Organic light-emitting diode with high efficiency

1. An organic light-emitting diode, comprising: a first electrode; a second electrode facing the first electrode; and a light-emitting layer and an electron density control layer sequentially arranged between the first electrode and the second electrode wherein the light-emitting layer includes at least one of the amine compounds represented by the following Chemical Formulas A and B and the electron density control layer includes at least one of the compounds represented by the following Chemical Formulas F to H:

wherein,

A 1 , A 2 , E, and F may be the same or different, and are each independently a substituted or unsubstituted aromatic hydrocarbon ring of 6 to 50 carbon atoms, or a substituted or unsubstituted heteroaromatic ring of 2 to 40 carbon atoms, wherein two adjacent carbon atoms of the aromatic ring A 1 and two adjacent carbon atoms of the aromatic ring A 2 form a 5-membered fused ring together with a carbon atom connected to both substituents R 1 and R 2 ;

linkers L 1 to L 12 may be the same or different and are each independently selected from among a direct bond, a substituted or unsubstituted alkylene of 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene of 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene of 2 to 60 carbon atoms, a substituted or unsubstituted cycloalkylene of 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene of 2 to 60 carbon atoms, a substituted or unsubstituted arylene of 6 to 60 carbon atoms, and a substituted or unsubstituted heteroarylene of 2 to 60 carbon atoms;

M is any one selected from among N—R 3 , CR 4 R 5 , SiR 6 R 7 , GeR 8 R 9 , O, S, and Se;

R 1 to R 9 and Ar 1 to Ar 8 may be the same or different and are each independently any one selected from among a hydrogen atom, an deuterium atom, a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted aryl of 6 to 50 carbon atoms, a substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl of 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl of 5 to 30 carbon atoms, a substituted or unsubstituted heteroaryl of 2 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl of 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy of 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy of 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy of 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy of 6 to 30 carbon atoms, a substituted or unsubstituted alkylamine of 1 to 30 carbon atoms, a substituted or unsubstituted arylamine of 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl of 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl of 6 to 30 carbon atoms, a substituted or unsubstituted alkylgermanium of 1 to 30 carbon atoms, a substituted or unsubstituted arylgermanium of 1 to 30 carbon atoms, a cyano, a nitro, and a halogen, with the proviso that R 1 and R 2 may be bonded to each other to form a mono- or polycyclic aliphatic or aromatic ring, which may be a heterocyclic ring bearing a heteroatom selected from among N, O, P, Si, S, Ge, Se, and Te as a ring member;

p1 to p4, r1 to r4, and s1 to s4 are each independently an integer of 1 to 3, with the proviso that when any of them is 2 or greater, the corresponding linkers may be the same or different;

x is an integer of 1 or 2, and y and z may be the same or different and are each independently an integer of 0 to 3; and

Ar 1 may form a ring with Ar 2 , Ar 3 may form a ring with Ar 4 , Ar 5 may form a ring with Ar 6 , and Ar 7 may form a ring with Ar 8 ;

two adjacent carbon atoms of the A 2 ring moiety of Chemical Formula A may occupy respective positions * of Structural Formula Q 1 to form a fused ring, and

two adjacent carbon atoms of the A 1 ring moiety of Chemical Formula B may occupy respective positions * of structural Formula Q 2 to form a fused ring, and two adjacent carbon atoms of the A 2 ring moiety of Chemical Formula B may occupy respective positions * of Structural Formula Q 1 to form a fused ring;

wherein,

substituents R11 to R 18 may be the same or different and are each independently selected from among a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl of 5 to 30 carbon atoms, a substituted or unsubstituted aryl of 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl of 3 to 50 carbon atoms, a substituted or unsubstituted alkoxy of 2 to 30 carbon atoms, a substituted or unsubstituted aryloxy of 6 to 50 carbon atoms, a substituted or unsubstituted alkylamine of 1 to 30 carbon atoms, a substituted or unsubstituted arylamine of 6 to 50 carbon atoms, a substituted or unsubstituted silyl, a halogen, and a cyano;

wherein,

X 1 to X 3 may be the same or different and are each independently a nitrogen atom or CR′, with the proviso that

at least one of X 1 to X 3 is a nitrogen atom, wherein

R′ is selected from among a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl of 5 to 30 carbon atoms, a substituted or unsubstituted aryl of 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl of 3 to 50 carbon atoms, a substituted or unsubstituted alkoxy of 2 to 30 carbon atoms, a substituted or unsubstituted aryloxy of 6 to 50 carbon atoms, a substituted or unsubstituted alkylamine of 1 to 30 carbon atoms, a substituted or unsubstituted arylamine of 6 to 50 carbon atoms, a substituted or unsubstituted silyl, a halogen, and a cyano;

Ar is selected from among a substituted or unsubstituted alkyl of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted aryl of 6 to 50 carbon atoms, and a substituted or unsubstituted heteroaryl of 3 to 50 carbon atoms;

Z 1 and Z 2 may be the same or different and are each independently a substituted or unsubstituted aryl of 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl of 3 to 30 carbon atoms, or a substituent represented by the following Structural Formula A:

* L 13 t HAr  [Structural Formula A]

wherein,

L 13 is selected from among a single bond, a substituted or unsubstituted alkylene of 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene of 3 to 30 carbon atoms, a substituted or unsubstituted arylene of 6 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene of 3 to 50 carbon atoms,

HAr is a substituted or unsubstituted heteroaryl of 3 to 50 carbon atoms, and

t is an integer of 0 to 3, with the proviso that when t is 2 or greater, the corresponding substituents L 13 's may be the same or different; and

wherein,

substituents Z 11 and Z 12 may be the same or different and are each independently a substituted or unsubstituted aryl of 6 to 50 carbon atoms or a substituted or unsubstituted heteroaryl of 3 to 50 carbon atoms,

linker L 14 is a single bond or a substituted or unsubstituted aryl of 6 to 50 carbon atoms,

u is an integer of 0 to 2, with the proviso that when u is 2, the corresponding linkers L 14 's may be the same or different, and

substituents R 21 to R 28 may be the same or different and are each independently selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted aryl of 6 to 50 carbon atoms, a substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl of 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl of 5 to 30 carbon atoms, a substituted or unsubstituted heteroaryl of 2 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl of 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy of 2 to 30 carbon atoms, a substituted or unsubstituted aryloxy of 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy of 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy of 6 to 30 carbon atoms, a substituted or unsubstituted alkylamine of 1 to 30 carbon atoms, a substituted or unsubstituted arylamine of 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl of 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl of 6 to 30 carbon atom, a substituted or unsubstituted alkylgermanium of 1 to 30 carbon atoms, a substituted or unsubstituted arylgermanium of 1 to 30 carbon atoms, a cyano, a nitro, and a halogen;

wherein the term ‘substituted’ in the expression ‘substituted or unsubstituted’ used in Chemical Formulas A, B, and F to H means having at least one substituent selected from the group consisting of a deuterium atom, a cyano, a halogen, a hydroxy, a nitro, an alkyl of 1 to 24 carbon atoms, a halogenated alkyl of 1 to 24 carbon atoms, an alkenyl of 2 to 24 carbon atoms, an alkynyl of 2 to 24 carbon atoms, a heteroalkyl of 1 to 24 carbon atoms, an aryl of 6 to 24 carbon atoms, an arylalkyl of 7 to 24 carbon atoms, a heteroaryl of 2 to 24 carbon atoms or a heteroarylalkyl of 2 to 24 carbon atoms, an alkoxy of 1 to 24 carbon atoms, an alkylamino of 1 to 24 carbon atoms, an arylamino of 6 to 24 carbon atoms, a hetero arylamino of 2 to 24 carbon atoms, an alkylsilyl of 1 to 24 carbon atoms, an arylsilyl of 6 to 24 carbon atoms, and an aryloxy of 6 to 24 carbon atoms.

2. The organic light-emitting diode of claim 1 , wherein A 1 , A 2 , E, and F in Chemical Formula A or B may be the same or different and are each independently substituted or unsubstituted aromatic hydrocarbon rings of 6 to 50 carbon atoms.

3. The organic light-emitting diode of claim 2 , wherein the substituted or unsubstituted aromatic hydrocarbon rings of 6 to 50 carbon atoms in Chemical Formula A or B may be the same or different and are each independently selected from among compounds represented by Structural Formulas 10 to 21:

wherein

“-*” denotes a bonding site for forming a 5-membered ring bearing the carbon atom connected to the substituents R 1 and R 2 or a bonding site for forming a 5-membered ring bearing M of Structural Formula Q 1 and Q 2 ;

when one of the aromatic hydrocarbon rings of [Structural Formula 10] to [Structural Formula 21] for A 1 or A 2 is bonded to Structural Formula Q 1 or Structural Formula Q 2 , two adjacent carbon atoms of the aromatic hydrocarbon ring occupy respective positions * of Structural Formula Q 1 or Q 2 to form a fused ring;

R's are the same as defined above for R 1 and R 2 , and m is an integer of 1 to 8, with the proviso that when m is 2 or greater or when two or more R's exist, the corresponding R's may be the same or different.

4. The organic light-emitting diode of claim 1 , wherein the first electrode is an anode and the second electrode is a cathode, with the interposition of a hole transport layer between the cathode and the light-emitting layer and an electron transport layer between the electron density control layer and the anode.

5. The organic light-emitting diode of claim 1 , wherein R 18 in Chemical Formula F is a substituted or unsubstituted aryl of 6 to 18 carbon atoms.

6. The organic light-emitting diode of claim 1 , wherein at least one of Z 1 and Z 2 in Chemical Formula G is represented by the following Structural Formula B:

* L 19 o Cz  [Structural Formula B]

wherein, Cz is a substituted or unsubstituted carbazole,

L 13 is selected from among a single bond, a substituted or unsubstituted arylene of 6 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene of 3 to 50 carbon atoms, and

o is an integer of 0 to 2.

7. The organic light-emitting diode of claim 1 , wherein HAr in Structural Formula A is a substituent represented by the following Structural Formula C:

wherein,

X 11 to X 18 may be the same or different and are each independently N or CR 31 , with the proviso that one of them may be a carbon atom linked to the substituent L 13 in Structural Formula A via a single bond and that when two or more CR 31 's exist, they are the same or different,

Y 3 is O or S, and

R 31 is as defined for R′ in Chemical Formula G.

8. The organic light-emitting diode of claim 1 , wherein at least two of X 1 to X 3 in Chemical Formula G] are N.

9. The organic light-emitting diode of claim 1 , wherein, in Chemical Formula H, L 14 is a single bond or an aryl of 6 to 18 carbon atoms, and substituents Z 11 and Z 12 may be the same or different and are each independently a substituted or unsubstituted aryl of 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl of 2 to 20 carbon atoms, with the proviso that at least one of Z 11 and Z 12 is a substituted or unsubstituted heteroaryl of 3 to 20 carbon atoms.

10. The organic light-emitting diode of claim 1 , wherein the compound represented by Chemical Formula H is one of the compounds represented by Chemical Formulas H-1 to H-4:

wherein,

substituents R 41 to R 48 and R 51 to R 63 may be the same or different and are each independently selected from among a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl of 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl of 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy of 2 to 30 carbon atoms, a substituted or unsubstituted aryloxy of 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy of 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy of 6 to 30 carbon atoms, a substituted or unsubstituted alkylamine of 1 to 30 carbon atoms, a substituted or unsubstituted arylamine of 6 to 30 carbon atoms, a substituted or unsubstituted aryl of 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl of 2 to 50 carbon atoms bearing O, N, or S as a heteroatom, a cyano, a nitro, a halogen, a substituted or unsubstituted silyl of 1 to 30 carbon atoms, a substituted or unsubstituted alkyl germanium of 1 to 30 carbon atoms, a substituted or unsubstituted alkyl boron of 1 to 30 carbon atoms, a substituted or unsubstituted alkyl aluminum of 1 to 30 carbon atoms, a carbonyl, a phosphoryl, an amino, a thiol, a hydroxy, a selenium, a tellurium, an amide, an ether, and an ester,

substituents Ar 15 to Ar 18 are each a substituted or unsubstituted aryl of 6 to 50 carbon atoms or a substituted or unsubstituted heteroaryl of 2 to 50 carbon atoms;

linkers L 15 to L 16 are each independently selected from among a single bond, a substituted or unsubstituted alkylene of 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene of 3 to 30 carbon atoms, a substituted or unsubstituted arylene of 6 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene of 3 to 50 carbon atoms;

R 52 and R 53 , or two adjacent substituents of R 54 to R 57 in Chemical Formula H-2 are respectively single bonds involved in forming a 5-membered ring as a fused ring with the carbon atom to which substituents R 62 and R 63 in Q 3 are both bonded,

two adjacent substituents of R 51 to R 53 or of R 54 to R 57 in Chemical Formula H-4 are respectively single bonds involved in forming a 5-membered ring as a fused ring with the carbon atom to which substituents R 62 and R 63 in Q 4 are both bonded,

R 62 and R 63 may be linked to each other to form a ring,

wherein the term ‘substituted’ in the expression ‘substituted or unsubstituted’ means having at least one substituent selected from the group consisting of a deuterium atom, a cyano, a halogen, a hydroxy, a nitro, an alkyl of 1 to 24 carbon atoms, a halogenated alkyl of 1 to 24 carbon atoms, an alkenyl of 1 to 24 carbon atoms, an alkynyl of 1 to 24 carbon atoms, a heteroalkyl of 1 to 24 carbon atoms, an aryl of 6 to 24 carbon atoms, an arylalkyl of 7 to 24 carbon atoms, a heteroaryl of 2 to 24 carbon atoms or a heteroarylalkyl of 2 to 24 carbon atoms, an alkoxy of 1 to 24 carbon atoms, an alkylamino of 1 to 24 carbon atoms, an arylamino of 6 to 24 carbon atoms, a hetero arylamino of 2 to 24 carbon atoms, an alkylsilyl of 1 to 24 carbon atoms, an arylsilyl of 6 to 24 carbon atoms, and an aryloxy of 6 to 24 carbon atoms.

11. The organic light-emitting diode of claim 1 , wherein the compound represented by Chemical Formula F is one selected from the group consisting of the following Compounds 1 to 30:

12. The organic light-emitting diode of claim 1 , wherein the compound represented by Chemical Formula G is one selected from the group consisting of the following Compounds 101 to 132:

13. The organic light-emitting diode of claim 1 , wherein the substituents Z 11 's in Chemical Formula H are each a substituted or unsubstituted aryl of 6 to 18 carbon atoms.

14. The organic light-emitting diode of claim 1 , wherein the compound, represented by Chemical Formulas H is one selected from the group consisting of the following Compounds 201 to 348:

15. The organic light-emitting diode of claim 1 , wherein the linkers L 1 to L 12 in Chemical Formulas A and B are each a single bond or any one selected from among the following Structural Formulas 22 to 30:

wherein each of the unsubstituted carbon atoms of the aromatic ring moiety is bound with a hydrogen atom or a deuterium atom.

16. The organic light-emitting diode of claim 1 , wherein the amine compound is one selected from among the compounds represented by the following Chemical Formulas 1 to 239:

17. The organic light-emitting diode of claim 1 , wherein the light-emitting layer includes a host and a dopant and the compound represented by Chemical Formula A or B is used as the dopant.

18. The organic light-emitting diode of claim 4 , comprising a hole injection layer between the anode and the hole transport layer and an electron injection layer between the electron transport layer and the cathode.

19. The organic light-emitting diode of claim 1 , wherein at least one of the layers is formed using a deposition process or a solution process.

20. The organic light-emitting diode of claim 1 , wherein the organic light-emitting diode is used for a device selected from among a flat display device; a flexible display device; a monochrome or white flat illumination device; and a monochrome or white flexible illumination device.