised to room temperature and stirred for 0.5 hour. Then the mixture was cooled back to 0° C. and EtNiPr ₂ (5.5 g) was added. The mixture was stirred at room temperature until heat generation ceased. Then, the temperature of the mixture was raised to 100° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, cooled aqueous sodium acetate solution and ethyl acetate were added, and the mixture was partitioned. The organic layer was concentrated and a crude product was obtained through silica-gel short pass column chromatography using toluene as a developing solvent. The crude product was reprecipitated with heptane to obtain Dopant 11-1 (6.5 g).

Synthesis Example 7: Synthesis of Dopant 21-2

(1) Intermediate I-N synthesis

[Scheme 7-1]

Under nitrogen condition, the intermediate IM (22.5 g), 4-bromo-t-butylbenzene-D4 (17.0 g), Pd-132 (0.57 g), NaOtBu (11.5 g), xylene (150 mL) was placed in a flask for 2 hours while stirring while heating. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed twice with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene and heptane (volume ratio = 2:8) as a developing solvent to obtain an intermediate I-N (30.0 g).

(2) intermediate I-O synthesis

[Scheme 7-2]

Under nitrogen condition, Intermediate I-C (12.0 g), Intermediate I-N (10.7 g), Pd-132 (0.19 g), NaOtBu (3.9 g), and xylene (60 mL) were placed in a flask and heated at 120° C. for 1.5 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed twice with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel column chromatography using toluene and heptane (volume ratio = 2:8) as a developing solvent to obtain an intermediate I-O (18.0 g).

(3) Synthesis of Dopant 21-2

[Scheme 7-3]

Under nitrogen and 0 °C conditions, 1.62 M t-butyllithium pentane solution (40.0 mL) was added dropwise to the flask containing the intermediate IO (18.0 g) and t-butylbenzene (90 mL). After completion of the dropwise addition of the t-butyllithium pentane solution, the temperature of the mixture was raised to 60° C. and stirred for 1 hour. Components having a lower boiling point than t-butylbenzene were distilled under reduced pressure. The residue was cooled to -50 °C and boron tribromide (16.5 g) was added. The temperature of the mixture was raised to room temperature and stirred for 0.5 hour. Then, the mixture was cooled back to 0° C. and EtNiPr ₂ (5.7 g) was added. The mixture was stirred at 100° C. for 1 h. After the reaction, sodium acetate aqueous solution was added to the reaction solution and stirred. Then, ethyl acetate was added and stirred. The organic layer was separated to obtain a crude product, and the crude product was purified through silica-gel column chromatography using toluene and heptane (volume ratio = 3:7) as a developing solvent to obtain Dopant 21-2 (0.6 g). .

Synthesis Example 8: Synthesis of Dopant 21-3

(1) Intermediate I-B synthesis

[Scheme 8-1]

Under nitrogen condition, intermediate IA (22.5 g), 4-bromo-t-butylbenzene (17.0 g), Pd-132 (0.57 g), NaOtBu (11.5 g), xylene (150 mL) was placed in a flask and heated for 1 hour. while stirring. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed twice with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene and heptane (volume ratio = 2:8) as a developing solvent to obtain Intermediate I-B (31.0 g).

(2) Intermediate I-D synthesis

[Scheme 8-2]

Under nitrogen condition, Intermediate I-C (12.0 g), Intermediate I-B (10.7 g), Pd-132 (0.19 g), NaOtBu (3.9 g), and xylene (60 mL) were placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed twice with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel column chromatography using toluene and heptane (volume ratio = 2:8) as a developing solvent to obtain Intermediate I-D (19.9 g).

(3) Synthesis of Dopant 21-3

[Scheme 8-3]

Under nitrogen and 0 °C conditions, 1.62 M t-butyllithium pentane solution (40.0 mL) was added dropwise to the flask containing Intermediate ID (18.0 g) and t-butylbenzene (90 mL). After completion of the dropwise addition of the t-butyllithium pentane solution, the temperature of the mixture was raised to 60° C. and stirred for 1 hour. Components having a lower boiling point than t-butylbenzene were distilled under reduced pressure. The residue was cooled to -50 °C and boron tribromide (16.5 g) was added. The temperature of the mixture was raised to room temperature and stirred for 0.5 hours. Then the mixture was cooled back to 0° C. and EtNiPr ₂ (5.7 g) was added. The mixture was stirred at 100° C. for 1 h. After the reaction, an aqueous sodium acetate solution was added to the reaction solution and stirred. Then, ethyl acetate was added and stirred. The organic layer was separated to obtain a crude product, and the crude product was purified through silica-gel column chromatography using toluene and heptane (volume ratio = 2:8) as a developing solvent to obtain Dopant 21-3 (4.0 g). .

Synthesis Example 9: Synthesis of Dopant 21-4

(1) Intermediate I-J synthesis

[Scheme 9-1]

Under nitrogen condition, Intermediate IA (22.5 g), 4-bromo-t-butylbenzene-D4 (17.0 g), Pd-132 (0.57 g), NaOtBu (11.5 g), xylene (150 mL) were placed in a flask, 1 Stir while heating for hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed twice with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene and heptane (volume ratio = 2:8) as a developing solvent to obtain Intermediate I-J (31.0 g).

(2) Intermediate I-L synthesis

[Scheme 9-2]

Under nitrogen condition, Intermediate IK (12.0 g), Intermediate IJ (10.7 g), Pd-132 (0.19 g), NaOtBu (3.9 g), and xylene (60 mL) were placed in a flask and heated at 120° C. for 1 hour. . After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed twice with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel column chromatography using toluene and heptane (volume ratio = 2:8) as a developing solvent to obtain Intermediate I-L (19.9 g).

(3) Synthesis of Dopant 21-4

[Scheme 9-3]

Under nitrogen and 0°C conditions, 1.62 M t-butyllithium pentane solution (40.0 mL) was added dropwise to the flask containing the intermediate IL (18.0 g) and t-butylbenzene (90 mL). After completion of the dropwise addition of the t-butyllithium pentane solution, the temperature of the mixture was raised to 60° C. and stirred for 1 hour. Components having a lower boiling point than t-butylbenzene were distilled under reduced pressure. The residue was cooled to -50 °C and boron tribromide (16.5 g) was added. The temperature of the mixture was raised to room temperature and stirred for 0.5 hours. Then the mixture was cooled back to 0° C. and EtNiPr ₂ (5.7 g) was added. The mixture was stirred at 100° C. for 1 h. After the reaction, an aqueous sodium acetate solution was added to the reaction solution and stirred. Then, ethyl acetate was added and stirred. The organic layer was separated to obtain a crude product, and the crude product was purified through silica-gel column chromatography using toluene and heptane (volume ratio = 2:8) as a developing solvent to obtain Dopant 21-4 (4.0 g). .

Synthesis Example 10: Synthesis of Dopant 21-1

(1) Synthesis of Intermediate I-2

[Scheme 10-1]

Under nitrogen condition, Intermediate I-1 (22.5 g), 4-bromo-t-butylbenzene (17.0 g), Pd-132 (0.57 g), NaOtBu (11.5 g), xylene (150 mL) were placed in a flask, 1 Stir while heating for hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed twice with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel short column chromatography using toluene and heptane (volume ratio = 2:8) as a developing solvent to obtain Intermediate I-2 (31.0 g).

(2) Intermediate I-4 synthesis

[Scheme 10-2]

Under nitrogen condition, put Intermediate I-3 (12.0 g), Intermediate I-2 (10.7 g), Pd-132 (0.19 g), NaOtBu (3.9 g), and xylene (60 mL) in a flask at 120°C for 1 hour heated while After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Then, the organic layer was separated and washed twice with water. Next, the organic layer was concentrated to obtain a crude product. The crude product was purified through silica-gel column chromatography using toluene and heptane (volume ratio = 2:8) as developing solvents to obtain Intermediate I-4 (19.9 g).

(3) Synthesis of Dopant 21-1

[Scheme 10-3]

Under nitrogen and 0 °C conditions, 1.62 M t-butyllithium pentane solution (40.0 mL) was added dropwise to the flask containing Intermediate I-4 (18.0 g) and t-butylbenzene (90 mL). After completion of the dropwise addition of t-butyllithium pentane solution, the temperature of the mixture was raised to 60° C. and stirred for 1 hour. Components having a lower boiling point than t-butylbenzene were distilled under reduced pressure. The residue was cooled to -50 °C and boron tribromide (16.5 g) was added. The temperature of the mixture was raised to room temperature and stirred for 0.5 hours. Then the mixture was cooled back to 0° C. and EtNiPr ₂ (5.7 g) was added. The mixture was stirred at 100° C. for 1 h. After the reaction, an aqueous sodium acetate solution was added to the reaction solution and stirred. Then, ethyl acetate was added and stirred. The organic layer was separated to obtain a crude product, and the crude product was purified through silica-gel column chromatography using toluene and heptane (volume ratio = 2:8) as a developing solvent to obtain Dopant 21-1 (4.0 g). .

Example 1 (Ex. 1): Organic light emitting diode manufacturing

Host 1 synthesized in Synthesis Example 1 was used as a host of the light emitting material layer (EML), Dopant 21-1 synthesized in Synthesis Example 10 was used as a dopant, and E1 of Formula 6, holes in the electron blocking layer (EBL) An organic light emitting diode in which 2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene was applied to the blocking layer (HBL), respectively, was prepared. First, a glass substrate with an ITO electrode of 40 mm x 40 mm x 0.5 mm thick was ultrasonically cleaned with isopropyl alcohol, acetone, and DI water for 5 minutes, and then dried in an oven at 100 ° C. _{After cleaning the substrate, O 2} plasma treatment was carried out for 2 minutes in a vacuum state and transferred to a deposition chamber to deposit other layers thereon. An organic material layer was deposited in the following order by evaporation from a heating boat under a vacuum of about 10 ^{-7 Torr.}

A hole injection layer (97 wt% of a compound of Formula 11, 3 wt% doping of a compound of Formula 12, 100 Å), a hole transport layer (a compound of Formula 11, 100 Å), an electron blocking layer (E1, 100 Å), a light emitting material layer (Host 1 98 wt% dopant 21-1 2 wt% doping, 200 Å), hole blocking layer (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene, 100 Å) An electron injection layer (1,3-bis(9-phenyl-1,10-phenathrolin-2-yl)benzene 98 wt% doped with 2 wt% Li, 200 Å) and a cathode (Al, 500 Å) were sequentially stacked.

After CPL (capping layer) was formed, it was encapsulated with glass. After deposition of these layers, they were transferred from the deposition chamber into a drying box for film formation and subsequently encapsulated using UV curing epoxy and moisture getter.

[Formula 11]

[Formula 12]

Examples 2 to 3: Preparation of organic light emitting diodes

The same material as in Example 1 and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 1 to 3: Preparation of organic light emitting diodes

Host 1-1 of the following formula 13 is used as a host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1, 1'-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 1, respectively (Comparative Example 1, Ref. 1), repeating the same materials and procedures as in Example 2 (Comparative Example 2, Ref. 2), by repeating the same materials and procedures as in Example 3 (Comparative Example 3, Ref. 3) to prepare an organic light emitting diode, respectively.

Comparative Examples 4 to 6: Preparation of organic light emitting diodes

Host 1-2 of the following formula 13 is used as a host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1, 1'-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 1, respectively (Comparative Example 4, Ref. 4), repeating the same materials and procedures as in Example 2 (Comparative Example 5, Ref. 5), by repeating the same materials and procedures as in Example 3 (Comparative Example 6, Ref. 6) to prepare an organic light emitting diode, respectively.

Comparative Examples 7 to 9: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, Repeating the same materials and procedures as in Example 1 (Comparative Example 7, Ref. 7), repeating the same materials and procedures as in Example 2 (Comparative Example 8, Ref. 8), and repeating the same materials and procedures as in Example 3 Each of the organic light emitting diodes was manufactured by repeating (Comparative Example 9, Ref. 9).

Comparative Examples 10 to 12: Preparation of organic light emitting diodes

Host 1-3 of the following formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1, 1'-biphenyl) -4,4'-diamine), the same materials and procedures as in Example 1 were repeated, respectively (Comparative Example 10, Ref. 10), and the same materials and procedures as in Example 2 were repeated (Comparative Example 11, Ref. 11), by repeating the same materials and procedures as in Example 3 (Comparative Example 12, Ref. 12) to prepare an organic light emitting diode, respectively.

Comparative Examples 13 to 15: Preparation of organic light emitting diodes

Host 1-4 of the following formula 13 is used as a host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1, 1'-biphenyl) -4,4'-diamine), the same materials and procedures as in Example 1 were repeated, respectively (Comparative Example 13, Ref. 13), and the same materials and procedures as in Example 2 were repeated (Comparative Example 14, Ref. 14), by repeating the same materials and procedures as in Example 3 (Comparative Example 15, Ref. 15) to prepare an organic light emitting diode, respectively.

[Formula 13]

Experimental Example 1: Measurement of optical properties of organic light emitting diodes

The optical properties of each of the organic light emitting diodes prepared in Examples 1 to 3 and Comparative Examples 1 to 15 were measured. Each organic light emitting diode having an emission area of 9 mm 2 was connected to an external power source, and the optical properties of the device were evaluated at room temperature using a current source (KEITHLEY) and a photometer (PR 650). For each organic light emitting diode, the driving voltage (V), current efficiency (cd/A), CIE color coordinates for each device at a current density of 10 mA/cm2, and at 40°C, at a current density of 22.5 mA/cm2 _{The device lifetime (T 95} ) at which the luminance fell from 100% to 95% was measured, respectively. The measurement results are shown in Table 1 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Host V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 1 ^a Host 1-1 3.76 2.32 0.136 0.077 40 Ref. 2 ^b Host 1-1 3.71 2.55 0.135 0.076 45 Ref. 3 ^c Host 1-1 3.76 2.44 0.135 0.077 50 Ref. 4 ^a Host 1-2 3.77 2.35 0.134 0.077 43 Ref. 5 ^b Host 1-2 3.70 2.61 0.135 0.078 45 Ref. 6 ^c Host 1-2 3.77 2.41 0.135 0.077 54 Ref. 7 ^a host 1 3.78 2.44 0.135 0.076 68 Ref. 8 ^b host 1 3.74 2.69 0.134 0.077 74 Ref. 9 ^c host 1 3.76 2.38 0.135 0.076 78 Ref. 10 ^a Host 1-3 3.77 2.13 0.134 0.077 44 Ref. 11 ^b Host 1-3 3.72 2.24 0.135 0.078 47 Ref. 12 ^c Host 1-3 3.76 2.19 0.135 0.077 48 Ref. 13 ^a Host 1-4 3.77 2.11 0.135 0.076 60 Ref. 14 ^b Host 1-4 3.73 2.35 0.134 0.077 68 Ref. 15 ^c Host 1-4 3.77 2.19 0.135 0.076 74 Ex. 1 ^d host 1 3.78 4.43 0.135 0.077 143 Ex. 2 ^e host 1 3.73 4.59 0.135 0.077 184 Ex. 3 ^f host 1 3.76 4.42 0.135 0.077 227 Dopant 21-1 was used in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^b : EBL (NPB), HBL (H1);
^c : EBL (NPB), HBL (H31);
^d : EBL (E1), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthraecne);
^e : EBL (E1), HBL (H1);
^f : EBL (E1), HBL (H31)

As shown in Table 1, in the organic light emitting diode (Comparative Example 7-9) in which Host 1 in which only the anthracene core was substituted with deuterium was introduced into the light emitting material layer, Host 1-1 was not substituted with deuterium or only the substituent was substituted with deuterium. , Host 1-2, Host 1-3 was significantly increased compared to the organic light emitting diode (Comparative Example 1-6, Comparative Example 10-12) introduced into the light emitting material layer. In addition, compared with the organic light emitting diode (Comparative Example 13-15) in which Host 1-4 substituted with deuterium in both the anthracene core and the substituents was introduced into the light emitting material layer, Host 1 in which only the anthracene core was substituted with deuterium was added to the light emitting material layer. The introduced organic light emitting diode (Comparative Examples 7-9) has improved current efficiency and light emitting lifetime. This means that sufficient luminous efficiency and lifetime increase can be realized while containing less expensive deuterium.

In addition, compared with the organic light emitting diode in which NPB was introduced into the electron blocking layer (Comparative Examples 7-9), the current of the organic light emitting diode (Example 1-3) in which the E1 compound included in Formula 6 was introduced into the electron blocking layer (Example 1-3) Efficiency is improved by up to 85.7% and luminous lifetime by up to 191.0%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, the current efficiency and light emission lifetime of the organic light emitting diode were significantly improved.

Example 4 (Ex. 4): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 1, except that Dopant 21-2 was used as a dopant for the light emitting material layer.

Examples 5 to 6: Preparation of organic light emitting diodes

The same materials and procedures as in Example 4, except that H1 of Formula 8 (Example 5, Ex. 5) and H31 of Formula 10 (Example 6, Ex 6) were used as the material of the hole blocking layer (HBL), respectively. was repeated to prepare organic light emitting diodes, respectively.

Comparative Examples 16 to 18: Preparation of organic light emitting diodes

Host 1-1 of Chemical Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 4 (Comparative Example 16, Ref. 16), repeating the same materials and procedures as in Example 5 ( Comparative Example 17, Ref. 17) and the same materials and procedures as in Example 6 were repeated (Comparative Example 18, Ref. 18) to manufacture organic light emitting diodes, respectively.

Comparative Examples 19 to 21: Preparation of organic light emitting diodes

Host 1-2 of Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 4 (Comparative Example 19, Ref. 19), repeating the same materials and procedures as in Example 5 ( Comparative Example 20, Ref. 20) and the same materials and procedures as in Example 6 were repeated (Comparative Example 21, Ref. 21) to manufacture organic light emitting diodes, respectively.

Comparative Examples 22 to 24: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, The same materials and procedures as those of Example 4 were repeated (Comparative Example 22, Ref. 22), the same materials and procedures as those of Example 5 were repeated (Comparative Example 23, Ref. 23), and the same materials and procedures as those of Example 6 were repeated. Each of the organic light emitting diodes was manufactured by repeating (Comparative Example 24, Ref. 24).

Comparative Examples 25 to 27: Preparation of organic light emitting diodes

Host 1-3 of Chemical Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 4 (Comparative Example 25, Ref. 25), repeating the same materials and procedures as in Example 5 ( Comparative Example 26, Ref. 26) and the same materials and procedures as in Example 6 were repeated (Comparative Example 27, Ref. 27) to manufacture organic light emitting diodes, respectively.

Comparative Examples 28 to 30: Preparation of organic light emitting diodes

Host 1-4 of Chemical Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 4 (Comparative Example 28, Ref. 28), repeating the same materials and procedures as in Example 5 ( Comparative Example 29, Ref. 29) and the same materials and procedures as in Example 6 were repeated (Comparative Example 30, Ref. 30) to manufacture organic light emitting diodes, respectively.

Experimental Example 2: Evaluation of optical properties of organic light emitting diodes

The optical properties of each of the organic light emitting diodes prepared in Examples 4 to 6 and Comparative Examples 16 to 30 were measured according to the same procedure as in Experimental Example 1. The measurement results are shown in Table 2 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Host V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 16 ^a Host 1-1 3.76 2.09 0.136 0.077 40 Ref. 17 ^b Host 1-1 3.74 2.22 0.135 0.076 44 Ref. 18 ^c Host 1-1 3.76 2.08 0.135 0.077 51 Ref. 19 ^a Host 1-2 3.77 1.82 0.134 0.077 41 Ref. 20 ^b Host 1-2 3.72 2.07 0.135 0.078 44 Ref. 21 ^c Host 1-2 3.77 1.84 0.135 0.077 50 Ref. 22 ^a host 1 3.76 2.04 0.135 0.076 54 Ref. 23 ^b host 1 3.74 2.19 0.134 0.077 60 Ref. 24 ^c host 1 3.76 2.06 0.135 0.076 64 Ref. 25 ^a Host 1-3 3.77 2.13 0.136 0.077 40 Ref. 26 ^b Host 1-3 3.73 2.22 0.135 0.076 41 Ref. 27 ^c Host 1-3 3.77 2.16 0.135 0.077 48 Ref. 28 ^a Host 1-4 3.76 2.09 0.136 0.077 60 Ref. 29 ^b Host 1-4 3.70 2.25 0.135 0.076 64 Ref. 30 ^c Host 1-4 3.76 2.11 0.135 0.077 71 Ex. 4 ^d host 1 3.76 4.42 0.135 0.077 145 Ex. 5 ^e host 1 3.73 4.52 0.135 0.077 198 Ex. 6 ^f host 1 3.76 4.43 0.135 0.077 228 Dopant 21-2 was used in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^b : EBL (NPB), HBL (H1);
^c : EBL (NPB), HBL (H31);
^d : EBL (E1), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^e : EBL (E1), HBL (H1);
^f : EBL (E1), HBL (H31)

As shown in Table 2, the organic light emitting diodes introducing Host 1 in which only the anthracene core was substituted with deuterium (Comparative Examples 22-24) were not substituted with deuterium, or only the substituents were substituted with deuterium, Host 1-1, Host 1- 2, compared with the organic light emitting diodes (Comparative Examples 16-21, Comparative Examples 25-27) to which Host 1-3 was introduced, the lifespan was significantly increased. In addition, compared with the organic light emitting diode introducing Host 1-4 substituted with deuterium in both the anthracene core and the substituent (Comparative Example 28-30), the organic light emitting diode introducing Host 1 in which only the anthracene core is substituted with deuterium (Comparative Example) 22-24) had equal or slightly decreased current efficiency and luminescence lifetime. This means that sufficient luminous efficiency and lifetime increase can be realized while containing less expensive deuterium.

In addition, compared with the organic light emitting diode (Comparative Examples 22-24) in which NPB was introduced into the electron blocking layer, the current efficiency of the organic light emitting diode (Example 4-6) to which the E1 compound included in Formula 6 was introduced (Example 4-6) was up to 116.7 %, the luminescence lifetime was improved by up to 256.3%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, current efficiency and light emission lifetime were significantly improved.

Example 7 (Ex. 7): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 1, except that Dopant 21-3 was used as a dopant for the light emitting material layer.

Examples 8 to 9: Preparation of organic light emitting diodes

The same material as in Example 7, except that H1 of Formula 8 (Example 8, Ex. 8) and H31 of Formula 10 (Example 9, Ex. 9) were used as the material of the hole blocking layer (HBL), respectively, and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 31 to 33: Preparation of organic light emitting diodes

Host 1-1 of Chemical Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 7 (Comparative Example 31, Ref. 31), repeating the same materials and procedures as in Example 8 ( Comparative Example 32, Ref. 32) and the same materials and procedures as in Example 9 were repeated (Comparative Example 33, Ref. 33) to manufacture an organic light emitting diode, respectively.

Comparative Examples 34 to 36: Preparation of organic light emitting diodes

Host 1-2 of Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 7 (Comparative Example 34, Ref. 34), repeating the same materials and procedures as in Example 8 ( Comparative Example 35, Ref. 35) and the same materials and procedures as in Example 9 were repeated (Comparative Example 36, Ref. 36) to manufacture organic light emitting diodes, respectively.

Comparative Examples 37 to 39: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, Repeat the same materials and procedures as in Example 7 (Comparative Example 37, Ref. 37), repeat the same materials and procedures as in Example 8 (Comparative Example 38, Ref. 38), and repeat the same materials and procedures as in Example 9 Each of the organic light emitting diodes was manufactured by repeating (Comparative Example 39, Ref. 39).

Comparative Examples 40 to 42: Preparation of organic light emitting diodes

Host 1-3 of Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 7 (Comparative Example 40, Ref. 40), repeating the same materials and procedures as in Example 8 ( Comparative Examples 41, Ref. 41) and the same materials and procedures as in Example 9 were repeated (Comparative Example 42, Ref. 42) to manufacture organic light emitting diodes, respectively.

Comparative Examples 43 to 45: Preparation of organic light emitting diodes

Host 1-4 of Chemical Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 7 (Comparative Example 43, Ref. 43), repeating the same materials and procedures as in Example 8 ( Comparative Example 44, Ref. 44) and the same materials and procedures as in Example 9 were repeated (Comparative Example 45, Ref. 45) to manufacture an organic light emitting diode, respectively.

Experimental Example 3: Evaluation of optical properties of organic light emitting diodes

The optical properties of each of the organic light emitting diodes prepared in Examples 7 to 9 and Comparative Examples 31 to 45 were measured according to the same procedure as in Experimental Example 1. The measurement results are shown in Table 3 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Host V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 31 ^a Host 1-1 3.76 2.18 0.136 0.077 43 Ref. 32 ^b Host 1-1 3.69 2.38 0.135 0.076 45 Ref. 33 ^c Host 1-1 3.76 2.20 0.135 0.077 51 Ref. 34 ^a Host 1-2 3.77 2.09 0.134 0.077 40 Ref. 35 ^b Host 1-2 3.70 2.31 0.135 0.078 43 Ref. 36 ^c Host 1-2 3.77 2.14 0.135 0.077 52 Ref. 37 ^a host 1 3.77 2.17 0.135 0.076 52 Ref. 38 ^b host 1 3.73 2.34 0.135 0.076 60 Ref. 39 ^c host 1 3.77 2.22 0.134 0.077 67 Ref. 40 ^a Host 1-3 3.76 2.14 0.135 0.077 44 Ref. 41 ^b Host 1-3 3.71 2.30 0.136 0.077 45 Ref. 42 ^c Host 1-3 3.76 2.16 0.135 0.076 54 Ref. 43 ^a Host 1-4 3.79 2.15 0.135 0.077 62 Ref. 44 ^b Host 1-4 3.69 2.27 0.134 0.077 65 Ref. 45 ^c Host 1-4 3.74 2.17 0.135 0.078 75 Ex. 7 ^d host 1 3.78 4.44 0.135 0.076 119 Ex. 8 ^e host 1 3.74 4.54 0.135 0.077 193 Ex. 9 ^f host 1 3.77 4.42 0.135 0.077 231 Dopant 21-3 was used in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^b : EBL (NPB), HBL (H1);
^c : EBL (NPB), HBL (H31);
^d : EBL (E1), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^e : EBL (E1), HBL (H1);
^f : EBL (E1), HBL (H31)

As shown in Table 3, in the organic light emitting diode (Comparative Examples 37-39) in which Host 1 in which only the anthracene core was substituted with deuterium was introduced into the light emitting material layer, Host 1-1 was not substituted with deuterium or only the substituent was substituted with deuterium. , Host 1-2, Host 1-3 was significantly increased compared to the organic light emitting diodes (Comparative Examples 31-36, Comparative Examples 40-42) introduced into the light emitting material layer. In addition, compared with the organic light emitting diode (Comparative Examples 43-45) in which Host 1-4 substituted with deuterium in both the anthracene core and the substituents was introduced into the light emitting material layer, Host 1 in which only the anthracene core was substituted with deuterium was added to the light emitting material layer. In the introduced organic light emitting diodes (Comparative Examples 37-39), the current efficiency was slightly improved, and the light emission lifetime was equal or slightly decreased. This means that sufficient luminous efficiency and lifetime increase can be realized while containing less expensive deuterium.

In addition, compared with the organic light emitting diode in which NPB was introduced into the electron blocking layer (Comparative Examples 37-39), the current of the organic light emitting diode (Example 7-9) in which the E1 compound included in Formula 6 was introduced into the electron blocking layer Efficiency is improved by up to 104.6% and luminous lifetime by up to 244.8%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, the current efficiency and light emission lifetime of the organic light emitting diode were significantly improved.

Example 10 (Ex. 10): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 1, except that Dopant 21-4 was used as a dopant for the light emitting material layer.

Examples 11 to 12: Organic light emitting diode manufacturing

The same material as in Example 10 and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 46 to 48: Preparation of organic light emitting diodes

Host 1-1 of Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 10 (Comparative Example 46, Ref. 46), repeating the same materials and procedures as in Example 11 ( Comparative Example 47, Ref. 47) and the same materials and procedures as in Example 12 were repeated (Comparative Example 48, Ref. 48) to manufacture organic light emitting diodes, respectively.

Comparative Examples 49 to 51: Preparation of organic light emitting diodes

Host 1-2 of Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 10 (Comparative Example 49, Ref. 49), repeating the same materials and procedures as in Example 11 ( Comparative Example 50, Ref. 50) and the same materials and procedures as in Example 12 were repeated (Comparative Example 51, Ref. 51) to manufacture organic light emitting diodes, respectively.

Comparative Examples 52 to 54: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, Repeat the same materials and procedures as in Example 10 (Comparative Example 52, Ref. 52), repeat the same materials and procedures as in Example 11 (Comparative Example 53, Ref. 53), and repeat the same materials and procedures as in Example 12 Each of the organic light emitting diodes was manufactured by repeating (Comparative Example 54, Ref. 54).

Comparative Examples 55 to 57: Preparation of organic light emitting diodes

Host 1-3 of Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), each repeating the same materials and procedures as in Example 10 (Comparative Example 55, Ref. 55), repeating the same materials and procedures as in Example 11 ( Comparative Example 56, Ref. 56) and the same materials and procedures as in Example 12 were repeated (Comparative Example 57, Ref. 57) to manufacture organic light emitting diodes, respectively.

Comparative Examples 58 to 60: Preparation of organic light emitting diodes

Host 1-4 of Chemical Formula 13 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 10 (Comparative Example 58, Ref. 58), repeating the same materials and procedures as in Example 11 ( Comparative Example 59, Ref. 59) and the same materials and procedures as in Example 12 were repeated (Comparative Example 60, Ref. 60) to manufacture an organic light emitting diode, respectively.

Experimental Example 4: Evaluation of optical properties of organic light emitting diodes

The optical properties of each of the organic light emitting diodes prepared in Examples 10 to 12 and Comparative Examples 46 to 60 were measured according to the same procedure as in Experimental Example 1. The measurement results are shown in Table 4 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Host V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 46 ^a Host 1-1 3.79 2.18 0.134 0.077 67 Ref. 47 ^b Host 1-1 3.73 2.29 0.134 0.077 69 Ref. 48 ^c Host 1-1 3.77 2.22 0.135 0.078 82 Ref. 49 ^a Host 1-2 3.78 2.16 0.134 0.077 65 Ref. 50 ^b Host 1-2 3.74 2.31 0.135 0.076 68 Ref. 51 ^c Host 1-2 3.77 2.17 0.135 0.077 81 Ref. 52 ^a host 1 3.78 2.16 0.135 0.076 86 Ref. 53 ^b host 1 3.73 2.32 0.135 0.077 88 Ref. 54 ^c host 1 3.78 2.19 0.136 0.077 111 Ref. 55 ^a Host 1-3 3.78 2.14 0.135 0.076 64 Ref. 56 ^b Host 1-3 3.73 2.27 0.135 0.077 65 Ref. 57 ^c Host 1-3 3.76 2.16 0.136 0.077 81 Ref. 58 ^a Host 1-4 3.79 2.15 0.135 0.078 101 Ref. 59 ^b Host 1-4 3.73 2.29 0.135 0.077 102 Ref. 60 ^c Host 1-4 3.78 2.17 0.135 0.077 119 Ex. 10 ^d host 1 3.77 4.48 0.135 0.076 187 Ex. 11 ^e host 1 3.74 4.59 0.135 0.077 309 Ex. 12 ^f host 1 3.76 4.46 0.136 0.077 354 Dopant 21-4 was used in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^b : EBL (NPB), HBL (H1);
^c : EBL (NPB), HBL (H31);
^d : EBL (E1), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^e : EBL (E1), HBL (H1);
^f : EBL (E1), HBL (H31)

As shown in Table 4, in the organic light emitting diode (Comparative Examples 52-54) in which Host 1 in which only the anthracene core was substituted with deuterium was introduced into the light emitting material layer, Host 1-1 was not substituted with deuterium or only the substituent was substituted with deuterium. , Host 1-2, Host 1-3 was significantly increased compared to the organic light emitting diode (Comparative Example 46-51, Comparative Example 55-57) introduced into the light emitting material layer. In addition, compared with the organic light emitting diode (Comparative Example 58-60) in which Host 1-4 substituted with deuterium in both the anthracene core and the substituents was introduced into the light emitting material layer, Host 1 in which only the anthracene core was substituted with deuterium was added to the light emitting material layer. The introduced organic light emitting diodes (Comparative Examples 52-54) had equal or slightly reduced current efficiency and light emission lifetime. This means that sufficient luminous efficiency and lifetime increase can be realized while containing less expensive deuterium.

In addition, compared with the organic light emitting diode in which NPB was introduced into the electron blocking layer (Comparative Examples 52-54), the current of the organic light emitting diode (Example 10-12) in which the E1 compound included in Formula 6 was introduced into the electron blocking layer Efficiency is improved by up to 107.4% and luminous lifetime by up to 251.1%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, the current efficiency and light emission lifetime of the organic light emitting diode were significantly improved.

Example 13 (Ex. 13): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 1, except that Host 2 was used as a host of the light emitting material layer.

Examples 14 to 15: Organic light emitting diode manufacturing

The same material as in Example 13, except that H1 of Formula 8 (Example 14, Ex. 14) and H31 of Formula 10 (Example 15, Ex. 15) were used as the material of the hole blocking layer (HBL), respectively, and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 61 to 63: Preparation of organic light emitting diodes

Host 2-1 of the following formula 14 is used as a host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1, 1'-biphenyl) -4,4'-diamine), the same materials and procedures as in Example 13 were repeated (Comparative Example 61, Ref. 61), and the same materials and procedures as in Example 14 were repeated. (Comparative Example 62, Ref. 62), by repeating the same materials and procedures as in Example 15 (Comparative Example 63, Ref. 63) to prepare an organic light emitting diode, respectively.

Comparative Examples 64 to 66: Preparation of organic light emitting diodes

Host 2-2 of the following formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1, 1'-biphenyl) -4,4'-diamine), the same materials and procedures as in Example 13 were repeated (Comparative Example 64, Ref. 64), and the same materials and procedures as in Example 14 were repeated. (Comparative Example 65, Ref. 65), by repeating the same materials and procedures as in Example 15 (Comparative Example 66, Ref. 66) to prepare an organic light emitting diode, respectively.

Comparative Examples 67 to 69: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, Repeating the same materials and procedures as in Example 13 (Comparative Example 67, Ref. 67), repeating the same materials and procedures as in Example 14 (Comparative Example 68, Ref. 68), and repeating the same materials and procedures as in Example 15 Each of the organic light emitting diodes was manufactured by repeating (Comparative Example 69, Ref. 69).

Comparative Examples 70 to 72: Preparation of organic light emitting diodes

Host 2-3 of the following formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1, 1'-biphenyl) -4,4'-diamine), the same materials and procedures as in Example 13 were repeated (Comparative Example 70, Ref. 70), respectively, and the same materials and procedures as in Example 14 were repeated (Comparative Example 71, Ref. 71), by repeating the same materials and procedures as in Example 15 (Comparative Example 72, Ref. 72) to prepare an organic light emitting diode, respectively.

Comparative Examples 73 to 75: Preparation of organic light emitting diodes

Host 2-4 of the following formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1, 1'-biphenyl) -4,4'-diamine), the same materials and procedures as in Example 13 were repeated (Comparative Example 73, Ref. 73), respectively, and the same materials and procedures as in Example 14 were repeated. (Comparative Example 74, Ref. 74), by repeating the same materials and procedures as in Example 15 (Comparative Example 75, Ref. 75) to prepare an organic light emitting diode, respectively.

[Formula 14]

Experimental Example 5: Evaluation of optical properties of organic light emitting diodes

The optical properties of each of the organic light emitting diodes prepared in Examples 13 to 15 and Comparative Examples 61 to 75 were measured according to the same procedure as in Experimental Example 1. The measurement results are shown in Table 5 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Host V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 61 ^a Host 2-1 3.79 2.20 0.134 0.077 40 Ref. 62 ^b Host 2-1 3.71 2.36 0.135 0.078 43 Ref. 63 ^c Host 2-1 3.77 2.21 0.135 0.077 49 Ref. 64 ^a Host 2-2 3.78 2.17 0.135 0.076 45 Ref. 65 ^b Host 2-2 3.72 2.34 0.134 0.077 47 Ref. 66 ^c Host 2-2 3.76 2.18 0.135 0.076 57 Ref. 67 ^a host 2 3.80 2.16 0.136 0.077 64 Ref. 68 ^b host 2 3.73 2.35 0.135 0.076 67 Ref. 69 ^c host 2 3.77 2.17 0.135 0.077 79 Ref. 70 ^a Host 2-3 3.76 2.18 0.136 0.077 44 Ref. 71 ^b Host 2-3 3.73 2.30 0.135 0.076 45 Ref. 72 ^c Host 2-3 3.75 2.19 0.135 0.077 57 Ref. 73 ^a Host 2-4 3.80 2.17 0.134 0.077 61 Ref. 74 ^b Host 2-4 3.74 2.35 0.135 0.078 62 Ref. 75 ^c Host 2-4 3.78 2.19 0.135 0.077 77 Ex. 13 ^d host 2 3.78 4.48 0.136 0.077 146 Ex. 14 ^e host 2 3.74 4.56 0.135 0.076 188 Ex. 15 ^f host 2 3.76 4.46 0.135 0.077 234 Dopant 21-1 was used in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^b : EBL (NPB), HBL (H1);
^c : EBL (NPB), HBL (H31);
^d : EBL (E1), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^e : EBL (E1), HBL (H1);
^f : EBL (E1), HBL (H31)

As shown in Table 5, in the organic light emitting diode (Comparative Examples 67-69) in which Host 2 in which only the anthracene core was substituted with deuterium was introduced into the light emitting material layer, Host 2-1 was not substituted with deuterium or only the substituent was substituted with deuterium. , Host 2-2, Host 2-3 was significantly increased compared to the organic light emitting diodes (Comparative Examples 61-66, Comparative Examples 70-72) introduced into the light emitting material layer. In addition, compared with the organic light emitting diode (Comparative Examples 73-75) in which Host 2-4 substituted with deuterium in both the anthracene core and the substituents was introduced into the light emitting material layer, Host 2 in which only the anthracene core was substituted with deuterium was added to the light emitting material layer. The introduced organic light emitting diodes (Comparative Examples 67-69) had equal or slightly higher current efficiency and light emission lifetime. This means that sufficient luminous efficiency and lifetime increase can be realized while containing less expensive deuterium.

In addition, compared with the organic light emitting diode in which NPB was introduced into the electron blocking layer (Comparative Examples 67-69), the current of the organic light emitting diode (Example 13-15) in which the E1 compound included in Formula 6 was introduced into the electron blocking layer Efficiency is improved by up to 107.4% and luminous lifetime by up to 196.2%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, the current efficiency and light emission lifetime of the organic light emitting diode were significantly improved.

Example 16 (Ex. 16): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 13, except that Dopant 21-2 was used as the dopant of the light emitting material layer.

Examples 17 to 18: Organic light emitting diode manufacturing

The same material as in Example 16, except that H1 of Formula 8 (Example 17, Ex. 17) and H31 of Formula 10 (Example 18, Ex. 18) were used as the material of the hole blocking layer (HBL), respectively, and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 76 to 78: Preparation of organic light emitting diodes

Host 2-1 of Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 16 (Comparative Example 76, Ref. 76), repeating the same materials and procedures as in Example 17 ( Comparative Example 77, Ref. 77) and the same materials and procedures as in Example 18 were repeated (Comparative Example 78, Ref. 78) to manufacture organic light emitting diodes, respectively.

Comparative Examples 79 to 81: Preparation of organic light emitting diodes

Host 2-2 of Chemical Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 16 (Comparative Example 79, Ref. 79), repeating the same materials and procedures as in Example 17 ( Comparative Example 80, Ref. 80) and the same materials and procedures as in Example 18 were repeated (Comparative Example 81, Ref. 81) to manufacture organic light emitting diodes, respectively.

Comparative Examples 82 to 84: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, The same materials and procedures as those of Example 16 were repeated (Comparative Example 82, Ref. 82), the same materials and procedures as those of Example 17 were repeated (Comparative Example 83, Ref. 83), and the same materials and procedures as those of Example 18 were repeated. Each of the organic light emitting diodes was manufactured by repeating (Comparative Example 84, Ref. 84).

Comparative Examples 85 to 87: Preparation of organic light emitting diodes

Host 2-3 of Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 16 (Comparative Example 85, Ref. 85), repeating the same materials and procedures as in Example 17 ( Comparative Example 86, Ref. 86) and the same materials and procedures as in Example 18 were repeated (Comparative Example 87, Ref. 87) to manufacture organic light emitting diodes, respectively.

Comparative Examples 88 to 90: Preparation of organic light emitting diodes

Host 2-4 of Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 16 (Comparative Example 88, Ref. 88), repeating the same materials and procedures as in Example 17 ( Comparative Example 89, Ref. 89) and the same materials and procedures as in Example 18 were repeated (Comparative Example 90, Ref. 90) to manufacture organic light emitting diodes, respectively.

Experimental Example 6: Evaluation of optical properties of organic light emitting diodes

The optical properties of each of the organic light emitting diodes prepared in Examples 16 to 18 and Comparative Examples 76 to 90 were measured according to the same procedure as in Experimental Example 1. The measurement results are shown in Table 6 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Host V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 76 ^a Host 2-1 3.79 2.21 0.135 0
076 38 Ref. 77 ^b Host 2-1 3.73 2.24 0.134 0.077 41 Ref. 78 ^c Host 2-1 3.78 2.17 0.135 0.076 54 Ref. 79 ^a Host 2-2 3.76 2.18 0.134 0.077 41 Ref. 80 ^b Host 2-2 3.72 2.30 0.135 0.078 44 Ref. 81 ^c Host 2-2 3.77 2.16 0.135 0.077 48 Ref. 82 ^a host 2 3.79 2.18 0.134 0.077 55 Ref. 83 ^b host 2 3.73 2.28 0.135 0.078 58 Ref. 84 ^c host 2 3.79 2.19 0.135 0.077 67 Ref. 85 ^a Host 2-3 3.78 2.18 0.135 0.076 38 Ref. 86 ^b Host 2-3 3.75 2.36 0.134 0.077 40 Ref. 87 ^c Host 2-3 3.76 2.17 0.135 0.076 47 Ref. 88 ^a Host 2-4 3.79 2.20 0.136 0.077 61 Ref. 89 ^b Host 2-4 3.74 2.34 0.135 0.076 62 Ref. 90 ^c Host 2-4 3.76 2.22 0.135 0.077 69 Ex. 16 ^d host 2 3.78 4.44 0.135 0.077 143 Ex. 17 ^e host 2 3.72 4.53 0.135 0.076 196 Ex. 18 ^f host 2 3.77 4.44 0.134 0.077 231 Dopant 21-2 was used in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^b : EBL (NPB), HBL (H1);
^c : EBL (NPB), HBL (H31);
^d : EBL (E1), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^e : EBL (E1), HBL (H1);
^f : EBL (E1), HBL (H31)

As shown in Table 6, in the organic light emitting diode (Comparative Examples 82-84) in which Host 2 in which only the anthracene core was substituted with deuterium was introduced into the light emitting material layer, Host 2-1 was not substituted with deuterium or only the substituent was substituted with deuterium. , Host 2-2, Host 2-3 was significantly increased as compared with the organic light emitting diodes (Comparative Examples 76-81, Comparative Examples 85-87) introduced into the light emitting material layer. In addition, in comparison with the organic light emitting diode (Comparative Examples 88-90) in which Host 2-4 substituted with deuterium in both the anthracene core and the substituents was introduced into the light emitting material layer, Host 2 in which only the anthracene core was substituted with deuterium was added to the light emitting material layer. The introduced organic light emitting diodes (Comparative Examples 82-84) had equal or slightly reduced current efficiency and light emission lifetime. This means that sufficient luminous efficiency and lifetime increase can be realized while containing less expensive deuterium.

In addition, compared with the organic light emitting diode in which NPB was introduced into the electron blocking layer (Comparative Examples 82-84), the current of the organic light emitting diode (Example 16-18) in which the E1 compound included in Formula 6 was introduced into the electron blocking layer Efficiency is improved by up to 103.7% and luminous lifetime by up to 244.8%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, the current efficiency and light emission lifetime of the organic light emitting diode were significantly improved.

Example 19 (Ex. 19): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 13, except that Dopant 21-3 was used as a dopant for the light emitting material layer.

Examples 20 to 21: Organic light emitting diode manufacturing

The same material as in Example 19 and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 91 to 93: Preparation of organic light emitting diodes

Host 2-1 of Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 19 (Comparative Example 91, Ref. 91), repeating the same materials and procedures as in Example 20 ( Comparative Example 92, Ref. 92) and the same materials and procedures as in Example 21 were repeated (Comparative Example 93, Ref. 93) to manufacture organic light emitting diodes, respectively.

Comparative Examples 94 to 96: Preparation of organic light emitting diodes

Host 2-2 of Chemical Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 19 (Comparative Example 94, Ref. 94), repeating the same materials and procedures as in Example 20 ( Comparative Example 95, Ref. 95) and the same materials and procedures as in Example 21 were repeated (Comparative Example 96, Ref. 96) to manufacture organic light emitting diodes, respectively.

Comparative Examples 97 to 99: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, Repeating the same materials and procedures as in Example 19 (Comparative Example 97, Ref. 97), repeating the same materials and procedures as in Example 20 (Comparative Example 98, Ref. 98), and repeating the same materials and procedures as in Example 21, respectively Each of the organic light emitting diodes was manufactured by repeating (Comparative Example 99, Ref. 99).

Comparative Examples 100 to 102: Preparation of organic light emitting diodes

Host 2-3 of Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl) -4,4'-diamine), repeating the same materials and procedures as in Example 19 (Comparative Example 100, Ref. 100), repeating the same materials and procedures as in Example 20 ( Comparative Examples 101 and Ref. 101) and the same materials and procedures as in Example 21 were repeated (Comparative Examples 102 and Ref. 102) to manufacture organic light emitting diodes, respectively.

Comparative Examples 103 to 105: Preparation of organic light emitting diodes

Host 2-4 of Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 19 (Comparative Example 103, Ref. 103), repeating the same materials and procedures as in Example 20 ( Comparative Example 104, Ref. 104) and the same materials and procedures as in Example 21 were repeated (Comparative Example 105, Ref. 105) to manufacture organic light emitting diodes, respectively.

Experimental Example 7: Evaluation of optical properties of organic light emitting diodes

The optical properties of each of the organic light emitting diodes prepared in Examples 19 to 21 and Comparative Examples 91 to 105 were measured according to the same procedure as in Experimental Example 1. The measurement results are shown in Table 7 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Host V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 91 ^a Host 2-1 3.79 2.19 0.134 0.077 43 Ref. 92 ^b Host 2-1 3.74 2.37 0.135 0.078 44 Ref. 93 ^c Host 2-1 3.77 2.20 0.135 0.077 54 Ref. 94 ^a Host 2-2 3.76 2.15 0.135 0.076 41 Ref. 95 ^b Host 2-2 3.74 2.34 0.135 0.077 43 Ref. 96 ^c Host 2-2 3.77 2.19 0.135 0.077 48 Ref. 97 ^a host 2 3.78 2.14 0.135 0.077 55 Ref. 98 ^b host 2 3.70 2.29 0.135 0.077 60 Ref. 99 ^c host 2 3.76 2.15 0.135 0.076 71 Ref. 100 ^a Host 2-3 3.78 2.17 0.135 0.076 45 Ref. 101 ^b Host 2-3 3.72 2.30 0.135 0.077 48 Ref. 102 ^c Host 2-3 3.77 2.19 0.135 0.077 57 Ref. 103 ^a Host 2-4 3.78 2.18 0.135 0.077 61 Ref. 104 ^b Host 2-4 3.74 2.35 0.136 0.077 67 Ref. 105 ^c Host 2-4 3.77 2.19 0.135 0.076 81 Ex. 19 ^d host 2 3.75 4.41 0.134 0.077 125 Ex. 20 ^e host 2 3.69 4.52 0.135 0.076 196 Ex. 21 ^f host 2 3.74 4.43 0.134 0.077 232 Dopant 21-3 was used in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^b : EBL (NPB), HBL (H1);
^c : EBL (NPB), HBL (H31);
^d : EBL (E1), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^e : EBL (E1), HBL (H1);
^f : EBL (E1), HBL (H31)

As shown in Table 7, in the organic light emitting diode (Comparative Examples 97-99) in which Host 2 in which only the anthracene core was substituted with deuterium was introduced into the light emitting material layer, Host 2-1 was not substituted with deuterium or only the substituent was substituted with deuterium. , Host 2-2, Host 2-3 was significantly increased compared to the organic light emitting diode (Comparative Examples 91-96, Comparative Examples 100-102) introduced into the light emitting material layer. In addition, in comparison with the organic light emitting diode (Comparative Example 103-105) in which Host 2-4 substituted with deuterium in both the anthracene core and the substituents was introduced into the light emitting material layer, Host 2 in which only the anthracene core was substituted with deuterium was added to the light emitting material layer. The introduced organic light emitting diodes (Comparative Examples 97-99) had comparable current efficiencies, and the light emitting lifetime was slightly decreased. This means that sufficient luminous efficiency and lifetime increase can be realized while containing less expensive deuterium.

In addition, compared with the organic light emitting diode in which NPB was introduced into the electron blocking layer (Comparative Examples 97-99), the current of the organic light emitting diode (Examples 19-21) in which the E1 compound included in Formula 6 was introduced into the electron blocking layer Efficiency is improved by up to 106.1% and luminous lifetime by up to 226.8%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, the current efficiency and light emission lifetime of the organic light emitting diode were significantly improved.

Example 22 (Ex. 22): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 13, except that Dopant 21-4 was used as a dopant for the light emitting material layer.

Examples 23 to 24: Organic light emitting diode manufacturing

The same material as in Example 22 and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 106 to 108: Preparation of organic light emitting diodes

Host 2-1 of Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 22 (Comparative Example 106, Ref. 106), repeating the same materials and procedures as in Example 23 ( Comparative Example 107, Ref. 107) and the same materials and procedures as in Example 24 were repeated (Comparative Example 108, Ref. 108) to manufacture organic light emitting diodes, respectively.

Comparative Examples 109 to 111: Preparation of organic light emitting diodes

Host 2-2 of Chemical Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 22 (Comparative Example 109, Ref. 109), repeating the same materials and procedures as in Example 23 ( Comparative Example 110, Ref. 110) and the same materials and procedures as in Example 24 were repeated (Comparative Example 111, Ref. 111) to prepare organic light emitting diodes, respectively.

Comparative Examples 112 to 114: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, The same materials and procedures as those of Example 22 were repeated (Comparative Example 112, Ref. 112), the same materials and procedures as those of Example 23 were repeated (Comparative Example 113, Ref. 113), and the same materials and procedures as those of Example 24 were repeated. Each of the organic light emitting diodes was manufactured by repeating (Comparative Example 114, Ref. 114).

Comparative Examples 115 to 117: Preparation of organic light emitting diodes

Host 2-3 of Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 22 (Comparative Example 105, Ref. 105), repeating the same materials and procedures as in Example 23 ( Comparative Examples 116 and Ref. 116) and the same materials and procedures as in Example 24 were repeated (Comparative Examples 117 and Ref. 117) to manufacture organic light emitting diodes, respectively.

Comparative Examples 118 to 120: Preparation of organic light emitting diodes

Host 2-4 of Formula 14 is used as the host of the light emitting material layer, respectively, and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1) as the material of the electron blocking layer, respectively. '-biphenyl)-4,4'-diamine), repeating the same materials and procedures as in Example 22 (Comparative Example 118, Ref. 118), respectively repeating the same materials and procedures as in Example 23 ( Comparative Example 119, Ref. 119) and the same materials and procedures as in Example 24 were repeated (Comparative Example 120, Ref. 120) to manufacture organic light emitting diodes, respectively.

Experimental Example 8: Evaluation of optical properties of organic light emitting diodes

The optical properties of each of the organic light emitting diodes prepared in Examples 22 to 24 and Comparative Examples 106 to 120 were measured according to the same procedure as in Experimental Example 1. The measurement results are shown in Table 8 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Host V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 106 ^a Host 2-1 3.78 2.17 0.135 0.077 64 Ref. 107 ^b Host 2-1 3.74 2.32 0.136 0.077 67 Ref. 108 ^c Host 2-1 3.77 2.19 0.135 0.076 85 Ref. 109 ^a Host 2-2 3.79 2.15 0.135 0.077 65 Ref. 110 ^b Host 2-2 3.74 2.34 0.135 0.077 67 Ref. 111 ^c Host 2-2 3.78 2.18 0.135 0.076 78 Ref. 112 ^a host 2 3.79 2.17 0.134 0.077 88 Ref. 113 ^b host 2 3.74 2.32 0.135 0.076 91 Ref. 114 ^c host 2 3.78 2.19 0.135 0.077 113 Ref. 115 ^a Host 2-3 3.77 2.17 0.135 0.078 65 Ref. 116 ^b Host 2-3 3.73 2.31 0.135 0.077 68 Ref. 117 ^c Host 2-3 3.76 2.18 0.135 0.077 85 Ref. 118 ^a Host 2-4 3.77 2.14 0.134 0.077 102 Ref. 119 ^b Host 2-4 3.72 2.30 0.135 0.076 105 Ref. 120 ^c Host 2-4 3.75 2.17 0.135 0.077 125 Ex. 22 ^d host 2 3.77 4.43 0.135 0.077 210 Ex. 23 ^e host 2 3.72 4.56 0.135 0.077 315 Ex. 24 ^f host 2 3.76 4.44 0.134 0.077 356 Dopant 21-4 was used in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^b : EBL (NPB), HBL (H1);
^c : EBL (NPB), HBL (H31);
^d : EBL (E1), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^e : EBL (E1), HBL (H1);
^f : EBL (E1), HBL (H31)

As shown in Table 8, in the organic light emitting diode (Comparative Example 112-114) in which Host 2 in which only the anthracene core was substituted with deuterium was introduced into the light emitting material layer, Host 2-1 was not substituted with deuterium or only the substituent was substituted with deuterium. , Host 2-2, Host 2-3 was significantly increased compared to the organic light emitting diode (Comparative Examples 106-111, Comparative Examples 115-117) introduced into the light emitting material layer. In addition, compared with the organic light emitting diode (Comparative Examples 118-120) in which Host 2-4 substituted with deuterium in both the anthracene core and the substituents was introduced into the light emitting material layer, Host 2 in which only the anthracene core was substituted with deuterium was added to the light emitting material layer. The introduced organic light emitting diodes (Comparative Examples 112-114) had almost equal or slightly reduced current efficiency and light emission lifetime. This means that sufficient luminous efficiency and lifetime increase can be realized while containing less expensive deuterium.

In addition, compared with the organic light emitting diode in which NPB was introduced into the electron blocking layer (Comparative Examples 112-114), the current of the organic light emitting diode (Example 22-24) in which the E1 compound included in Formula 6 was introduced into the electron blocking layer Efficiency is improved by up to 104.1% and luminous lifetime by up to 246.2%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, the current efficiency and light emission lifetime of the organic light emitting diode were significantly improved.

Example 25 (Ex. 25): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 1, except that Host 2 was used as the host of the light emitting material layer and E4 was used as the material of the electron transport layer.

Examples 26 to 27: Organic light emitting diode manufacturing

The same material as in Example 25, except that H1 of Formula 8 (Example 26, Ex. 26) and H31 of Formula 10 (Example 27, Ex. 27) were used as the material of the hole blocking layer (HBL), respectively, and Each organic light emitting diode was manufactured by repeating the procedure.

Example 28 (Ex. 28): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 25, except that 21-2 was used as the dopant of the light emitting material layer.

Examples 29 to 30: Organic light emitting diode manufacturing

The same material as in Example 28 and Each organic light emitting diode was manufactured by repeating the procedure.

Example 31 (Ex. 31): organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 25, except that 21-3 was used as the dopant of the light emitting material layer.

Examples 32 to 33: Organic light emitting diode manufacturing

The same material as in Example 31, except that H1 of Formula 8 (Example 32, Ex. 32) and H31 of Formula 10 (Example 33, Ex. 33) were used as the material of the hole blocking layer (HBL), respectively, and Each organic light emitting diode was manufactured by repeating the procedure.

Example 34 (Ex. 34): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 25, except that 21-4 was used as the dopant of the light emitting material layer.

Examples 35 to 36: Organic light emitting diode manufacturing

The same material as in Example 34, except that H1 of Formula 8 (Example 35, Ex. 35) and H31 of Formula 10 (Example 36, Ex. 36) were used as the material of the hole blocking layer (HBL), respectively, and Each organic light emitting diode was manufactured by repeating the procedure.

Experimental Example 9: Evaluation of optical properties of organic light emitting diodes

The optical properties of the organic light emitting diodes prepared in Examples 25 to 36 and Comparative Examples 68-69, 83-84, 98-99, and 113-114, respectively, were measured according to the same procedure as in Experimental Example 1. The measurement results are shown in Table 9 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Dopant V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 68 ^a 21-1 3.73 2.35 0.135 0.076 67 Ref. 69 ^b 21-1 3.77 2.17 0.135 0.077 79 Ex. 25 ^c 21-1 3.73 4.71 0.136 0.077 134 Ex. 26 ^d 21-1 3.69 5.02 0.135 0.076 183 Ex. 27 ^e 21-1 3.66 4.82 0.135 0.0771 222 Ref. 83 ^a 21-2 3.73 2.28 0.135 0.078 58 Ref. 84 ^b 21-2 3.79 2.19 0.135 0.077 67 Ex. 28 ^c 21-2 3.73 4.66 0.135 0.077 132 Ex. 29 ^d 21-2 3.67 4.98 0.135 0.076 190 Ex. 30 ^e 21-2 3.67 4.79 0.134 0.077 219 Ref. 98 ^a 21-3 3.70 2.29 0.135 0.077 60 Ref. 99 ^b 21-3 3.76 2.15 0.135 0.076 71 Ex. 31 ^c 21-3 3.70 4.63 0.134 0.077 115 Ex. 32 ^d 21-3 3.64 4.97 0.135 0.076 190 Ex. 33 ^e 21-3 3.64 4.78 0.134 0.077 221 Ref. 113 ^a 21-4 3.74 2.32 0.135 0.076 91 Ref. 114 ^b 21-4 3.78 2.19 0.135 0.077 113 Ex. 34 ^c 21-4 3.72 4.65 0.135 0.077 193 Ex. 35 ^d 21-4 3.67 5.02 0.135 0.077 305 Ex. 36 ^e 21-4 3.66 4.79 0.134 0.077 338 Host 2 in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (H1)
^b : EBL (NPB), HBL (H31);
^c : EBL (E4), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^d : EBL (E4), HBL (H1);
^e : EBL (E4), HBL (H31)

As shown in Table 9, compared to the organic light emitting diodes (Comparative Examples 68-69, 83-84, 98-99, 113-114) in which NPB was introduced into the electron blocking layer, the E4 compound included in Formula 6 was The current efficiency of the organic light emitting diodes (Examples 25-36) introduced into the blocking layer was improved by up to 122.1% and the light emitting lifetime by up to 235.2%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, the current efficiency and light emission lifetime of the organic light emitting diode were significantly improved.

Example 37 (Ex. 37): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 1, except that Host 2 was used as the host of the light emitting material layer and Doapnt 11-1 was used as the dopant.

Examples 38 to 39: Organic light emitting diode manufacturing

The same material as in Example 37, except that H1 of Formula 8 (Example 38, Ex. 38) and H31 of Formula 10 (Example 39, Ex. 39) were used as the material of the hole blocking layer (HBL), respectively, and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 121 to 122: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, The same materials and procedures as those of Example 38 were repeated (Comparative Example 121, Ref. 121), and the same materials and procedures as those of Example 39 were repeated (Comparative Example 122, Ref. 122) to manufacture organic light emitting diodes, respectively.

Example 40 (Ex. 40): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 37, except that Doapnt 11-2 was used as the dopant of the light emitting material layer.

Examples 41 to 42: Organic light emitting diode manufacturing

The same material as in Example 40 and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 123 to 124: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, The same materials and procedures as those of Example 41 were repeated (Comparative Example 123, Ref. 123), and the same materials and procedures as those of Example 42 were repeated (Comparative Example 124, Ref. 124) to manufacture organic light emitting diodes, respectively.

Example 43 (Ex. 43): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 37, except that Doapnt 11-3 was used as a dopant for the light emitting material layer.

Examples 44 to 45: Organic light emitting diode manufacturing

The same material as in Example 43, except that H1 of Formula 8 (Example 44, Ex. 44) and H31 of Formula 10 (Example 45, Ex. 45) were used as the material of the hole blocking layer (HBL), respectively, and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 125 to 126: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, The same materials and procedures as those of Example 44 were repeated (Comparative Example 125, Ref. 125), and the same materials and procedures as those of Example 45 were repeated (Comparative Example 126, Ref. 126) to manufacture organic light emitting diodes, respectively.

Example 46 (Ex. 46): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 37, except that Doapnt 11-4 was used as a dopant for the light emitting material layer.

Examples 47 to 48: Organic light emitting diode manufacturing

The same material as in Example 46 and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 127 to 128: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, The same materials and procedures as those of Example 47 were repeated (Comparative Example 127, Ref. 128), and the same materials and procedures as those of Example 48 were repeated (Comparative Example 128, Ref. 128) to manufacture organic light emitting diodes, respectively.

Experimental Example 10: Evaluation of optical properties of organic light emitting diodes

The optical properties of the organic light emitting diodes prepared in Examples 37 to 48 and Comparative Examples 121 to 128, respectively, were measured according to the same procedure as in Experimental Example 1. The measurement results are shown in Table 10 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Dopant V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 121 ^a 11-1 3.73 2.11 0.135 0.076 53 Ref. 122 ^b 11-1 3.77 1.95 0.135 0.077 63 Ex. 37 ^c 11-1 3.78 4.03 0.136 0.077 117 Ex. 38 ^d 11-1 3.74 4.10 0.135 0.076 151 Ex. 39 ^e 11-1 3.76 4.01 0.135 0.771 187 Ref. 123 ^a 11-2 3.73 2.05 0.135 0.078 46 Ref. 124 ^b 11-2 3.79 1.97 0.135 0.077 53 Ex. 40 ^c 11-2 3.78 3.99 0.135 0.077 114 Ex. 41 ^d 11-2 3.72 4.07 0.135 0.076 156 Ex. 42 ^e 11-2 3.77 3.99 0.134 0.077 185 Ref. 125 ^a 11-3 3.70 2.06 0.135 0.077 48 Ref. 126 ^b 11-3 3.76 1.93 0.135 0.076 57 Ex. 43 ^c 11-3 3.75 3.96 0.134 0.077 100 Ex. 44 ^d 11-3 3.69 4.06 0.135 0.076 156 Ex. 45 ^e 11-3 3.74 3.98 0.134 0.077 186 Ref. 127 ^a 11-4 3.74 2.09 0.135 0.076 73 Ref. 128 ^b 11-4 3.78 1.97 0.135 0.077 91 Ex. 46 ^c 11-4 3.77 3.98 0.135 0.077 168 Ex. 47 ^d 11-4 3.72 4.10 0.135 0.077 252 Ex. 48 ^e 11-4 3.76 3.99 0.134 0.077 284 Host 2 in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (H1)
^b : EBL (NPB), HBL (H31);
^c : EBL (E1), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^d : EBL (E1), HBL (H1);
^e : EBL (E1), HBL (H31)

As shown in Table 10, compared to the organic light emitting diode in which NPB was introduced in the electron blocking layer (Comparative Example 121-128), the organic light emitting diode in which the E1 compound included in Formula 6 was introduced into the electron blocking layer (Example 37) -48), the current efficiency was improved by up to 106.2% and the luminescence lifetime by up to 245.2%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, the current efficiency and light emission lifetime of the organic light emitting diode were significantly improved.

Example 49 (Ex. 49): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 1, except that Host 2 was used as the host of the light emitting material layer, 11-1 was used as the dopant, and E4 was used as the material of the electron blocking layer. did

Examples 50 to 51: Organic light emitting diode manufacturing

The same material as Example 49 and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 129 to 130: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, The same materials and procedures as those of Example 50 were repeated (Comparative Example 129, Ref. 129), and the same materials and procedures as those of Example 51 were repeated (Comparative Example 130, Ref. 130) to manufacture organic light emitting diodes, respectively.

Example 52 (Ex. 50): Organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 49, except that Doapnt 11-2 was used as the dopant of the light emitting material layer.

Examples 53 to 54: Organic light emitting diode manufacturing

The same material as in Example 52, except that H1 of Formula 8 (Example 53, Ex. 53) and H31 of Formula 10 (Example 54, Ex. 54) were used as the material of the hole blocking layer (HBL), respectively, and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 131 to 132: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, The same materials and procedures as those of Example 53 were repeated (Comparative Example 131, Ref. 131), and the same materials and procedures as those of Example 54 were repeated (Comparative Example 132, Ref. 132) to manufacture organic light emitting diodes, respectively.

Example 55 (Ex. 55): organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 49, except that Doapnt 11-3 was used as a dopant for the light emitting material layer.

Examples 56 to 57: Organic light emitting diode manufacturing

The same material as in Example 55, except that H1 of Formula 8 (Example 56, Ex. 56) and H31 of Formula 10 (Example 57, Ex. 57) were used as the material of the hole blocking layer (HBL), respectively, and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 133 to 134: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, The same materials and procedures as those of Example 56 were repeated (Comparative Example 133, Ref. 133), and the same materials and procedures as those of Example 57 were repeated (Comparative Example 134, Ref. 134) to manufacture organic light emitting diodes, respectively.

Example 58 (Ex. 58): organic light emitting diode manufacturing

An organic light emitting diode was manufactured by repeating the same materials and procedures as in Example 49, except that Doapnt 11-4 was used as the dopant of the light emitting material layer.

Examples 59 to 60: Organic light emitting diode manufacturing

The same material as in Example 58 and Each organic light emitting diode was manufactured by repeating the procedure.

Comparative Examples 135 to 136: Preparation of organic light emitting diodes

Except for using NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) as the material of the electron blocking layer, respectively, Each of the same materials and procedures as in Example 59 (Comparative Example 135, Ref. 136) and the same materials and procedures as in Example 60 (Comparative Example 136, Ref. 136) were repeated to manufacture organic light emitting diodes, respectively.

Experimental Example 11: Evaluation of optical properties of organic light emitting diodes

The optical properties of each of the organic light emitting diodes prepared in Examples 49 to 60 and Comparative Examples 129 to 136 were measured according to the same procedure as in Experimental Example 1. The measurement results are shown in Table 11 below.

Optical Characteristics of Organic Light-Emitting Diodes Sample Dopant V cd/A (CIE x, y) (T ₉₅ , hr) Ref. 129 ^a 11-1 3.73 2.11 0.135 0.076 53 Ref. 130 ^b 11-1 3.77 1.95 0.135 0.077 63 Ex. 49 ^c 11-1 3.73 4.24 0.136 0.077 63 Ex. 50 ^d 11-1 3.69 4.51 0.135 0.076 107 Ex. 51 ^e 11-1 3.66 4.34 0.135 0.0771 178 Ref. 131 ^a 11-2 3.73 2.05 0.135 0.078 46 Ref. 132 ^b 11-2 3.79 1.97 0.135 0.077 53 Ex. 52 ^c 11-2 3.73 4.19 0.135 0.077 105 Ex. 53 ^d 11-2 3.67 4.48 0.135 0.076 152 Ex. 54 ^e 11-2 3.67 4.31 0.134 0.077 175 Ref. 133 ^a 11-3 3.70 2.06 0.135 0.077 48 Ref. 134 ^b 11-3 3.76 1.93 0.135 0.076 57 Ex. 55 ^c 11-3 3.70 4.16 0.134 0.077 92 Ex. 56 ^d 11-3 3.64 4.47 0.135 0.076 152 Ex. 57 ^e 11-3 3.64 4.30 0.134 0.077 177 Ref. 135 ^a 11-4 3.74 2.09 0.135 0.076 73 Ref. 136 ^b 11-4 3.78 1.97 0.135 0.077 91 Ex. 58 ^c 11-4 3.72 4.18 0.135 0.077 154 Ex. 59 ^d 11-4 3.67 4.51 0.135 0.077 244 Ex. 60 ^e 11-4 3.66 4.31 0.134 0.077 270 Host 2 in both Comparative Examples and Examples;
^a : EBL (NPB), HBL (H1)
^b : EBL (NPB), HBL (H31);
^c : EBL (E4), HBL (2-phenyl-9,10-bis(2,2'-bipyridin-5-yl)anthracene);
^d : EBL (E4), HBL (H1);
^e : EBL (E4), HBL (H31)

As shown in Table 11, compared with the organic light emitting diode (Comparative Examples 129-136) in which NPB was introduced in the electron blocking layer, the organic light emitting diode in which the E4 compound included in Chemical Formula 6 was introduced into the electron blocking layer (Example 49) -60), the current efficiency was improved by up to 118.5% and the luminescence lifetime by up to 230.4%. In particular, when H1 and H31 compounds included in Formula 8 or Formula 10 were introduced into the hole transport layer, the current efficiency and light emission lifetime of the organic light emitting diode were significantly improved.

In the above, the present invention has been described based on exemplary embodiments and examples of the present invention, but the present invention is not limited to the technical ideas described in the above embodiments and examples. Rather, those of ordinary skill in the art to which the present invention pertains can easily propose various modifications and changes based on the above-described embodiments and examples. However, it is clear from the appended claims that all such modifications and changes fall within the scope of the present invention.

100, 600, 1300: organic light emitting display device
D, D1, D2, D3, D4: organic light emitting diode
210, 710, 1410: first electrode
220, 720, 1420: second electrode
230, 230A, 730, 730A, 1430: organic light emitting layer
330, 430, 530, 830, 930, 1030, 1130, 1230: electron blocking layer
340, 440, 540, 840, 940, 1040, 1140, 1240: light emitting material layer
350, 450, 550, 850, 850, 1050, 1150, 1250: hole blocking layer
Tr: thin film transistor

Claims (19)

Board; and
A first electrode, a second electrode facing the first electrode, at least one light-emitting material layer positioned between the first electrode and the second electrode, and the first electrode and the at least one light-emitting material layer A light emitting layer including at least one electron blocking layer positioned therebetween, and an organic light emitting diode positioned on the substrate,
The at least one light-emitting material layer includes a first host that is an anthracene-based compound, and a first dopant that is a boron-based compound,
The anthracene core of the first host is substituted with deuterium, and the first dopant has a structure of Formula 3 below,
The at least one electron blocking layer is an organic light emitting device comprising an amine-based compound having a structure of the following formula (5).
[Formula 3]

In Formula 3, _{each of R 11} to R _14, each of R ₂₁ to R _24, each of R ₃₁ to R _{35, and} each of R ₄₁ to R ₄₅ are independently hydrogen, deuterium, C ₁ -C ₁₀ alkyl, C ₆ -C ₃₀ selected from the group consisting of aryl, C ₆ -C ₃₀ arylamino and C ₅ -C _{30 heteroaryl, R 11} to R ₁₄ , R ₂₁ to R ₂₄ , R ₃₁ to R ₃₅ , R ₄₁ to R ₄₅ are each other may be the same or different, and each of the C ₆ -C ₃₀ aryls may be independently unsubstituted or substituted with C ₁ -C ₁₀ alkyl; R ₅₁ is selected from the group consisting of hydrogen, deuterium, C ₁ -C ₁₀ alkyl and C ₃ -C _{15 cycloalkyl.}
[Formula 5]

In Formula 5, L ₂ is a C ₆ ~ C ₃₀ arylene group; c is 0 or 1; R ₆₁ to R ₆₄ are each independently C ₆ ~ C ₃₀ aryl or C ₅ ~ C ₃₀ heteroaryl, C ₆ ~ C ₃₀ aryl C ₅ ~ C ₃₀ and heteroaryl are each independently unsubstituted or C ₁ -C ₁₀ may be substituted with at least one of an alkyl group and C ₆ -C _{30 aryl.}
The method of claim 1,
The first host is an organic light emitting device comprising an anthracene-based compound having a structure of the following formula (1).
[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, L ₁ is C ₆ -C ₃₀ arylene, a is an integer of 0 or 1, b is an integer from 1 to 8;
3. The method of claim 2,
The first host is an organic light emitting device comprising any one compound having a structure of the following formula (2).
[Formula 2]

The method of claim 1,
The first dopant is an organic light emitting device including any one compound having a structure of the following formula (4).
[Formula 4]

The method of claim 1,
The amine-based compound is an organic light emitting device comprising any one compound having a structure of the following formula (6).
[Formula 6]

The method of claim 1,
The light emitting layer may further include at least one hole blocking layer positioned between the at least one light emitting material layer and the second electrode.
7. The method of claim 6,
The at least one hole blocking layer is an organic light emitting device comprising an azine-based compound having a structure of the following Chemical Formula 7 or a benzimidazole-based compound having a structure of the following Chemical Formula 9.
[Formula 7]

In Formula 7, Y ₁ to Y ₅ are each independently CR ₇₁ or nitrogen (N), 1 to 3 of which are nitrogen, and R ₇₁ is C ₆ -C ₃₀ aryl; L ₃ is a C ₆ -C ₃₀ arylene group; R ₇₂ is C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, C ₆ -C ₃₀ aryl is unsubstituted, substituted with another C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, or may form a spiro structure with a C ₁₀ -C ₃₀ fused aryl ring or a C ₁₀ -C ₃₀ fused heteroaryl ring, wherein the other C ₆ -C ₃₀ aryl is unsubstituted, another C ₆ -C ₃₀ aryl or may be substituted with another C ₅ -C ₃₀ heteroaryl, or form a spiro structure with a _{C 10} -C _{30 fused aryl ring;} R ₇₃ is hydrogen or adjacent groups combine to form a fused aromatic ring; f is 0 or 1, g is 1 or 2, and h is an integer from 0 to 4.
[Formula 9]

In Formula 9, Ar is a C ₁₀ -C ₃₀ arylene group; R ₈₁ is C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, C ₆ -C ₃₀ aryl and C ₅ -C ₃₀ heteroaryl may each be unsubstituted or substituted with C ₁ -C ₁₀ alkyl; R ₈₂ and R ₈₃ are each independently hydrogen, C ₁ -C ₁₀ alkyl or C ₆ -C ₃₀ aryl.
8. The method of claim 7,
The azine-based compound includes any one azine-based compound having the structure of the following formula (8),
The benzimidazole-based compound is an organic light emitting device comprising any one compound having a structure of the following formula (10).
[Formula 8]

[Formula 10]

The method of claim 1,
The light emitting layer is located between the first electrode and the second electrode, and includes a first light emitting material layer and a first electron blocking layer located between the first electrode and the first light emitting material layer. a light emitting unit, a second light emitting unit positioned between the first light emitting unit and the second electrode, the second light emitting unit including a second light emitting material layer, and a first light emitting unit positioned between the first light emitting unit and the second light emitting unit Further comprising a charge generation layer,
At least one of the first light emitting material layer and the second light emitting material layer includes the first host and the first dopant.
10. The method of claim 9,
The second light emitting unit further includes a second electron blocking layer positioned between the first charge generating layer and the second light emitting material layer, wherein at least one of the first electron blocking layer and the second electron blocking layer is An organic light emitting device comprising an amine-based compound having the structure of Formula 5.
11. The method of claim 10,
The light emitting layer may include at least a first hole blocking layer positioned between the first light emitting material layer and the first charge generating layer and a second hole blocking layer positioned between the second light emitting material layer and the second electrode. An organic light emitting device further comprising one hole blocking layer.
12. The method of claim 11,
The at least one hole blocking layer is an organic light emitting device comprising an azine-based compound having a structure of the following Chemical Formula 7 or a benzimidazole-based compound having a structure of the following Chemical Formula 9.
[Formula 7]

In Formula 7, Y ₁ to Y ₅ are each independently CR ₇₁ or nitrogen (N), 1 to 3 of which are nitrogen, and R ₇₁ is C ₆ -C ₃₀ aryl; L ₃ is a C ₆ -C ₃₀ arylene group; R ₇₂ is C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, C ₆ -C ₃₀ aryl is unsubstituted, substituted with another C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, or may form a spiro structure with a C ₁₀ -C ₃₀ fused aryl ring or a C ₁₀ -C ₃₀ fused heteroaryl ring, wherein the other C ₆ -C ₃₀ aryl is unsubstituted, another C ₆ -C ₃₀ aryl or may be substituted with another C ₅ -C ₃₀ heteroaryl, or form a spiro structure with a _{C 10} -C _{30 fused aryl ring;} R ₇₃ is hydrogen or adjacent groups combine to form a fused aromatic ring; f is 0 or 1, g is 1 or 2, and h is an integer from 0 to 4.
[Formula 9]

In Formula 9, Ar is a C ₁₀ -C ₃₀ arylene group; R ₈₁ is C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, C ₆ -C ₃₀ aryl and C ₅ -C ₃₀ heteroaryl may each be unsubstituted or substituted with C ₁ -C ₁₀ alkyl; R ₈₂ and R ₈₃ are each independently hydrogen, C ₁ -C ₁₀ alkyl or C ₆ -C ₃₀ aryl.
10. The method of claim 9,
The second light emitting material layer is an organic light emitting device that emits light in yellow-green or cyan.
14. The method of claim 13,
The light emitting layer is located between the second light emitting unit and the second electrode, and includes a third light emitting unit including a third light emitting material layer, and a second light emitting unit located between the second light emitting unit and the third light emitting unit. Further comprising a charge generation layer,
At least one of the first light emitting material layer and the third light emitting material layer includes the first host and the first dopant.
15. The method of claim 14,
The third light emitting unit further includes a third electron blocking layer positioned between the second charge generating layer and the third light emitting material layer, wherein at least one of the first electron blocking layer and the third electron blocking layer is An organic light emitting device comprising an amine-based compound having the structure of Formula 5.
16. The method of claim 15,
The light emitting layer includes a first hole blocking layer positioned between the first light emitting material layer and the first charge generating layer, and a second hole blocking layer positioned between the second light emitting material layer and the second charge generating layer. and at least one hole blocking layer among a third hole blocking layer positioned between the third light emitting material layer and the second electrode.
17. The method of claim 16,
The at least one hole blocking layer is an organic light emitting device comprising an azine-based compound having a structure of the following Chemical Formula 7 or a benzimidazole-based compound having a structure of the following Chemical Formula 9.
[Formula 7]

In Formula 7, Y ₁ to Y ₅ are each independently CR ₇₁ or nitrogen (N), 1 to 3 of which are nitrogen, and R ₇₁ is C ₆ -C ₃₀ aryl; L ₃ is a C ₆ -C ₃₀ arylene group; R ₇₂ is C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, C ₆ -C ₃₀ aryl is unsubstituted, substituted with another C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, or may form a spiro structure with a C ₁₀ -C ₃₀ fused aryl ring or a C ₁₀ -C ₃₀ fused heteroaryl ring, wherein the other C ₆ -C ₃₀ aryl is unsubstituted, another C ₆ -C ₃₀ aryl or may be substituted with another C ₅ -C ₃₀ heteroaryl, or form a spiro structure with a _{C 10} -C _{30 fused aryl ring;} R ₇₃ is hydrogen or adjacent groups combine to form a fused aromatic ring; f is 0 or 1, g is 1 or 2, and h is an integer from 0 to 4.
[Formula 9]

In Formula 9, Ar is a C ₁₀ -C ₃₀ arylene group; R ₈₁ is C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl, C ₆ -C ₃₀ aryl and C ₅ -C ₃₀ heteroaryl may each be unsubstituted or substituted with C ₁ -C ₁₀ alkyl; R ₈₂ and R ₈₃ are each independently hydrogen, C ₁ -C ₁₀ alkyl or C ₆ -C ₃₀ aryl.
15. The method of claim 1, 9 or 14,
A red pixel, a green pixel, and a blue pixel are defined on the substrate, and the organic light emitting diode is positioned to correspond to the red pixel, the green pixel, and the blue pixel;
and a color conversion layer positioned between the substrate and the organic light emitting diode or above the organic light emitting diode to correspond to the red pixel, the green pixel, and the blue pixel.
15. The method of claim 1, 9 or 14,
A red pixel, a green pixel, and a blue pixel are defined on the substrate, and the organic light emitting diode is positioned to correspond to the red pixel, the green pixel, and the blue pixel;
and a color filter layer positioned between the substrate and the organic light emitting diode or above the organic light emitting diode corresponding to the red pixel, the green pixel, and the blue pixel.

Images