Heterocyclic compound and organic light-emitting device including same

Abstract

Disclosed are a heterocyclic compound of chemical formula 1 and an organic light emitting device including the heterocyclic compound. The heterocyclic compound is represented by the following Chemical Formula 1: In Chemical Formula 1, the definition of each substituent is the same as that defined in the specification.

Description

[0001] Cross Reference to Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0122364, filed on September 9, 2024, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present specification relates to a heterocyclic compound and an organic light emitting device including the same. BACKGROUND

[0004] An electroluminescent device is a self-emissive display device, and has advantages of a wide viewing angle, excellent contrast, and fast response speed.

[0005] An organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having the structure, electrons and holes injected from the two electrodes combine with each other in the organic thin film to form a pair, and then emit light while disappearing. If necessary, the organic thin film can be composed of a single layer or multiple layers.

[0006] If necessary, a material for the organic thin film can have a light emitting function. For example, as a material for the organic thin film, a compound which can individually constitute a light emitting layer itself, or a compound which can be used as a host or a dopant of a host-dopant type light emitting layer can also be used. In addition, as a material for the organic thin film, a compound which can play a role such as hole injection, hole transport, electron blocking, hole blocking, electron transport, or electron injection can also be used.

[0007] In order to improve the performance, service life, or efficiency of an organic light emitting device, there is a continuous need to develop a material for an organic thin film.

[0008] [Related Art Documents]

[0009] [Patent Documents]

[0010] (Patent Document 1) U.S. Patent No. 4,356,429 SUMMARY

[0011] The present specification is directed to providing a heterocyclic compound and an organic light emitting device including the same.

[0012] An exemplary embodiment of the present application provides a heterocyclic compound of the following Chemical Formula 1.

[0013] [Chemical Formula 1]

[0014]

[0015] In chemical formula 1,

[0016] M is: a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

[0017] Ar represents: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C6 to C60 aryl; or substituted or unsubstituted C2 to C60 heteroaryl.

[0018] R1 to R3 are each independently: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; or substituted or unsubstituted C2 to C60 heterocyclic alkyl.

[0019] R4 represents: hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

[0020] o is an integer from 0 to 5, and when o is 2 or greater, R4 are either the same or different from each other.

[0021] Het is a group represented by any one of the following chemical formulas H-1 to H-3.

[0022] [Chemical formula H-1]

[0023]

[0024] [Chemical formula H-2]

[0025]

[0026] [Chemical formula H-3]

[0027]

[0028] In chemical formulas H-1 to H-3,

[0029] Z represents: hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

[0030] m is an integer from 0 to 4, and when m is 2 or greater, Z are either the same or different from each other.

[0031] R5 and R6 are each independently: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; substituted or unsubstituted C6 to C60 aryl; or substituted or unsubstituted C2 to C60 heteroaryl.

[0032] p is an integer from 1 to 3, q ​​is an integer from 1 to 5, and R5 and R6 are either the same or different from each other when p and q are both 2 or greater.

[0033] Another exemplary embodiment provides an organic light-emitting device, the organic light-emitting device comprising: a first electrode; a second electrode; and an organic material layer having one or more layers provided between the first electrode and the second electrode, wherein the one or more layers of the organic material layer comprise one or more compounds.

[0034] When used in organic light-emitting devices, the heterocyclic compounds described in this specification can reduce the driving voltage of the device, improve luminous efficiency, and improve the lifespan characteristics of the device.

[0035] Specifically, the heterocyclic compound includes a phenanthroline with a substituent at a specific position as a first substituent and a pyridine or quinoline linking group as a second substituent around the benzene ring, with the first and second substituents substituted at the meta position of the benzene ring. When substituted at the meta position as described above, the amine of quinoline or pyridine forms a strong coordination bond with the metal, increasing the bond energy with the metal to be doped (Li or Yb).

[0036] Furthermore, the linking groups of pyridine and quinoline, as the second substituents, are bonded to the benzene ring only at specific positions, and the linking structure between pyridine and quinoline is also specific. Moreover, when pyridine / quinoline is linked to a meta-substituted quinoline / pyridine as described above, the amine of pyridine / quinoline can additionally bond to the metal, resulting in a stronger bond. Therefore, excellent performance in terms of driving voltage and efficiency can be achieved.

[0037] Heterocyclic compounds incorporating this structural feature possess suitable electron transport capabilities, are structurally stable, and can efficiently transfer electrons. Therefore, when the heterocyclic compounds of the present invention are used as materials for organic material layers (especially electron transport layers or charge generation layers) in organic light-emitting devices, the performance of organic light-emitting devices can be improved. Attached Figure Description

[0038] Figures 1 to 4 Each of the above diagrams exemplarily illustrates a stacked structure of an organic light-emitting device according to an exemplary embodiment of this specification. Detailed Implementation

[0039] This instruction manual will be described in more detail below.

[0040] In this specification, when a part "includes" a constituent element, unless otherwise specifically described, this does not mean that another constituent element is excluded, but rather that another constituent element may be included.

[0041] In this specification, "N to N′" means N or more and N′ or fewer.

[0042] In this specification, Cn (n: an integer of 1 or greater) refers to the number of carbon atoms. For example, C1 to C60 refer to 1 to 60 carbon atoms.

[0043] In this specification, chemical formulas Or *- indicates the location where the constituent elements are bonded.

[0044] The term “substitution” means that a hydrogen atom bonded to a carbon or nitrogen atom in a compound is replaced by another substituent, and the position to be substituted is not restricted, as long as the position is where the hydrogen atom is substituted (i.e., the position where the substituent can be substituted), and when two or more are substituted, the two or more substituents can be the same as or different from each other.

[0045] In this specification, "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; halogen group; cyano (-CN); C1 to C60 alkyl; C2 to C60 alkenyl; C2 to C60 alkynyl; C1 to C60 haloalkyl; C1 to C60 alkoxy; C6 to C60 aryloxy; C1 to C60 alkylthio; C6 to C60 arylthio; C1 to C60 alkylsulfonyl; C6 to C60 arylsulfonyl; C3 to C60 cycloalkyl; C2 to C60 heterocycloalkyl; C6 to C60 aryl; C2 to C60 heteroaryl; silyl; phosphine oxide; and amino, or a substituent connected to two or more substituents selected from the examples.

[0046] In this specification, "when no substituent is indicated in the chemical formula or structure of the compound" means that the hydrogen atom is bonded to the carbon atom. However, because deuterium ( 2 H is an isotope of hydrogen, so some hydrogen atoms can be deuterium.

[0047] In exemplary embodiments of this application, "when no substituent is indicated in the chemical formula or the structure of the compound" can mean that all positions that the substituent can reach are hydrogen or deuterium. That is, deuterium is an isotope of hydrogen, and some hydrogen atoms can be deuterium as an isotope, and in this case, the deuterium content can be from 0% to 100%, and the deuterium content can be expressed as the deuterium substitution rate.

[0048] In an exemplary embodiment of this application, in the case where "no substituents are indicated in the chemical formula or the structure of the compound", when the content of deuterium is 0%, the content of hydrogen is 100%, and all substituents do not explicitly exclude deuterium (such as hydrogen), hydrogen and deuterium can be mixed and used in the compound.

[0049] In an exemplary embodiment of this application, deuterium is one of the isotopes of hydrogen. Deuterium is an element having a deuterium nucleus consisting of one proton and one neutron as its atomic nucleus, and can be represented by hydrogen-2. The element symbol can also be represented as D or 2 H.

[0050] In exemplary embodiments of this application, isotopes refer to atoms having the same atomic number (Z) but different mass numbers (A), and can also be interpreted as elements having the same number of protons but different numbers of neutrons.

[0051] In an exemplary embodiment of this application, when the total number of substituents in the basic compound is defined as T1 and the number of specific substituents among the substituents is defined as T2, the substitution rate T% of the specific substituent can be defined as T2 / T1×100=T.

[0052] That is, in the example, when the total number of substituents that a phenyl group can have is 5 (T1 in the formula) and the number of deuterium substituents is 1 (T2 in the formula), by The 20% deuterium substitution rate in the phenyl group can be represented by 20%. That is, the 20% deuterium substitution rate in the phenyl group can be represented by the following structural formula.

[0053]

[0054] Furthermore, in exemplary embodiments of this application, "phenyl with a 0% deuterium substitution rate" may mean a phenyl that does not include deuterium atoms as substituents (i.e., has five hydrogen atoms).

[0055] In this specification, halogen can be fluorine, chlorine, bromine or iodine.

[0056] In this specification, alkyl groups comprise straight or branched chains having 1 to 60 carbon atoms and may be additionally substituted by another substituent. The number of carbon atoms in an alkyl group can be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl.

[0057] In this specification, alkenyl groups comprise straight or branched chains having 2 to 60 carbon atoms and may be further substituted with another substituent. The number of carbon atoms in an alkenyl group can be 2 to 60, specifically 2 to 40, and more specifically 2 to 20. Specific examples of alkenyl groups include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, bis(diphenyl-1-yl)vinyl-1-yl, styreneyl, and styreneyl.

[0058] In this specification, the alkynyl group comprises a straight or branched chain having 2 to 60 carbon atoms and may be further substituted by another substituent. The number of carbon atoms in the alkynyl group can be 2 to 60, specifically 2 to 40, and more specifically 2 to 20.

[0059] In this specification, alkyl halogroup means an alkyl group substituted with a halogen group, and specific examples of alkyl halogroups include, but are not limited to, -CF3 and -CF2CF3.

[0060] In this specification, alkoxy groups are represented by -O (R101), and the above examples of alkyl groups can be applied to R101.

[0061] In this specification, aryl groups are represented by -O (R102), and the above examples of aryl groups can be applied to R102.

[0062] In this specification, alkylthio groups are represented by -S(R103), and the above examples of alkyl groups can be applied to R103.

[0063] In this specification, arylthio groups are represented by -S(R104), and the above examples of aryl groups can be applied to R104.

[0064] In this specification, alkyl sulfonyl groups are represented by -S(=O)2(R105), and the above examples of alkyl groups can be applied to R105.

[0065] In this specification, arylsulfonyl group is represented by -S(=O)2(R106), and the above examples of aryl groups can be applied to R106.

[0066] In this specification, cycloalkyl groups include monocyclic or polycyclic groups having 3 to 60 carbon atoms and may be further substituted with another substituent. Here, polycyclic means a group in which the cycloalkyl group is directly attached to or fused with another cyclic group. The other cyclic group may also be cycloalkyl, but may also be another type of cyclic group, such as heterocycloalkyl, aryl, and heteroaryl. The number of carbon atoms in a cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specific examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl.

[0067] In this specification, heterocyclic alkyl groups include O, S, Se, N, or Si as heteroatoms, and include monocyclic or polycyclic groups having 2 to 60 carbon atoms, and may be further substituted with another substituent. Here, polycyclic means a group in which the heterocyclic alkyl group is directly attached to or fused with another cyclic group. Here, the other cyclic group may also be a heterocyclic alkyl group, but may also be another type of cyclic group, such as cycloalkyl, aryl, and heteroaryl. The number of carbon atoms in a heterocyclic alkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

[0068] In this specification, aryl groups comprise monocyclic or polycyclic compounds having 6 to 60 carbon atoms and may be further substituted with another substituent. Here, polycyclic means a group in which the aryl group is directly attached to or fused with another cyclic group. This other cyclic group may also be an aryl group, but may also be another type of cyclic group, such as cycloalkyl, heterocycloalkyl, and heteroaryl groups. Aryl groups include spirocyclic groups. The number of carbon atoms in an aryl group can be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of aryl groups include phenyl, biphenyl, terphenyl, naphthyl, anthracene, etc. The group may include, but is not limited to, phenanthrene, perylene, fluoranyl, benzophenanthrene, phenatenyl, pyrene, tetraphenyl, pentaphenyl, fluorenyl, indene, acenaphthene, benzofluorenyl, spirodifluorenyl, 2,3-dihydro-1H-indene and its fused-ring groups.

[0069] In this specification, terphenyl may be selected from the following structures.

[0070]

[0071] In this specification, the fluorene group may be substituted, and adjacent substituents may bond to each other to form a ring. That is, substituted or unsubstituted fluorene groups may also include spirodifluorene groups.

[0072] When the fluorenyl group is substituted, it can be, for example, the structure shown below, and any carbon in the structure below can be bonded to another structure, but is not limited thereto.

[0073]

[0074] In this specification, heteroaryl groups include S, O, Se, N, or Si as heteroatoms, and include monocyclic or polycyclic groups having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic means a group in which the heteroaryl group is directly attached to or fused with another cyclic group. Here, the other cyclic group may also be a heteroaryl group, but may also be another type of cyclic group, such as cycloalkyl, heterocycloalkyl, and aryl groups. The number of carbon atoms in a heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of heteroaryl groups include pyridyl, pyrroloyl, pyrimidinyl, pyridazinyl, furanyl, thiopheneyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, furazolyl, oxadiazolyl, thiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiaranyl, diazinyl, oxazinyl, thiazolyl, dioxinyl, triazinyl, tetraazinyl, quinolinyl, isoquinolinyl, quinazolinyl, isoquinazolinyl, quinazolinyl, naphridinyl, acridineyl, phenanthridineyl, imidazopyridyl, di... Azanaphthyl, triazaindenyl, indole, indazinyl, benzothiazolyl, benzoxazolyl, benzoimidazolyl, benzothiophene, benzofuranyl, dibenzothiophene, dibenzofuranyl, carbazole, benzocarbazole, dibenzocarbazole, phenazinyl, dibenzothiophenolyl, spirodi(dibenzothiophene), dihydrophenazinyl, phenoxazinyl, indolo[2,3-a]carbazole, indolo[2,3-b]carbazole, indolinyl, 10,11-dihydro-dibenzo[b,f]aza The group includes, but is not limited to, 9,10-dihydroacridinyl, tetrabenzophenanthreneyl, phenothiazinyl, phthalazinyl, phenanthrolinel, naphthobenzofuranyl, naphthobenzothiopheneyl, benzo[c][1,2,5]thiadiazolyl, 2,3-dihydrobenzo[b]thiopheneyl, 2,3-dihydrobenzofuranyl, 5,10-dihydrodibenzo[b,e][1,4]azasilyl, pyrazolo[1,5-c]quinazolinyl, pyrido[1,2-b]inzolyl, pyrido[1,2-a]imidazo[1,2-e]indololinyl, and 5,11-dihydroindoxazo[1,2-b]carbazoleyl.

[0075] In this specification, the benzocarbazoyl group can be any of the following structures, and the nitrogen or any carbon in the following structures is bonded to another structure. When any carbon is bonded to another structure, the nitrogen may be bonded to hydrogen or may have additional substituents.

[0076]

[0077] In this specification, the dibenzocarbazoyl group can be any of the following structures, and the nitrogen or any carbon in the following structures is bonded to another structure. When any carbon is bonded to another structure, the nitrogen may be bonded to hydrogen or may have additional substituents.

[0078]

[0079] In this specification, when the substituent is carbazolyl, benzocarbazolyl, or dibenzocarbazolyl, it means that the nitrogen or carbon of the carbazolyl, benzocarbazolyl, or dibenzocarbazolyl group is bonded to another structure.

[0080] In this specification, when carbazolyl, benzocarbazolyl, or dibenzocarbazolyl is substituted, it means that the nitrogen or carbon of carbazolyl, benzocarbazolyl, or dibenzocarbazolyl is substituted with another substituent.

[0081] In this specification, the naphthobenzofuranyl group can be any of the following structures, and any carbon in the following structures is bonded to another structure.

[0082]

[0083] In this specification, the naphthobenzothiophene group can be any of the following structures, and any carbon in the following structures is bonded to another structure.

[0084]

[0085] In this specification, silyl groups include Si and are substituents to which Si atoms are directly attached as free radicals, and are represented by -Si(R107)(R108)(R109), and R107 to R109 may be the same as or different from each other, and R107 to R109 may each be a substituent consisting of at least one of the following groups: hydrogen; deuterium; halogen group; alkyl; alkenyl; alkoxy; cycloalkyl; heterocycloalkyl; aryl; and heteroaryl.

[0086] Depending on the substituents bonded to the Si element, silyl groups can include alkylsilyl, arylsilyl, heteroarylsilyl, alkylarylsilyl, and arylheteroarylsilyl groups. Alkylsilyl, arylsilyl, or heteroarylsilyl respectively indicate that the alkyl, aryl, or heteroaryl group is replaced by the Si element of the silyl group; alkylarylsilyl means that both the alkyl and aryl groups are replaced by the Si element of the silyl group; and arylheteroarylsilyl means that both the aryl and heteroaryl groups are replaced by the Si element of the silyl group.

[0087] In this specification, triarylsilyl means a silyl group substituted with three aryl groups. The number of carbon atoms in the aryl groups can be 6 to 60, 6 to 30, or 6 to 20, and the number of carbon atoms in the triarylsilyl group can be 18 to 180, 18 to 90, or 18 to 60.

[0088] Specific examples of silanes include, but are not limited to, the structures described below.

[0089] (trimethylsilyl) (triethylsilyl) (tert-butyldimethylsilyl) (vinyl dimethylsilyl) (propyl dimethylsilyl) (triphenylsilyl) (diphenylsilyl) and (Phenylsilyl)

[0090] In this specification, the phosphine oxide group is represented by -P(=O)(R110)(R111), and R110 and R111 may be the same as or different from each other, and R110 and R111 may each be independently a substituent consisting of at least one of the following groups: hydrogen; deuterium; halogen group; alkyl; alkenyl; alkoxy; cycloalkyl; heterocycloalkyl; aryl; and heteroaryl. Specifically, the phosphine oxide group may be substituted with alkyl or aryl groups, and the above examples can be applied to alkyl and aryl groups. Examples of phosphine oxide groups include, but are not limited to, dimethylphosphine oxide, diphenylphosphine oxide, and dinaphthylphosphine oxide.

[0091] In this specification, the amino group is represented by -N(R112)(R113), and R112 and R113 may be the same as or different from each other, and R112 and R113 may each be a substituent consisting of at least one of the following groups: hydrogen; deuterium; halogen group; alkyl; alkenyl; alkoxy; cycloalkyl; heterocycloalkyl; aryl; and heteroaryl. The amino group may be selected from the group consisting of: -NH2; monoalkylamino; monoarylamino; monoheteroarylamino; dialkylamino; diarylamino; diheteroarylamino; alkylarylamino; alkylheteroarylamino; and arylheteroarylamino, and the number of carbon atoms in the amino group is not particularly limited, but preferably from 1 to 30. Specific examples of amino groups include, but are not limited to, methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, naphthylamino, biphenylamino, diphenylamino, anthraceneamino, 9-methyl-anthraylamino, diphenylamino, phenylnaphthylamino, xylylamino, phenyltolylamino, triphenylamino, biphenylnaphthylamino, phenylbiphenylamino, biphenylfluorenylamino, phenyltriphenylamino, and biphenyltriphenylamino.

[0092] In this specification, the above description of aryl can be applied to arylene (except that arylene is a divalent group).

[0093] In this specification, the above description of heteroaryl groups can be applied to heteroaryl groups (except that heteroaryl groups are divalent groups).

[0094] Exemplary embodiments of this specification provide heterocyclic compounds of the following chemical formula 1.

[0095] [Chemical Formula 1]

[0096]

[0097] In chemical formula 1,

[0098] Each substituent is defined as described above.

[0099] The heterocyclic compound according to exemplary embodiments of this specification is characterized in that it includes a phenanthroline having a substituent at a specific position as a first substituent and a linking group of pyridine and quinoline as a second substituent around a benzene ring, wherein the first and second substituents are substituted at the meta position of the benzene ring.

[0100] In heterocyclic compounds with this structure, the amines of quinoline and pyridine form strong coordination bonds with the metal, increasing the bond energy with the metal to be doped (Li or Yb), and thus achieving excellent results in terms of driving voltage and efficiency. Heterocyclic compounds also possess suitable electron transport capabilities, are structurally stable, and can efficiently transfer electrons.

[0101] In exemplary embodiments of this specification, chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-3.

[0102] [Chemical Formula 1-1]

[0103]

[0104] [Chemical Formula 1-2]

[0105]

[0106] [Chemical Formulas 1-3]

[0107]

[0108] In chemical formulas 1-1 to 1-3,

[0109] Each substituent is defined in the same way as in Formula 1.

[0110] In exemplary embodiments of this specification, chemical formula 1 may be represented by chemical formula 1-1-1, chemical formula 1-1-2, chemical formula 1-2-1 or chemical formula 1-3-1.

[0111] [Chemical Formula 1-1-1]

[0112]

[0113] [Chemical Formula 1-1-2]

[0114]

[0115] [Chemical Formula 1-2-1]

[0116]

[0117] [Chemical Formula 1-3-1]

[0118]

[0119] In chemical formulas 1-1-1, 1-1-2, 1-2-1, and 1-3-1,

[0120] Each substituent is defined in the same way as in Formula 1.

[0121] In exemplary embodiments of this specification, chemical formula 1-3-1 may be represented by chemical formula 1-3-A or chemical formula 1-3-B.

[0122] [Chemical Formula 1-3-A]

[0123]

[0124] [Chemical Formula 1-3-B]

[0125]

[0126] In chemical formulas 1-3-A and 1-3-B,

[0127] Each substituent is defined in the same way as in Formula 1.

[0128] In exemplary embodiments of this specification, M is: a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

[0129] In exemplary embodiments of this specification, M may be: a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.

[0130] In exemplary embodiments of this specification, M may be: a substituted or unsubstituted C1 to C20 alkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group.

[0131] In exemplary embodiments of this specification, M may be: a substituted or unsubstituted C1 to C10 alkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group.

[0132] In exemplary embodiments of this specification, M may be: a substituted or unsubstituted C1 to C10 alkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group including N.

[0133] In exemplary embodiments of this specification, M may be: a substituted or unsubstituted C1 to C10 alkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group including a C=N bond.

[0134] In exemplary embodiments of this specification, M may be: substituted or unsubstituted tert-butyl; substituted or unsubstituted phenyl; or substituted or unsubstituted pyridyl.

[0135] In exemplary embodiments of this specification, M may be: an unsubstituted or deuterated C1 to C40 alkyl group; an unsubstituted or deuterated, alkyl, or deuterated alkyl group of C6 to C40 aryl group; or an unsubstituted or deuterated C2 to C40 heteroaryl group.

[0136] In exemplary embodiments of this specification, M may be: an unsubstituted or deuterated C1 to C20 alkyl group; an unsubstituted or deuterated, alkyl, or deuterated alkyl group of C6 to C20 aryl group; or an unsubstituted or deuterated C2 to C20 heteroaryl group.

[0137] In exemplary embodiments of this specification, M may be: an unsubstituted or deuterated C1 to C10 alkyl group; an unsubstituted or deuterated, alkyl, or deuterated alkyl group of C6 to C20 aryl group; or an unsubstituted or deuterated C2 to C20 heteroaryl group.

[0138] In exemplary embodiments of this specification, M may be: an unsubstituted or deuterated C1 to C10 alkyl group; an unsubstituted or deuterated, alkyl, or deuterated alkyl group of C6 to C20 aryl group; or an unsubstituted or deuterated C2 to C20 heteroaryl group that includes N.

[0139] In exemplary embodiments of this specification, M may be: an unsubstituted or deuterated C1 to C10 alkyl group; an unsubstituted or deuterated, alkyl, or deuterated alkyl group of C6 to C20 aryl group; or an unsubstituted or deuterated C2 to C20 heteroaryl group including a C=N bond.

[0140] In exemplary embodiments of this specification, M may be: unsubstituted or deuterated tert-butyl; unsubstituted or deuterated, tert-butyl, or deuterated tert-butyl-substituted phenyl; or unsubstituted or deuterated pyridyl.

[0141] In exemplary embodiments of this specification, Ar is: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C6 to C60 aryl; or substituted or unsubstituted C2 to C60 heteroaryl.

[0142] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C40 alkyl; substituted or unsubstituted C6 to C40 aryl; or substituted or unsubstituted C2 to C40 heteroaryl.

[0143] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C20 alkyl; substituted or unsubstituted C6 to C20 aryl; or substituted or unsubstituted C2 to C20 heteroaryl.

[0144] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; substituted or unsubstituted C1 to C10 alkyl; substituted or unsubstituted C6 to C20 aryl; or substituted or unsubstituted C2 to C20 heteroaryl.

[0145] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; substituted or unsubstituted C1 to C10 alkyl; substituted or unsubstituted C6 to C20 aryl; or substituted or unsubstituted C2 to C20 heteroaryl including O or S.

[0146] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; substituted or unsubstituted tert-butyl; substituted or unsubstituted phenyl; substituted or unsubstituted benzofuranyl; or substituted or unsubstituted benzothiopheneyl.

[0147] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; halogen group; cyano; unsubstituted or deuterated C1 to C40 alkyl; unsubstituted or deuterated, alkyl or deuterated alkyl-substituted C6 to C40 aryl; or unsubstituted or deuterated C2 to C40 heteroaryl.

[0148] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; halogen group; cyano; unsubstituted or deuterated C1 to C20 alkyl; unsubstituted or deuterated, alkyl or deuterated alkyl-substituted C6 to C20 aryl; or unsubstituted or deuterated C2 to C20 heteroaryl.

[0149] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; unsubstituted or deuterated C1 to C10 alkyl; unsubstituted or deuterated, alkyl, or deuterated alkyl-substituted C6 to C20 aryl; or unsubstituted or deuterated C2 to C20 heteroaryl.

[0150] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; unsubstituted or deuterated C1 to C10 alkyl; unsubstituted or deuterated, alkyl, or deuterated alkyl-substituted C6 to C20 aryl; or unsubstituted or substituted C2 to C20 heteroaryl including O or S.

[0151] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; unsubstituted or deuterated tert-butyl; unsubstituted or deuterated, alkyl or deuterated alkyl-substituted phenyl; unsubstituted or deuterated benzofuranyl; or unsubstituted or deuterated benzothiophenyl.

[0152] In exemplary embodiments of this specification, Ar can be: hydrogen; deuterium; unsubstituted or deuterated tert-butyl; unsubstituted or deuterated, tert-butyl or deuterated tert-butyl phenyl; unsubstituted or deuterated benzofuranyl; or unsubstituted or deuterated benzothiophene.

[0153] In exemplary embodiments of this specification, R1 to R3 are each independently: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; or substituted or unsubstituted C2 to C60 heterocycloalkyl.

[0154] In exemplary embodiments of this specification, R1 to R3 may each be independently: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C40 alkyl; substituted or unsubstituted C3 to C40 cycloalkyl; or substituted or unsubstituted C2 to C40 heterocycloalkyl.

[0155] In exemplary embodiments of this specification, R1 to R3 may each be independently: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C20 alkyl; substituted or unsubstituted C3 to C20 cycloalkyl; or substituted or unsubstituted C2 to C20 heterocycloalkyl.

[0156] In exemplary embodiments of this specification, R1 to R3 may each be independently: hydrogen; deuterium; or substituted or unsubstituted C1 to C20 alkyl groups.

[0157] In the exemplary embodiments described in this specification, R1 to R3 may each be hydrogen or deuterium independently.

[0158] In the exemplary embodiments described in this specification, R1 to R3 can be hydrogen.

[0159] In exemplary embodiments of this specification, R4 may be: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; or substituted or unsubstituted C2 to C60 heterocycloalkyl.

[0160] In exemplary embodiments of this specification, R4 may be: hydrogen; deuterium; halogen group; cyano; or substituted or unsubstituted C1 to C60 alkyl group.

[0161] In an exemplary embodiment of this specification, R4 may be hydrogen or deuterium.

[0162] In an exemplary embodiment of this specification, R4 may be hydrogen.

[0163] In the exemplary embodiments described in this specification, o is 5, and R4 can be all hydrogen.

[0164] In an exemplary embodiment of this specification, R4 may be deuterium.

[0165] In the exemplary embodiments described in this specification, o is 5, and R4 can be all deuterium.

[0166] In the exemplary embodiments described in this specification, o can be an integer from 1 to 6.

[0167] In exemplary embodiments of this specification, Het is a group represented by any one of the following chemical formulas H-1 to H-3.

[0168] [Chemical formula H-1]

[0169]

[0170] [Chemical formula H-2]

[0171]

[0172] [Chemical formula H-3]

[0173]

[0174] In chemical formulas H-1 to H-3,

[0175] Z represents: hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

[0176] m is an integer from 0 to 4, and when m is 2 or greater, Z are either the same or different from each other.

[0177] R5 and R6 are each independently: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; substituted or unsubstituted C6 to C60 aryl; or substituted or unsubstituted C2 to C60 heteroaryl.

[0178] p is an integer from 1 to 3, q ​​is an integer from 1 to 5, and R5 and R6 are either the same or different from each other when p and q are both 2 or greater.

[0179] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C40 alkyl; substituted or unsubstituted C6 to C40 aryl; or substituted or unsubstituted C2 to C40 heteroaryl.

[0180] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C20 alkyl; substituted or unsubstituted C6 to C20 aryl; or substituted or unsubstituted C2 to C20 heteroaryl.

[0181] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C10 alkyl; substituted or unsubstituted C6 to C20 aryl; or substituted or unsubstituted C2 to C20 heteroaryl.

[0182] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C10 alkyl; substituted or unsubstituted C6 to C20 aryl; or substituted or unsubstituted C2 to C20 heteroaryl including N.

[0183] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C10 alkyl; substituted or unsubstituted C6 to C20 aryl; or substituted or unsubstituted C2 to C20 heteroaryl including C=N bonds.

[0184] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted tert-butyl; substituted or unsubstituted phenyl; substituted or unsubstituted naphthyl; substituted or unsubstituted pyridyl; or substituted or unsubstituted pyrimidinyl.

[0185] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; a halogen group; a cyano group; an unsubstituted or substituted C1 to C40 alkyl group; an unsubstituted or substituted C6 to C40 aryl group; or an unsubstituted or substituted C2 to C40 heteroaryl group.

[0186] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; a halogen group; a cyano group; an unsubstituted or substituted C1 to C20 alkyl group; an unsubstituted or substituted C6 to C20 aryl group; or an unsubstituted or substituted C2 to C20 heteroaryl group.

[0187] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; a halogen group; a cyano group; an unsubstituted or substituted C1 to C10 alkyl group; an unsubstituted or substituted C6 to C20 aryl group; or an unsubstituted or substituted C2 to C20 heteroaryl group.

[0188] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; a halogen group; a cyano group; an unsubstituted or substituted C1 to C10 alkyl group; an unsubstituted or substituted C6 to C20 aryl group; or an unsubstituted or substituted C2 to C20 heteroaryl group including a C=N bond.

[0189] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; a halogen group; a cyano group; an unsubstituted or halogen-substituted methyl group; an unsubstituted or deuterium-substituted tert-butyl group; an unsubstituted or deuterium-substituted phenyl group; a naphthyl group; a pyridyl group; or a pyrimidinyl group.

[0190] In exemplary embodiments of this specification, Z can be: hydrogen; deuterium; a halogen group; a cyano group; -CF3; an unsubstituted or deuterated tert-butyl group; an unsubstituted or deuterated, halogenated, cyano, or tert-butyl group; a naphthyl group; a pyridyl group; or a pyrimidinyl group.

[0191] In the exemplary embodiments described in this specification, m can be an integer from 1 to 4.

[0192] In the exemplary embodiments described in this specification, m can be 1.

[0193] In exemplary embodiments of this specification, when M, Ar, or Z are alkyl groups, M, Ar, or Z can be C2 to C10 branched alkyl groups.

[0194] In exemplary embodiments of this specification, R5 and R6 may each be independently: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; or substituted or unsubstituted C2 to C60 heterocycloalkyl.

[0195] In exemplary embodiments of this specification, R5 and R6 may each be independently: hydrogen; deuterium; halogen group; cyano; or substituted or unsubstituted C1 to C60 alkyl groups.

[0196] In an exemplary embodiment of this specification, R5 and R6 may each be hydrogen or deuterium independently.

[0197] In an exemplary embodiment of this specification, R5 may be hydrogen.

[0198] In an exemplary embodiment of this specification, p is 3, and R5 may be entirely hydrogen.

[0199] In an exemplary embodiment of this specification, R6 may be hydrogen.

[0200] In an exemplary embodiment of this specification, q is 5, and R6 may be entirely hydrogen.

[0201] In an exemplary embodiment of this specification, R5 may be deuterium.

[0202] In the exemplary embodiments described in this specification, p is 3, and R5 can be all deuterium.

[0203] In an exemplary embodiment of this specification, R6 may be deuterium.

[0204] In the exemplary embodiments described in this specification, q is 5, and R6 can be all deuterium.

[0205] In an exemplary embodiment of this specification, the sum of q and m in chemical formula H-1 is an integer from 1 to 6.

[0206] In an exemplary embodiment of this specification, the sum of q and m in chemical formula H-1 is 6.

[0207] In an exemplary embodiment of this specification, the sum of q and m in chemical formula H-2 is an integer from 1 to 6.

[0208] In an exemplary embodiment of this specification, the sum of q and m in the chemical formula H-2 is 6.

[0209] In an exemplary embodiment of this specification, the sum of p and m in chemical formula H-3 is an integer from 1 to 4.

[0210] In an exemplary embodiment of this specification, the sum of p and m in chemical formula H-3 is 4.

[0211] In the exemplary embodiments described in this specification, R4 to R6 may each be hydrogen or deuterium independently.

[0212] In exemplary embodiments of this specification, the deuterium substitution rate based on the total hydrogen and deuterium atoms in Formula 1 can be 0% or 5% to 100%.

[0213] In exemplary embodiments of this specification, the deuterium substitution rate of Formula 1 can be 0% or 10% to 100%.

[0214] In exemplary embodiments of this specification, the deuterium substitution rate of Formula 1 can be 0% or 15% to 100%.

[0215] In exemplary embodiments of this specification, the deuterium substitution rate of Formula 1 can be 0% or 20% to 100%.

[0216] In an exemplary embodiment of this specification, the deuterium substitution rate of Formula 1 can be 0%.

[0217] In an exemplary embodiment of this specification, the deuterium substitution rate of Formula 1 can be 100%.

[0218] In this specification, the deuterium substitution rate refers to the ratio of the number of deuterium atoms included in a particular structure (e.g., Formula 1) to the total number of hydrogen and deuterium atoms. For example, when a particular structure includes 20 hydrogen atoms and 20 deuterium atoms, the deuterium substitution rate is 50% because the ratio of 20 deuterium atoms to the total of 40 hydrogen and deuterium atoms is 50%.

[0219] In the exemplary embodiments of this specification, the deuterium ratio of the heterocyclic compound of Formula 1 satisfies the above range. The photochemical properties of the heterocyclic compound of Formula 1 containing deuterium and the compound that does not contain deuterium are almost similar. However, when deposited on a thin film, the deuterium-containing material tends to stack with a narrower intermolecular spacing.

[0220] Therefore, when manufacturing pure electronic devices (EOD) and pure hole devices (HOD) and confirming the current density of pure electronic devices (EOD) and pure hole devices (HOD) based on voltage, it can be confirmed that, among the heterocyclic compounds of Formula 1 of the present invention, compounds containing deuterium exhibit more balanced charge transport characteristics in the same structure compared to compounds not containing deuterium.

[0221] Furthermore, when the surface of the film was observed using atomic force microscopy (AFM), it was confirmed that the film deposited from compounds including deuterium had a more uniform surface without any aggregated areas.

[0222] Furthermore, since the single bond dissociation energy of carbon and deuterium is higher than that of carbon and hydrogen, when the heterocyclic compound of Formula 1 of the present invention includes deuterium, the overall molecular stability is enhanced, thereby improving the lifespan of the device.

[0223] In exemplary embodiments of this specification, the heterocyclic compound of Formula 1 may be represented by any of the following compounds.

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245] Furthermore, various substituents can be introduced into the structure of Formula 1 to synthesize compounds with the inherent properties of the introduced substituents. For example, materials that meet the requirements of each organic material layer can be synthesized by introducing substituents commonly used for preparing hole injection layer materials, hole transport layer materials, light emission layer materials, electron transport layer materials, and charge generation layer materials for organic light-emitting devices into the core structure.

[0246] In addition, the band gap can be finely tuned by introducing various substituents into the structure of Formula 1, and at the same time, the properties at the interface between organic materials can be improved and the applications of the materials can be diversified.

[0247] In another exemplary embodiment of this specification, an organic light-emitting device is provided, comprising: a first electrode; a second electrode; and an organic material layer having one or more layers provided between the first electrode and the second electrode, wherein the one or more layers of the organic material layer comprise one or more heterocyclic compounds of Formula 1.

[0248] In exemplary embodiments of this specification, the organic material layer includes an electron transport layer, and the electron transport layer includes one or more heterocyclic compounds of Formula 1.

[0249] The organic material layer of the organic light-emitting device of the present invention can be a single-layer structure, but it can also be a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light-emitting device of the present invention can have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer as organic material layers. However, the structure of the organic light-emitting device is not limited to this, and it can include fewer organic material layers.

[0250] In exemplary embodiments of this specification, an organic light-emitting device may include: a first electrode; a first stack provided on the first electrode and including a first light-emitting layer; a charge-generating layer provided on the first stack; a second stack provided on the charge-generating layer and including a second light-emitting layer; and a second electrode provided on the second stack.

[0251] In this case, the charge generation layer may comprise a heterocyclic compound represented by Formula 1. When a heterocyclic compound is used in the charge generation layer, the driving, efficiency, and lifetime of the organic light-emitting device can become excellent. Specifically, the heterocyclic compound of the present invention can be bonded to a metal, and therefore has the effect of promoting the injection of electrons generated from the p-type charge generation layer due to the high bonding effect with alkali metals or alkaline earth metals.

[0252] In addition, the first stack and the second stack may each independently include one or more of the hole injection layer, hole transport layer, hole blocking layer, electron transport layer and electron injection layer described above.

[0253] In an exemplary embodiment of this specification, the organic light-emitting device includes: a first electrode; a first stack provided on the first electrode and including a first light-emitting layer; a charge-generating layer provided on the first stack; a second stack provided on the charge-generating layer and including a second light-emitting layer; and a second electrode provided on the second stack, wherein the charge-generating layer may include one or more heterocyclic compounds.

[0254] In exemplary embodiments of this specification, the charge generation layer is an N-type charge generation layer, and the N-type charge generation layer may include one or more heterocyclic compounds.

[0255] In exemplary embodiments of this specification, in addition to heterocyclic compounds represented by Formula 1, the charge-generating layer may also include dopants known in the art.

[0256] In exemplary embodiments of this specification, the organic light-emitting device may further include a P-type charge-generating layer.

[0257] As an exemplary embodiment of the organic light-emitting device according to this application, the following... Figure 4 An organic light-emitting device with a 2-stacked tandem structure is illustrated in the example, but it is not limited thereto, and additional organic material layers may also be provided.

[0258] In this case, depending on the circumstances, the following can be omitted. Figure 4 The first electron blocking layer, the first hole blocking layer, and the second hole blocking layer are described in the text.

[0259] In an exemplary embodiment of this specification, the first electrode may be a positive electrode, and the second electrode may be a negative electrode.

[0260] In another exemplary embodiment of this specification, the first electrode may be a negative electrode, and the second electrode may be a positive electrode.

[0261] Organic light-emitting devices according to exemplary embodiments of this specification can be manufactured using typical methods and materials for manufacturing organic light-emitting devices, except that an organic material layer having one or more layers is formed by using a heterocyclic compound of chemical formula 1 described above.

[0262] When manufacturing organic light-emitting devices, heterocyclic compounds of Formula 1 can be formed as organic material layers not only by vacuum deposition but also by solution coating. In this paper, solution coating methods refer to spin coating, dip coating, inkjet printing, screen printing, spray coating, and roll coating, but are not limited to these.

[0263] In exemplary embodiments of this specification, the organic light-emitting device may be a blue organic light-emitting device, and a heterocyclic compound of Formula 1 may be used as a material for the blue organic light-emitting device. For example, a heterocyclic compound of Formula 1 may be included in the electron transport layer or charge generation layer of the blue organic light-emitting device.

[0264] In another exemplary embodiment of this specification, the organic light-emitting device can be a green organic light-emitting device, and a heterocyclic compound of Formula 1 can be used as a material for the green organic light-emitting device. For example, a heterocyclic compound of Formula 1 can be included in the electron transport layer or charge generation layer of the green organic light-emitting device.

[0265] In yet another exemplary embodiment of this specification, the organic light-emitting device may be a red organic light-emitting device, and a heterocyclic compound of Formula 1 may be used as the material for the red organic light-emitting device. For example, a heterocyclic compound of Formula 1 may be included in the electron transport layer or charge generation layer of the red organic light-emitting device.

[0266] The organic light-emitting device of the present invention may further include one or more layers selected from the group consisting of a light-emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

[0267] Figures 1 to 4 The stacking order of electrodes and organic material layers in an organic light-emitting device according to exemplary embodiments of this specification is illustrated. However, the scope of this application is not intended to be limited to these figures, and structures of organic light-emitting devices known in the art can also be applied to this application.

[0268] according to Figure 1 This illustrates an organic light-emitting device in which a positive electrode 200, an organic material layer 300, and a negative electrode 400 are sequentially stacked on a substrate 100. However, organic light-emitting devices are not limited to such structures, and as shown... Figure 2 As shown, an organic light-emitting device in which a negative electrode 400, an organic material layer 300, and a positive electrode 200 are sequentially stacked on a substrate 100 can also be realized.

[0269] Figure 3 This illustrates the case where the organic material has multiple layers. According to... Figure 3The organic light-emitting device includes a hole injection layer 301, a hole transport layer 302, a light-emitting layer 303, an electron transport layer 304, and an electron injection layer 305. However, the scope of this application is not limited to the stacked structure described above, and other layers besides the light-emitting layer may be omitted if necessary, and another necessary functional layer may be added.

[0270] If necessary, the organic material layer comprising the heterocyclic compound of formula 1 may additionally include other materials.

[0271] In the organic light-emitting devices according to exemplary embodiments of this specification, materials other than heterocyclic compounds of Formula 1 will be illustrated below, but these materials are merely illustrative and not intended to limit the scope of this application, and may be replaced with materials known in the art.

[0272] As positive electrode materials, materials with relatively high work functions can be used, and transparent conductive oxides, metals, or conductive polymers can be used. Specific examples of positive electrode materials include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline; and so on, but are not limited thereto.

[0273] Materials with relatively low work functions can be used as negative electrode materials, and metals, metal oxides, or conductive polymers can be used. Specific examples of negative electrode materials include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer materials such as LiF / Al or LiO2 / Al; and so on, but are not limited to these.

[0274] As a hole injection material, known hole injection materials can also be used, and for example, phthalocyanine compounds, such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429, or star-shaped amine derivatives described in the literature [Advanced Material, 6, p. 677 (1994)], such as tris(4-carbazolyl-9-ylphenyl)amine (TCTA), 4,4′,4"-tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline / dodecylbenzenesulfonic acid or poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate), polyaniline / camphorsulfonic acid or polyaniline / poly(4-styrenesulfonate), etc., can be used as soluble conductive polymers.

[0275] As hole transport materials, pyrazoline derivatives, arylamine derivatives, stilbene derivatives and triphenyldiamine derivatives can be used, as well as low molecular weight materials or polymer materials.

[0276] As electron transport materials, oxadiazole derivatives, anthraquinone dimethyl ether and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethyl ether and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, biphenylquinone derivatives, and metal complexes of 8-hydroxyquinoline and their derivatives can be used, as well as low molecular weight materials and polymer materials.

[0277] As an electron injection material, LiF is representatively used in the art, but this application is not limited thereto.

[0278] Red, green, or blue luminescent materials can be used, and two or more luminescent materials can be mixed and used if necessary. In this case, two or more luminescent materials are deposited and used as individual supply sources, or they are premixed for deposition and used as a single supply source. Furthermore, fluorescent or phosphorescent materials can also be used as luminescent materials. Materials that emit light by combining holes and electrons injected from the positive and negative electrodes can also be used alone as luminescent materials, but materials in which the host material and dopant material participate in light emission together can also be used.

[0279] When mixing and using luminescent materials as the substrate, substrates from the same series can be mixed and used, and substrates from different series can also be mixed and used. For example, any two or more materials, either N-type or P-type substrate materials, can be selected and used as the substrate materials for the luminescent layer.

[0280] Depending on the material to be used, the organic light-emitting device according to the exemplary embodiments of this specification can be a top-emitting, bottom-emitting, or dual-emitting type.

[0281] Based on principles similar to those applied to organic light-emitting devices, the compounds according to exemplary embodiments of this specification can even function in organic electronic devices, including organic solar cells, organic photoconductors, and organic transistors.

[0282] In addition, the band gap can be finely tuned by introducing various substituents into the structure of Formula 1, and at the same time, the properties at the interface between organic materials can be improved and the applications of the materials can be diversified.

[0283] Another exemplary embodiment of this specification provides a method for manufacturing an organic light-emitting device, the method comprising: preparing a substrate; forming a first electrode on the substrate; forming an organic material layer having one or more layers on the first electrode; and forming a second electrode on the organic material layer, wherein forming the organic material layer comprises forming an organic material layer having one or more layers using a composition for the organic material layer, and the composition for the organic material layer comprises a heterocyclic compound of formula 1 described above.

[0284] The present specification will be described in more detail below with reference to examples, but these examples are provided only for illustrative purposes and are not intended to limit the scope of the present application.

[0285] <Preparation Example>

[0286] <Preparation Example 1> Preparation of Compound 1

[0287]

[0288] 1) Preparation of compound 1-1

[0289] Compound A (2-bromo-9-phenyl-1,10-phenanthroline) (50 g, 0.149 mol, 1 equivalent), (3-chlorophenyl)boronic acid (26.2 g, 0.164 mol, 1.1 equivalent), Pd(PPh3)4 (8.61 g, 0.007 mol, 0.05 equivalent), K2CO3 (41.2 g, 0.298 mol, 2.0 equivalent), toluene (500 ml), EtOH (ethanol) (100 ml), and water (100 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 6 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 49.2 g of compound 1-1, in 90% yield.

[0290] 2) Preparation of compounds 1-2

[0291] Compound 1-1 (49.1 g, 0.134 mol, 1 equivalent), 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-1,3,2-dioxacyclopentaborane (37.8 g, 0.147 mol, 1.1 equivalent), Pd2(dba)3 (4.23 g, 0.007 mol, 0.05 equivalent), Xphos (6.38 g, 0.013 mmol, 0.1 equivalent), KOAc (potassium acetate) (32.8 g, 0.335 mol, 2.5 equivalent), and 1,4-dioxane (375 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 6 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 48.0 g of compounds 1-2, with a yield of 78%.

[0292] 3) Preparation of compounds 1-3

[0293] Compounds 1-2 (26.0 g, 0.057 mol, 1 equivalent), 1-(6-bromo-2-pyridyl)acetone (12.5 g, 0.062 mol, 1.1 equivalent), Pd(PPh3)4 (3.29 g, 0.003 mol, 0.05 equivalent), K2CO3 (15.8 g, 0.114 mol, 2.0 equivalent), 1,4-dioxane (250 ml), and water (50 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 10 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 20.2 g of compounds 1-3, in a yield of 79%.

[0294] 4) Preparation of Compound 1

[0295] Compounds 1-3 (20.0 g, 0.045 mol, 1 equivalent), compound B (2-aminobenzaldehyde) (10.7 g, 0.089 mol, 2.0 equivalent), NaOH (5.32 g, 0.133 mol, 3.0 equivalent), and isopropanol (IPA) (200 ml) were placed in a container, and the resulting mixture was stirred at 90 °C for 24 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 10.5 g of compound 1, in a yield of 44%.

[0296] The compounds in Table 1 below were obtained by performing the synthesis in the same manner as in Preparation Example 1, except that intermediates A and B in Table 1 below were used instead of compounds A and B.

[0297] [Table 1]

[0298]

[0299]

[0300] <Preparation Example 2> Preparation of Intermediate C

[0301]

[0302] 2-Amino-5-bromobenzaldehyde (30.0 g, 0.150 mol, 1 equivalent), phenylboronic acid (21.9 g, 0.180 mol, 1.2 equivalent), Pd(PPh3)4 (8.67 g, 0.008 mol, 0.05 equivalent), K2CO3 (41.5 g, 0.300 mol, 2.0 equivalent), 1,4-dioxane (300 ml), and water (60 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 5 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 26.1 g of intermediate C, in 88% yield.

[0303] Depending on the structure to be synthesized, 2-amino-4-bromobenzaldehyde or 2-amino-6-bromobenzaldehyde is used instead of 2-amino-5-bromobenzaldehyde, and pyridine-2-ylboronic acid or pyridine-4-ylboronic acid is used instead of phenylboronic acid in Preparation Example 2, so that intermediate C in Table 2 below can be obtained by performing the synthesis in the same manner.

[0304] <Preparation Example 3> Preparation of Compound 8

[0305]

[0306] Compounds 1-3 (20.0 g, 0.045 mol, 1 equivalent) prepared in Preparation Example 1, intermediate C (17.8 g, 0.089 mmol) prepared in Preparation Example 2, NaOH (5.32 g, 0.133 mol, 3.0 equivalent), and IPA (200 ml) were placed in a container, and the resulting mixture was stirred at 90 °C for 24 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 14.7 g of compound 8, in a yield of 53%.

[0307] The compounds in Table 2 below are obtained by replacing compounds 1-3 in Preparation Example 3 with compounds obtained by performing synthesis in the same manner as in Preparation Example 1 using intermediate A from Table 2 below instead of compound A in Preparation Example 1, and by performing synthesis in the same manner as in Preparation Example 1 using intermediate C from Table 2 below instead of intermediate C in Preparation Example 3.

[0308] [Table 2]

[0309]

[0310]

[0311]

[0312] <Preparation Example 4> Preparation of Intermediate C

[0313] 1) Intermediate C of compounds 145, 146, 150, 156, 161, 162, 168, 171, 173, 191, 209, 212 and 214

[0314]

[0315] 1-(6-bromo-2-pyridyl)acetone (20.0 g, 0.100 mol, 1 equivalent), 2-aminobenzaldehyde (12.1 g, 0.100 mol, 1.0 equivalent), NaOH (6.00 g, 0.150 mol, 1.5 equivalent), and EtOH (200 mL) were placed in a container, and the resulting mixture was stirred at 60 °C for 2 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 17.3 g of intermediate C, in a yield of 61%.

[0316] Depending on the structure to be synthesized, 3-amino-[1,1′-biphenyl]-4-carboxaldehyde, 2-amino-5-(pyridin-2-yl)benzaldehyde, or 2-amino-4-(pyridin-2-yl)benzaldehyde were used instead of 2-aminobenzaldehyde, and the synthesis was performed in the same manner as in Preparation Example 4 to obtain intermediate C in Table 3 below.

[0317] 2) Intermediate C of compound 321

[0318]

[0319] (2-Chloroquinoline-7-yl)boric acid (30.0 g, 0.145 mol, 1 equivalent), 2-bromopyridine (25.1 g, 0.159 mol, 1.1 equivalent), Pd(PPh3)4 (8.38 g, 0.007 mol, 0.05 equivalent), K2CO3 (40.1 g, 0.290 mol, 2.0 equivalent), 1,4-dioxane (300 ml), and water (60 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 4 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, the water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 25.3 g of intermediate C, with a yield of 72%.

[0320] <Preparation Example 5> Preparation of Compound 145

[0321]

[0322] 1) Preparation of compound 145-1

[0323] Compound A (2-bromo-9-phenyl-1,10-phenanthroline) (30 g, 0.089 mol, 1 equivalent), 2-(3-bromo-5-chloro-phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxane (31.2 g, 0.098 mol, 1.1 equivalent), Pd(PPh3)4 (5.14 g, 0.004 mol, 0.05 equivalent), K3PO4 (38.0 g, 0.179 mol, 2.0 equivalent), 1,4-dioxane (300 ml), and water (60 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 3 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, the water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 32.9 g of compound 145-1, in 83% yield.

[0324] 2) Preparation of compound 145-2

[0325] Compound 145-1 (25.0 g, 0.056 mol, 1 equivalent), compound B (phenylboronic acid) (7.68 g, 0.062 mol, 1.1 equivalent), Pd(PPh3)4 (3.24 g, 0.003 mol, 0.05 equivalent), Na2CO3 (11.9 g, 0.112 mol, 2.0 equivalent), 1,4-dioxane (250 ml), and water (50 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 10 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 22.0 g of compound 145-2, in 89% yield.

[0326] 3) Preparation of compound 145-3

[0327] Compound 145-2 (22.0 g, 0.050 mol, 1 equivalent), 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-1,3,2-dioxacyclopentaborane (14.0 g, 0.055 mol, 1.1 equivalent), Pd2(dba)3 (1.43 g, 0.002 mol, 0.05 equivalent), XPhos (2.37 g, 0.005 mmol, 0.1 equivalent), KOAc (12.2 g, 0.124 mol, 2.5 equivalent), and 1,4-dioxane (250 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 6 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 19.0 g of compound 145-3, with a yield of 72%.

[0328] 4) Preparation of compound 145

[0329] Compound 145-3 (18.0 g, 0.034 mol, 1 equivalent), compound C (2-(6-bromopyridin-2-yl)quinoline) (9.82 g, 0.041 mol, 1.2 equivalent), Pd(PPh3)4 (1.95 g, 0.002 mol, 0.05 equivalent), K2CO3 (9.31 g, 0.067 mol, 2.0 equivalent), 1,4-dioxane (200 ml), and water (40 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 24 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 13.0 g of compound 145, in a yield of 63%.

[0330] The compounds in Table 3 below were obtained by performing the synthesis in the same manner as in Preparation Example 5, except that intermediates A to C in Table 3 below were used instead of compounds A to C in Preparation Example 5.

[0331] [Table 3]

[0332]

[0333]

[0334] <Preparation Example 6> Preparation of Compound 147

[0335]

[0336] Compound 147 was obtained by performing the synthesis in the same manner as in Preparation Example 5, except that in the preparation of Compound 145-1 in Preparation Example 5, 2-(3-bromo-5-(tert-butyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane was used instead of 2-(3-bromo-5-chloro-phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane.

[0337] The compounds in Table 4 below were obtained by performing the synthesis in the same manner as in Preparation Example 6, except that intermediates A and B in Table 4 below were used instead of compounds A and B.

[0338] [Table 4]

[0339]

[0340] <Preparation Example 7> Preparation of Intermediate B

[0341]

[0342] 2-Chloro-6-(4,4,5,5-tetramethyl-1,3,2-dioxane-2-yl)pyridine (30.0 g, 0.125 mol, 1 equivalent), 3-chloroisoquinoline (22.5 g, 0.138 mol, 1.1 equivalent), Pd(PPh3)4 (7.22 g, 0.006 mol, 0.05 equivalent), K2CO3 (34.6 g, 0.250 mol, 2.0 equivalent), 1,4-dioxane (300 ml), and water (60 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 4 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, the water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 23.3 g of intermediate B, with a yield of 77%.

[0343] Depending on the structure to be synthesized, 3-chloro-7-phenylisoquinoline or 1-chloroisoquinoline was used instead of 3-chloroisoquinoline, and the intermediate B in Table 5 below was obtained by performing the synthesis in the same manner as in Preparation Example 7.

[0344] <Preparation Example 8> Preparation of Compound 232

[0345]

[0346] 1) Preparation of compound 232-1

[0347] Compound A (2-bromo-9-phenyl-1,10-phenanthroline) (50 g, 0.149 mol, 1 equivalent), (3-chlorophenyl)boronic acid (26.2 g, 0.164 mol, 1.1 equivalent), Pd(PPh3)4 (8.61 g, 0.007 mol, 0.05 equivalent), K2CO3 (41.2 g, 0.298 mol, 2.0 equivalent), toluene (500 ml), EtOH (100 ml), and water (100 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 6 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 49.2 g of compound 232-1, in 90% yield.

[0348] 2) Preparation of compound 232-2

[0349] Compound 232-1 (49.1 g, 0.134 mol, 1 equivalent), 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-1,3,2-dioxacyclopentaborane (37.8 g, 0.147 mol, 1.1 equivalent), Pd2(dba)3 (4.23 g, 0.007 mol, 0.05 equivalent), Xphos (6.38 g, 0.013 mmol, 0.1 equivalent), KOAc (32.8 g, 0.335 mol, 2.5 equivalent), and 1,4-dioxane (375 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 6 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 48.0 g of compound 232-2, with a yield of 78%.

[0350] 3) Preparation of compound 232

[0351] Compound 232-2 (15.0 g, 0.033 mol, 1 equivalent), compound B (3-(6-chloropyridin-2-yl)isoquinoline) (8.66 g, 0.036 mol, 1.1 equivalent), Pd(PPh3)4 (1.91 g, 0.002 mol, 0.05 equivalent), K2CO3 (9.12 g, 0.066 mol, 2.0 equivalent), 1,4-dioxane (150 mL), and water (30 mL) were placed in a container, and the resulting mixture was stirred at 100 °C for 24 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, the water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 15.0 g of compound 232, in 85% yield.

[0352] The compounds in Table 5 below were obtained by performing the synthesis in the same manner as in Preparation Example 8, except that intermediate A in Table 5 below was used instead of compound A and compound B, and intermediate B was used instead of 3-(6-chloropyridin-2-yl)isoquinoline (B).

[0353] [Table 5]

[0354]

[0355] <Preparation Example 9> Preparation of Compound 306

[0356]

[0357] 1) Preparation of compound 306-1

[0358] (3-acetylphenyl)boric acid (20 g, 0.122 mol, 1 equivalent), compound A (2-amino-4-bromobenzaldehyde) (24.4 g, 0.122 mol, 1.0 equivalent), NaOH (7.32 g, 0.183 mol, 1.5 equivalent), and EtOH (ethanol) (200 mL) were placed in a container, and the resulting mixture was stirred at 60 °C for 2 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 34.0 g of compound 306-1, in 85% yield.

[0359] 2) Preparation of compound 306-2

[0360] Compound 306-1 (28.3 g, 0.086 mol, 1.2 equivalents), compound B (2-bromo-9-phenyl-1,10-phenanthroline) (25.0 g, 0.75 mol, 1.0 equivalents), Pd2(dba)3 (4.30 g, 0.004 mol, 0.05 equivalents), K2CO3 (20.6 g, 0.149 mol, 2.0 equivalents), 1,4-dioxane (300 ml), and water (60 ml) were placed in a container, and the resulting mixture was stirred at 100 °C for 6 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 34.0 g of compound 306-2, in 84% yield.

[0361] 3) Preparation of compound 306

[0362] Compound 306-2 (15.0 g, 0.028 mol, 1 equivalent), compound C (pyridin-2-ylboronic acid) (3.77 g, 0.031 mol, 1.1 equivalent), Pd(PPh3)4 (1.61 g, 0.001 mol, 0.05 equivalent), K2CO3 (7.70 g, 0.056 mol, 2.0 equivalent), 1,4-dioxane (150 mL), and water (30 mL) were placed in a container, and the resulting mixture was stirred at 100 °C for 6 hours. After terminating the reaction by adding distilled water, extraction was performed using dichloromethane and distilled water. Subsequently, the water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 7.0 g of compound 306, in a yield of 47%.

[0363] The compounds in Table 6 below were obtained by performing the synthesis in the same manner as in Preparation Example 9, except that intermediates A to C in Table 6 below were used instead of compounds A to C.

[0364] [Table 6]

[0365]

[0366]

[0367] <Preparation Example 10> Preparation of Compound 401

[0368]

[0369] Compound 1 (5 g, 0.01 mol, 1 equivalent) from Preparation Example 1, trifluoromethanesulfonic acid (5.76 mL, 0.065 mol, 7 equivalents), and C6D6 (25 mL) were placed in a container, and the resulting mixture was stirred at 60 °C for 2 hours. D2O was added, the mixture was stirred for 30 minutes, and then neutralized by dropwise addition of triethylamine. After neutralization, extraction was performed using dichloromethane. Subsequently, water was removed with MgSO4. The residue was separated by silica gel column chromatography to obtain 3.4 g of compound 401, in a yield of 65%.

[0370] <Preparation Example 11> Preparation of Compound 402

[0371]

[0372] Compound 405 was obtained by performing the synthesis in the same manner as in Preparation Example 10, except that compound 1 was replaced with compound 145 from Preparation Example 5.

[0373] <Preparation Example 12> Preparation of Compound 411

[0374]

[0375] Compound 411 was obtained by performing the synthesis in the same manner as in Preparation Example 10, except that compound 1 was replaced with compound 306 from Preparation Example 9.

[0376] pass 1 1H-NMR and FD-mass spectrometry confirmed that the compound synthesized in the preparation example was the desired compound. This is shown in Table 7 below. 1 The measurements were obtained by H NMR (CDCl3, 200 MHz) and the measurements by field desorption mass spectrometry (FD-Mass) are shown in Table 8 below.

[0377] [Table 7]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383] [Table 8]

[0384]

[0385]

[0386] <Experimental Example>

[0387] <Experiment Example 1>

[0388] 1) Fabrication of organic light-emitting devices

[0389] <Comparison Example 1>

[0390] Trichloroethylene, acetone, ethanol, and distilled water were each used sequentially to ultrasonically clean the transparent electrode indium tin oxide (ITO) film obtained from glass used in OLEDs (manufactured by Samsung-Corning Co., Ltd.) for 5 minutes. The ITO film was then placed in isopropanol for storage and later use. Next, the ITO substrate was placed in the substrate clamp of a vacuum deposition apparatus, and the following 4,4′,4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in the cell of the vacuum deposition apparatus.

[0391]

[0392] Then, the air in the chamber is evacuated until the vacuum level in the chamber reaches 10. -6 Torx, and then deposited on an ITO substrate by applying current to the cells to evaporate 2-TNATA. A hole injection layer of a certain thickness is deposited on the hole injection layer by placing the following N,N′-bis(α-naphthyl)-N,N′-diphenyl-4,4′-diamine (NPB) in another cell of a vacuum deposition apparatus and applying current to the cell to evaporate the NPB. A hole transport layer of a certain thickness.

[0393]

[0394] A hole injection layer and a hole transport layer are formed as described above, and then a blue luminescent material having the following structure is deposited thereon as the luminescent layer. Specifically, a blue luminescent host material H1 is vacuum-deposited on one unit of a vacuum deposition apparatus to have... The thickness is such that, based on the host material, a blue luminescent dopant material D1 is vacuum deposited in an amount of 5%.

[0395]

[0396] Subsequently, a compound E1 with the following structural formula is deposited as an electron transport layer to have The thickness.

[0397]

[0398] By depositing lithium fluoride (LiF) as an electron injection layer to achieve The thickness and to make the Al negative electrode have The thickness is used to manufacture OLED devices. Meanwhile, all the organic compounds required for manufacturing OLED devices are within 10... -8 Up to 10 -6 The material undergoes vacuum sublimation purification and is then used to manufacture OLEDs.

[0399] <Examples 1 through 50 and Comparison Examples 2 through 11>

[0400] The organic light-emitting device was fabricated in the same manner as in Comparative Example 1, except that the compounds shown in Table 9 below were used instead of compound E1 used in Comparative Example 1 when forming the electron transport layer.

[0401] The structures of the comparative compounds used in Comparative Examples 2 to 11 are as follows.

[0402]

[0403] 2) Driving voltage and luminous efficiency of organic light-emitting devices

[0404] For the organic light-emitting device manufactured as described above, the electroluminescence (EL) characteristics were measured using an M7000 manufactured by McScience Inc., and based on the measurement results, when the reference luminance was 3,500 cd / m², 2 At that time, the lifespan measurement was performed using a lifespan measurement device (M6000) manufactured by McScience Inc. 95 The driving voltage, luminous efficiency, color coordinates (CIE), and lifetime (T) of the blue organic electroluminescent device manufactured according to the present invention were measured. 95 The results are shown in Table 9.

[0405] [Table 9]

[0406]

[0407]

[0408]

[0409] As can be seen from the results in Table 9, compared with Comparative Examples 1 to 11, the organic light-emitting device using the electron transport layer material of the blue organic light-emitting device of the present invention has a low driving voltage and significantly improved luminous efficiency and lifespan.

[0410] It was determined that these results are due to the appropriate electron transport capability of the skeleton of the present invention, and that the more stable compound can efficiently transfer electrons without decomposing or destroying the compound due to the stable bonding between the phenanthroline functional group and the metal used for the negative electrode.

[0411] Specifically, the comparative compounds A to J used in Comparative Examples 2 to 11 comprise partial structures of the heterocyclic compounds of the present invention, but do not satisfy Chemical Formula 1 of the present invention. Specifically, comparative compounds A to D and comparative compounds H to J have Het configurations different from those of the present invention, comparative compound E has a Het position different from that of the present invention, comparative compound F does not include the M configuration of the present invention, and comparative compound G comprises a naphthalene ring instead of the benzene ring of the present invention.

[0412] Therefore, it can be confirmed that even if a partial structure is used equally in the heterocyclic compound structure of the present invention, it cannot provide superior performance as a device compared with the heterocyclic compound of the present invention when the overall configuration of the present invention is not satisfied.

[0413] When comparing specific values, in the case of Comparative Examples 2 to 11, which are not included in the scope of this invention but use compounds including similar structures, the luminous efficiency and lifetime are improved compared to Comparative Example 1, which uses compound E1, but the maximum luminous efficiency is 7.12 cd / A and the maximum lifetime is only 72.

[0414] In contrast, in Examples 1 to 53 using the compounds of the present invention, the luminous efficiency is 7.54 cd / A to 7.84 cd / A, and the lifetime is 95 to 129. Compared with the material in the prior art (Comparative Example 1), the luminous efficiency is increased by at least 17%, and the lifetime is increased by at least 1.9 times. Furthermore, it can be seen that the luminous efficiency is improved by at least 5%, and the lifetime is improved by at least 30% compared with the comparative example.

[0415] Therefore, it has been determined that the heterocyclic compounds of the present invention satisfy all configurations of Formula 1, and thus have improved electron transport properties and stability compared to similar structures, thereby exhibiting superior performance in all aspects of driving voltage, efficiency and lifetime.

[0416] <Experimental Example 2>

[0417] 1) Fabrication of organic light-emitting devices

[0418] The glass substrate is ultrasonically cleaned with distilled water, wherein a thin layer of ITO is coated to have... The thickness of the film is determined. Upon completion of the rinsing with distilled water, the glass substrate is ultrasonically cleaned with solvents such as acetone, methanol, and isopropanol, dried, and then subjected to UVO treatment for 5 minutes using a UV cleaner. Afterward, the substrate is transferred to a plasma cleaner (PT) and then subjected to plasma treatment to achieve the ITO work function and remove residual film under vacuum. The substrate is then transferred to a thermal deposition apparatus for organic deposition.

[0419] An organic material with a 2-stacked white organic light-emitting device (WOLED) structure is formed on an ITO transparent electrode (positive electrode). For the first stack, TAPC is first deposited via thermal vacuum deposition to form an organic material with a 2-stacked white organic light-emitting device (WOLED) structure. The hole transport layer is formed to a certain thickness. The hole transport layer is formed, and then a light-emitting layer is deposited on it using thermal vacuum deposition as follows. A light-emitting layer with a concentration of 8% blue phosphorescent dopant FIrpic is used to dope the host TCz1 to deposit the light-emitting layer. A light-emitting layer of a certain thickness is formed using TmPyPB. An electron transport layer of a certain thickness was formed, and then a compound described in Table 10 below was formed by doping with Cs₂CO₃ at a concentration of 20%. A charge-generating layer of a certain thickness.

[0420] For the second stack, MoO3 is first deposited via thermal vacuum to have... The hole injection layer is formed to a certain thickness. The hole transport layer, serving as the common layer, is formed by doping TAPC with MoO3 at a concentration of 20%. The thickness, and then formed into a shape with by depositing Tapc. The thickness. A light-emitting layer was deposited on the host TCz1 by doping it with an 8% concentration of the green phosphorescent dopant Ir(ppy)3 to achieve the desired light emission. The thickness, and then using TmPyPB to form with The thickness is used as an electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to achieve the desired electron transport properties. The thickness is used to form the electron injection layer, and then an aluminum (Al) negative electrode is deposited on the electron injection layer to have... The thickness is used to form the negative electrode, thereby manufacturing organic electroluminescent devices.

[0421]

[0422] The comparative compounds in Table 10 below have the same structure as those in Experimental Example 1 above.

[0423] Meanwhile, all the organic compounds required to manufacture OLED devices are available for each material in 10... -8 Up to 10-6 The material undergoes vacuum sublimation purification and is then used to manufacture OLEDs.

[0424] 2) Driving voltage and luminous efficiency of organic light-emitting devices

[0425] For the organic electroluminescent device manufactured as described above, the electroluminescence (EL) characteristics were measured using an M7000 manufactured by McScience Inc., and based on the measurement results, when the reference luminance was 3,500 cd / m², 2 At that time, the lifespan measurement was performed using a lifespan measurement device (M6000) manufactured by McScience Inc. 95 The driving voltage, luminous efficiency, color coordinates (CIE), and lifetime (T) of the white organic electroluminescent device manufactured according to the present invention were measured. 95 The results are shown in Table 10.

[0426] [Table 10]

[0427]

[0428]

[0429] As can be seen from the results in Table 10, compared with Comparative Examples 12 to 22, the organic electroluminescent device using the charge generation layer material of the 2-stack white organic electroluminescent device of the present invention has a low driving voltage and improved lifetime and luminous efficiency.

[0430] It was determined that these results were due to the framework comprising a structure with appropriate electron transport capabilities and being constructed in the form of phenanthroline functional groups that can bond with metals such as Li and Yb used in forming N-type charge-generating layers.

[0431] It is believed that due to these structural features, when the compound used as the N-type charge generation layer is doped with a metal, interstitial states are stably formed in the N-type charge generation layer, and electrons generated from the P-type charge generation layer are readily injected into the electron transport layer through the interstitial states generated in the N-type charge generation layer. Therefore, it has been determined that electrons from the P-type charge generation layer are injected into the N-type charge generation layer and subsequently transferred well to the electron transport layer, thus reducing the driving voltage of the organic light-emitting device and improving efficiency and lifetime.

[0432] Furthermore, it was confirmed that, as described above in Experimental Example 1, the comparative compounds used in Comparative Examples 12 to 22 included only different configurations in some parts of the structure compared to the heterocyclic compounds of the present invention, but when used as materials for charge generation layers, the comparative compounds failed to exhibit superior performance compared to the present invention.

[0433] Therefore, it can be confirmed that even if a partial structure is used equally in the heterocyclic compound structure of the present invention, it cannot provide superior performance as a device compared with the heterocyclic compound of the present invention when the overall configuration of the present invention is not satisfied.

Claims

1. A heterocyclic compound represented by the following Chemical Formula 1: [Chemical Formula 1] wherein In Chemical Formula 1, M is: a substituted or unsubstituted C1 to C60 alkyl; a substituted or unsubstituted C6 to C60 aryl; or a substituted or unsubstituted C2 to C60 heteroaryl, Ar is: hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl; a substituted or unsubstituted C6 to C60 aryl; or a substituted or unsubstituted C2 to C60 heteroaryl, R1 to R3 are each independently: hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl; a substituted or unsubstituted C3 to C60 cycloalkyl; or a substituted or unsubstituted C2 to C60 heterocycloalkyl, R4 is: hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl; a substituted or unsubstituted C3 to C60 cycloalkyl; a substituted or unsubstituted C2 to C60 heterocycloalkyl; a substituted or unsubstituted C6 to C60 aryl; or a substituted or unsubstituted C2 to C60 heteroaryl, o is an integer of 0 to 6, and when o is 2 or more, R4 are the same as or different from each other, Het is a group represented by any one of the following Chemical Formula H-1 to Chemical Formula H-3, [Chemical Formula H-1] [Chemical Formula H-2] [Chemical Formula H-3] In Chemical Formula H-1 to Chemical Formula H-3, Z is: hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl; a substituted or unsubstituted C6 to C60 aryl; or a substituted or unsubstituted C2 to C60 heteroaryl, m is an integer of 0 to 4, and when m is 2 or more, Z are the same as or different from each other, R5 and R6 are each independently: hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl; a substituted or unsubstituted C3 to C60 cycloalkyl; a substituted or unsubstituted C2 to C60 heterocycloalkyl; a substituted or unsubstituted C6 to C60 aryl; or a substituted or unsubstituted C2 to C60 heteroaryl, and p is an integer of 1 to 3, q is an integer of 1 to 5, and when each of p and q is 2 or more, R5 and R6 are the same as or different from each other.

2. The heterocyclic compound according to claim 1, wherein, Chemical Formula 1 is represented by any one of the following Chemical Formula 1-1 to Chemical Formula 1-3: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] In Chemical Formula 1-1 to Chemical Formula 1-3, the definition of each substituent is the same as in Chemical Formula 1.

3. The heterocyclic compound according to claim 1, wherein, Chemical Formula 1 is represented by the following Chemical Formula 1-1-1, Chemical Formula 1-1-2, Chemical Formula 1-2-1, or Chemical Formula 1-3-1: [Chemical Formula 1-1-1] [Chemical Formula 1-1-2] [Chemical Formula 1-2-1] [Chemical Formula 1-3-1] In Chemical Formula 1-1-1, Chemical Formula 1-1-2, Chemical Formula 1-2-1, and Chemical Formula 1-3-1, the definition of each substituent is the same as in Chemical Formula 1.

4. The heterocyclic compound according to claim 1, wherein, Ar is: hydrogen; deuterium; a substituted or unsubstituted C1 to C10 alkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group including O or S.

5. The heterocyclic compound according to claim 1, wherein, M is: a substituted or unsubstituted C1 to C10 alkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group.

6. The heterocyclic compound according to claim 1, wherein, Z is: hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C10 alkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group.

7. The heterocyclic compound according to claim 1, wherein, R1 to R3 are each independently hydrogen or deuterium.

8. The heterocyclic compound according to claim 1, wherein, R4 to R6 are each independently hydrogen or deuterium.

9. The heterocyclic compound according to claim 1, wherein, The deuterium substitution rate of Chemical Formula 1 is 0%, or 10% to 100%.

10. The heterocyclic compound according to claim 1, wherein, Chemical Formula 1 is represented by any one of the following compounds:

11. An organic light emitting device comprising: a first electrode; a second electrode; and an organic material layer having one or more layers, provided between the first electrode and the second electrode, wherein the one or more layers of the organic material layer include one or more of the heterocyclic compounds according to any one of claims 1 to 10.

12. The organic light emitting device of claim 11, wherein, The organic material layer includes an electron transport layer, and the electron transport layer includes one or more of the heterocyclic compounds.

13. The organic light emitting device of claim 11, wherein, The organic light emitting device includes: the first electrode; a first stack provided on the first electrode and including a first light emitting layer; a charge generation layer provided on the first stack; a second stack provided on the charge generation layer and including a second light emitting layer; and a second electrode provided on the second stack, and the charge generation layer includes one or more of the heterocyclic compounds.

14. The organic light emitting device of claim 13, wherein, The charge generation layer is an N-type charge generation layer, and the N-type charge generation layer includes one or more of the heterocyclic compounds.

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