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Patent Analysis of

Organic electroluminescent materials and devices

Updated Time 12 June 2019

Patent Registration Data

Publication Number

US10003033

Application Number

US14/183100

Application Date

18 February 2014

Publication Date

19 June 2018

Current Assignee

UNIVERSAL DISPLAY CORPORATION

Original Assignee (Applicant)

UNIVERSAL DISPLAY CORPORATION

International Classification

H01L51/54,C09K11/06,H01L51/00,C07F15/00,H01L51/50

Cooperative Classification

H01L51/0085,C07F15/0033,C09K11/06,C09K2211/1029,C09K2211/1044

Inventor

BOUDREAULT, PIERRE-LUC T.,DYATKIN, ALEXEY BORISOVICH,XIA, CHUANJUN,YAMAMOTO, HITOSHI

Patent Images

This patent contains figures and images illustrating the invention and its embodiment.

US10003033 Organic electroluminescent materials devices 1 US10003033 Organic electroluminescent materials devices 2 US10003033 Organic electroluminescent materials devices 3
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Abstract

Compounds having the formula M(LA)x(LB)y(LC)z, devices containing the same, and formulations containing the same are described. The compounds include:

    • where M is a metal having an atomic number greater than 40; x is 1, or 2; y is 1, or 2; and z is 0, 1, or 2; where x+y+z is the oxidation state of the metal M, where X1, X2, X3, and X4 are C or N; where at least one of R1, R2, R3, and R4 has at least two C atoms; where RB represents di, tri, or tetra-substitution, and where two adjacent RB form a six-member carbocyclic or heterocyclic ring E fused to ring B; where, when ring E is heterocyclic, the only heteroatom is nitrogen; where ring E can be further substituted; and where (a) at least one of X1, X2, X3, and X4 is N, (b) ring E is heterocylic, or (c) both.

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Claims

1. A compound having a formula M(LA)x(LB)y(LC)z: wherein the ligand LA is wherein the ligand LB is wherein the ligand LC is wherein M is a metal having an atomic number greater than 40; wherein x is 1, or 2; wherein y is 1, or 2; wherein z is 0, 1, or 2; wherein x+y+z is the oxidation state of the metal M; wherein X1, X2, X3, and X4 are independently C or N, with the proviso that at least two of X1, X2, X3, and X4 that are adjacent to each other are carbon; wherein R1, R2, R3, and R4 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; wherein each one of R1, R2, R3, and R4 has at least two C atoms; wherein R5 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein rings A, C, and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; wherein RA, RC, and RD each independently represent mono, di, tri, or tetra-substitution, or no substitution; wherein RB represents di, tri, or tetra-substitution, with the proviso that RB is attached only to those of X1, X2, X3, and X4 that are carbon; wherein two adjacent RB form a six-member carbocyclic or heterocyclic ring E fused to ring B; wherein, when ring E is heterocyclic, the only heteroatom is nitrogen; and wherein ring E can be further substituted;wherein (a) at least one of X1, X2, X3, and X4 is N,(b) ring E is heterocyclic, or(c) both; wherein each RA, RC, and RD, and any RB other than the two that form ring E, is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any adjacent substituents of RA, RC, and RD are optionally joined to form a fused ring.

2. The compound of claim 1, wherein M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu.

3. The compound of claim 1, wherein M is Ir.

4. The compound of claim 1, wherein ring A is benzene.

5. The compound of claim 1, wherein z is 1 or 2, ring C is benzene, and ring D is pyridine.

6. The compound of claim 1, wherein R5 is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, and combinations thereof.

7. The compound of claim 1, wherein R5 is hydrogen.

8. The compound of claim 1, wherein R1, R2, R3, and R4 are alkyl or cycloalkyl.

9. The compound of claim 1, wherein R1, R2, R3, and R4 are independently selected from the group consisting of ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclobutyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.

10. The compound of claim 1, wherein the compound is selected from the group consisting of: wherein X5, X6, X7, and X8 are C or N; wherein R7, and R8 each independently represent mono, di, tri, or tetra-substitution, or no substitution; wherein R6, R7, and R8 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein, in Formula III, X3, X4 or both are N, RB is attached to X3 only when X3 is carbon, and RB is attached to X4 only when X4 is carbon; and wherein n is 1 or 2.

11. The compound of claim 10, wherein R6, and R7 are independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, and combinations thereof.

12. The compound of claim 10, wherein R8 is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, halide, and combinations thereof.

13. The compound of claim 10, wherein n is 2.

14. The compound of claim 1, wherein the compound is selected from the group consisting of: wherein R7, and R8 each independently represent mono, di, tri, or tetra-substitution, or no substitution; wherein R6, R7, and R8 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein n is 1 or 2.

15. The compound of claim 1, wherein LA is selected from the group consisting of LA1 to LA270 listed below:

16. The compound of claim 15, wherein x=1 or 2, y=1 or 2, and z=0, and wherein LB is selected from the group consisting of LB1, LB2, LB5, LB7, LB9, LB10, and LB13 listed below:

17. The compound of claim 1, wherein LB is selected from the group consisting of LB1, LB2, LB5, LB7, LB9, LB10, and LB13 listed below:

18. The compound of claim 1, wherein the compound is selected from the group consisting of:

19. A first device comprising a first organic light emitting device, the first organic light emitting device comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having a formula M(LA)x(LB)y(LC)z: wherein the ligand LA is wherein the ligand LB is wherein the ligand LC is wherein M is a metal having an atomic number greater than 40; wherein x is 1, or 2; wherein y is 1, or 2; wherein z is 0, 1, or 2; wherein x+y+z is the oxidation state of the metal M; wherein X1, X2, X3, and X4 are independently C or N, with the proviso that at least two of X1, X2, X3, and X4 that are adjacent to each other are carbon; wherein R1, R2, R3, and R4 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; wherein each one of R1, R2, R3, and R4 has at least two C atoms; wherein R5 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein rings A, C, and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; wherein RA, RC, and RD each independently represent mono, di, tri, or tetra-substitution, or no substitution; wherein RB represents di, tri, or tetra-substitution, with the proviso that RB is attached only to those of X1, X2, X3, and X4 that are carbon; wherein two adjacent RB form a six-member carbocyclic or heterocyclic ring E fused to ring B; wherein, when ring E is heterocyclic, the only heteroatom is nitrogen; and wherein ring E can be further substituted;wherein (a) at least one of X1, X2, X3, and X4 is N,(b) ring E is heterocyclic, or(c) both; wherein each RA, RC, and RD, and any RB other than the two that form ring E, is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any adjacent substituents of RA, RC, and RD are optionally joined to form a fused ring.

20. A formulation comprising a compound having a formula M(LA)x(LB)y(LC)z: wherein the ligand LA is wherein the ligand LB is wherein the ligand LC is wherein M is a metal having an atomic number greater than 40; wherein x is 1, or 2; wherein y is 1, or 2; wherein z is 0, 1, or 2; wherein x+y+z is the oxidation state of the metal M; wherein X1, X2, X3, and X4 are independently C or N, with the proviso that at least two of X1, X2, X3, and X4 that are adjacent to each other are carbon; wherein R1, R2, R3, and R are independently selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; wherein each one of R1, R2, R3, and R4 has at least two C atoms; wherein R5 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein rings A, C, and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; wherein RA, RC, and RD each independently represent mono, di, tri, or tetra-substitution, or no substitution; wherein RB represents di, tri, or tetra-substitution, with the proviso that RB is attached only to those of X1, X2, X3, and X4 that are carbon; wherein two adjacent RB form a six-member carbocyclic or heterocyclic ring E fused to ring B; wherein, when ring E is heterocyclic, the only heteroatom is nitrogen; and wherein ring E can be further substituted;wherein (a) at least one of X1, X2, X3, and X4 is N,(b) ring E is heterocyclic, or(c) both; wherein each RA, RC, and RD, and any RB other than the two that form ring E, is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any adjacent substituents of RA, RC, and RD are optionally joined to form a fused ring.

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Claim Tree

  • 1
    1. A compound having a formula M(LA)x(LB)y(LC)z: wherein the ligand LA is wherein the ligand LB is wherein the ligand LC is wherein M is a metal having an atomic number greater than 40; wherein x is 1, or 2; wherein y is 1, or 2; wherein z is 0, 1, or 2; wherein x+y+z is the oxidation state of the metal M; wherein X1, X2, X3, and X4 are independently C or N, with the proviso that at least two of X1, X2, X3, and X4 that are adjacent to each other are carbon; wherein R1, R2, R3, and R4 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; wherein each one of R1, R2, R3, and R4 has at least two C atoms; wherein R5 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein rings A, C, and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; wherein RA, RC, and RD each independently represent mono, di, tri, or tetra-substitution, or no substitution; wherein RB represents di, tri, or tetra-substitution, with the proviso that RB is attached only to those of X1, X2, X3, and X4 that are carbon; wherein two adjacent RB form a six-member carbocyclic or heterocyclic ring E fused to ring B; wherein, when ring E is heterocyclic, the only heteroatom is nitrogen; and wherein ring E can be further substituted;wherein
    • (a) at least one of X1, X2, X3, and X4 is N,
    • (b) ring E is heterocyclic, or
    • (c) both; wherein each RA, RC, and RD, and any RB other than the two that form ring E, is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any adjacent substituents of RA, RC, and RD are optionally joined to form a fused ring.
    • 2. The compound of claim 1, wherein
      • M is selected from the group consisting of
    • 3. The compound of claim 1, wherein
      • M is Ir.
    • 4. The compound of claim 1, wherein
      • ring A is benzene.
    • 5. The compound of claim 1, wherein
      • z is 1 or 2, ring C is benzene, and ring D is pyridine.
    • 6. The compound of claim 1, wherein
      • R5 is selected from the group consisting of
    • 7. The compound of claim 1, wherein
      • R5 is hydrogen.
    • 8. The compound of claim 1, wherein
      • R1, R2, R3, and R4 are alkyl or cycloalkyl.
    • 9. The compound of claim 1, wherein
      • R1, R2, R3, and R4 are independently selected from the group consisting of
    • 10. The compound of claim 1, wherein
      • the compound is selected from the group consisting of:
    • 14. The compound of claim 1, wherein
      • the compound is selected from the group consisting of:
    • 15. The compound of claim 1, wherein
      • LA is selected from the group consisting of
    • 17. The compound of claim 1, wherein
      • LB is selected from the group consisting of
    • 18. The compound of claim 1, wherein
      • the compound is selected from the group consisting of
  • 19
    19. A first device comprising a first organic light emitting device, the first organic light emitting device comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having a formula M(LA)x(LB)y(LC)z: wherein the ligand LA is wherein the ligand LB is wherein the ligand LC is wherein M is a metal having an atomic number greater than 40; wherein x is 1, or 2; wherein y is 1, or 2; wherein z is 0, 1, or 2; wherein x+y+z is the oxidation state of the metal M; wherein X1, X2, X3, and X4 are independently C or N, with the proviso that at least two of X1, X2, X3, and X4 that are adjacent to each other are carbon; wherein R1, R2, R3, and R4 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; wherein each one of R1, R2, R3, and R4 has at least two C atoms; wherein R5 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein rings A, C, and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; wherein RA, RC, and RD each independently represent mono, di, tri, or tetra-substitution, or no substitution; wherein RB represents di, tri, or tetra-substitution, with the proviso that RB is attached only to those of X1, X2, X3, and X4 that are carbon; wherein two adjacent RB form a six-member carbocyclic or heterocyclic ring E fused to ring B; wherein, when ring E is heterocyclic, the only heteroatom is nitrogen; and wherein ring E can be further substituted;wherein
    • (a) at least one of X1, X2, X3, and X4 is N,
    • (b) ring E is heterocyclic, or
    • (c) both; wherein each RA, RC, and RD, and any RB other than the two that form ring E, is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any adjacent substituents of RA, RC, and RD are optionally joined to form a fused ring.
  • 20
    20. A formulation comprising a compound having a formula M(LA)x(LB)y(LC)z: wherein the ligand LA is wherein the ligand LB is wherein the ligand LC is wherein M is a metal having an atomic number greater than 40; wherein x is 1, or 2; wherein y is 1, or 2; wherein z is 0, 1, or 2; wherein x+y+z is the oxidation state of the metal M; wherein X1, X2, X3, and X4 are independently C or N, with the proviso that at least two of X1, X2, X3, and X4 that are adjacent to each other are carbon; wherein R1, R2, R3, and R are independently selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; wherein each one of R1, R2, R3, and R4 has at least two C atoms; wherein R5 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein rings A, C, and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; wherein RA, RC, and RD each independently represent mono, di, tri, or tetra-substitution, or no substitution; wherein RB represents di, tri, or tetra-substitution, with the proviso that RB is attached only to those of X1, X2, X3, and X4 that are carbon; wherein two adjacent RB form a six-member carbocyclic or heterocyclic ring E fused to ring B; wherein, when ring E is heterocyclic, the only heteroatom is nitrogen; and wherein ring E can be further substituted;wherein
    • (a) at least one of X1, X2, X3, and X4 is N,
    • (b) ring E is heterocyclic, or
    • (c) both; wherein each RA, RC, and RD, and any RB other than the two that form ring E, is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any adjacent substituents of RA, RC, and RD are optionally joined to form a fused ring.
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Description

PARTIES TO A JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.

FIELD OF THE INVENTION

The present invention relates to compounds for use as emitters and devices, such as organic light emitting diodes, including the same.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.

One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)3, which has the following structure:

In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

SUMMARY OF THE INVENTION

According to one embodiment, a compound having a formula M(LA)x(LB)y(LC)z is disclosed. In the formula, the ligand LA is

the ligand LB is

and the ligand LC is

where:

M is a metal having an atomic number greater than 40;

x is 1, or 2;

y is 1, or 2;

z is 0, 1, or 2;

x+y+z is the oxidation state of the metal M;

X1, X2, X3, and X4 are C or N;

R1, R2, R3, and R4 are independently selected from group consisting of alkyl, cycloalkyl, aryl, and heteroaryl;

at least one of R1, R2, R3, and R4 has at least two C atoms;

R5 is selected from group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

rings A, C, and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring;

RA, RC, and RD each independently represent mono, di, tri, or tetra-substitution, or no substitution;

RB represents di, tri, or tetra-substitution;

two adjacent RB form a six-member carbocyclic or heterocyclic ring E fused to ring B; wherein, when ring E is heterocyclic, the only heteroatom is nitrogen; and wherein ring E can be further substituted;

each of RA, RB, RC, and RD are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

any adjacent substitutents of RA, RB, RC, and RD are optionally joined to form a fused ring; and where (a) at least one of X1, X2, X3, and X4 is N, (b) ring E is heterocylic, or (c) both.

According to another aspect of the disclosure, a first device is also provided. The first device includes a first organic light emitting device, that includes an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer can include a compound according to the formula M(LA)x(LB)y(LC)z, and the variations thereof as described herein.

In yet another aspect of the present disclosure, a formulation that comprises a compound according to the formula M(LA)x(LB)y(LC)z, and the variations thereof as described herein, are provided. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

FIG. 3 shows Ligands LA, LB and LC of the compounds described herein.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton.” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75. No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

The term “halo” or “halogen” as used herein includes fluorine, chlorine, bromine, and iodine.

The term “alkyl” as used herein contemplates both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, the alkyl group may be optionally substituted.

The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.

The term “alkenyl” as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted.

The term “alkynyl” as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.

The terms “aralkyl” or “arylalkyl” as used herein are used interchangeably and contemplate an alkyl group that has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted.

The term “heterocyclic group” as used herein contemplates non-aromatic cyclic radicals. Preferred heterocyclic groups are those containing 3 or 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. Additionally, the heterocyclic group may be optionally substituted.

The term “aryl” or “aromatic group” as used herein contemplates single-ring groups and polycyclic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Additionally, the aryl group may be optionally substituted.

The term “heteroaryl” as used herein contemplates single-ring hetero-aromatic groups that may include from one to three heteroatoms, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like. The term heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Additionally, the heteroaryl group may be optionally substituted.

The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl may be optionally substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant position, such as carbon. Thus, for example, where R1 is mono-substituted, then one R1 must be other than H. Similarly, where R1 is di-substituted, then two of R1 must be other than H. Similarly, where R1 is unsubstituted, R1 is hydrogen for all available positions.

The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.

It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.

The claimed compounds are organometallic complexes that include both quinazoline-based ligands and ligands formed from branched acetylacetone (acac) derivatives. The combination of these ligands allows red phosphorescent materials with good external quantum efficiency (EQE), color, and lifetime.

According to one embodiment, a compound having the formula M(LA)x(LB)y(LC)z is disclosed. In the formula M(LA)x(LB)y(LC)z, ligand LA is

ligand LB is

and ligand LC is

where:

M is a metal having an atomic number greater than 40;

x is 1, or 2;

y is 1, or 2;

z is 0, 1, or 2;

x+y+z is the oxidation state of the metal M;

X1, X2, X3, and X4 are C or N;

R1, R2, R3, and R4 are independently selected from group consisting of alkyl, cycloalkyl, aryl, and heteroaryl;

at least one of R1, R2, R3, and R4 has at least two C atoms;

R5 is selected from group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

rings A, C, and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring;

RA, RC, and RD each independently represent mono, di, tri, or tetra-substitution, or no substitution;

RB represents di, tri, or tetra-substitution;

two adjacent RB form a six-member carbocyclic or heterocyclic ring E fused to ring B; wherein, when ring E is heterocyclic, the only heteroatom is nitrogen; and wherein ring E can be further substituted;

each of RA, RB, RC, and RD are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

any adjacent substitutents of RA, RB, RC, and RD are optionally joined to form a fused ring; and where (a) at least one of X1, X2, X3, and X4 is N, (b) ring E is heterocylic, or (c) both.

In some embodiments, at least one of R1, R2, R3, and R4 has at least three C atoms, while in other embodiments at least one of R1, R2, R3, and R4 has at least four C atoms. In some embodiments, at least one of R1, R2, R3, and R4 is a branched alkyl.

In some embodiments, the M can be selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu.

In some embodiments, ring A is benzene. In some embodiments, ring C is benzene, and ring D is pyridine.

In some embodiments, R5 is selected from group consisting of hydrogen, deuterium, alkyl, cycloalkyl, and combinations thereof. In some embodiments, R5 is hydrogen.

In some embodiments, R1, R2, R3, and R4 are alkyl or cycloalkyl. In some more specific embodiments, R1, R2, R3, and R4 are independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclobutyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.

In some embodiments, the compound is selected from the group consisting of:

wherein X5, X6, X7, and X8 are C or N;

wherein R7, and R8 each independently represent mono, di, tri, or tetra-substitution, or no substitution;

wherein R6, R7, and R8 are independently selected from group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

wherein n is 1 or 2.

In some embodiments, n is 2. In some embodiments, at least one of X5, X6, X7, and X8 is N. In other embodiments, at least two of X5, X6, X7, and X8 are N.

In some embodiments, R6 and R7 are independently selected from group consisting of hydrogen, deuterium, alkyl, cycloalkyl, and combinations thereof. In some embodiments, R6 is branched alkyl or cycloalkyl. In some embodiments, R7 is at least monosubstituted and is branched alkyl or cycloalkyl.

In some embodiments, R8 is selected from group consisting of hydrogen, deuterium, alkyl, cycloalkyl, halide, and combinations thereof. In some embodiments, R8 comprises at least one halide, at least one alkyl, or both. In some embodiments, R8 comprises at least one halide and at least two alkyls.

In some embodiments, the compound is selected from the group consisting of:

wherein R7, and R8 each independently represent mono, di, tri, or tetra-substitution, or no substitution;

wherein R6, R7, and R8 are independently selected from group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

wherein n is 1 or 2.

In some embodiments, LA is selected from the group consisting of LA1 to LA270 listed below:

Some embodiments are drawn to compounds of formula M(LA)x(LB)y(LC)z, where x=1 or 2, y=1 or 2, and z=0.

In some embodiments, LB is selected from the group consisting of LB1-LB13 listed below:

In some embodiments, z=0, x=1 or 2, y=1 or 2, and the compound having the formula of Ir(LA)x(LB)y is selected from the group consisting of Compound 1 to Compound 3510 listed in the table below:


Compound
Number
LA
LB
1
LA1
LB1
2
LA2
LB1
3
LA3
LB1
4
LA4
LB1
5
LA5
LB1
6
LA6
LB1
7
LA7
LB1
8
LA8
LB1
9
LA9
LB1
10
LA10
LB1
11
LA11
LB1
12
LA12
LB1
13
LA13
LB1
14
LA14
LB1
15
LA15
LB1
16
LA16
LB1
17
LA17
LB1
18
LA18
LB1
19
LA19
LB1
20
LA20
LB1
21
LA21
LB1
22
LA22
LB1
23
LA23
LB1
24
LA24
LB1
25
LA25
LB1
26
LA26
LB1
27
LA27
LB1
28
LA28
LB1
29
LA29
LB1
30
LA30
LB1
31
LA31
LB1
32
LA32
LB1
33
LA33
LB1
34
LA34
LB1
35
LA35
LB1
36
LA36
LB1
37
LA37
LB1
38
LA38
LB1
39
LA39
LB1
40
LA40
LB1
41
LA41
LB1
42
LA42
LB1
43
LA43
LB1
44
LA44
LB1
45
LA45
LB1
46
LA46
LB1
47
LA47
LB1
48
LA48
LB1
49
LA49
LB1
50
LA50
LB1
51
LA51
LB1
52
LA52
LB1
53
LA53
LB1
54
LA54
LB1
55
LA55
LB1
56
LA56
LB1
57
LA57
LB1
58
LA58
LB1
59
LA59
LB1
60
LA60
LB1
61
LA61
LB1
62
LA62
LB1
63
LA63
LB1
64
LA64
LB1
65
LA65
LB1
66
LA66
LB1
67
LA67
LB1
68
LA68
LB1
69
LA69
LB1
70
LA70
LB1
71
LA71
LB1
72
LA72
LB1
73
LA73
LB1
74
LA74
LB1
75
LA75
LB1
76
LA76
LB1
77
LA77
LB1
78
LA78
LB1
79
LA79
LB1
80
LA80
LB1
81
LA81
LB1
82
LA82
LB1
83
LA83
LB1
84
LA84
LB1
85
LA85
LB1
86
LA86
LB1
87
LA87
LB1
88
LA88
LB1
89
LA89
LB1
90
LA90
LB1
91
LA91
LB1
92
LA92
LB1
93
LA93
LB1
94
LA94
LB1
95
LA95
LB1
96
LA96
LB1
97
LA97
LB1
98
LA98
LB1
99
LA99
LB1
100
LA100
LB1
101
LA101
LB1
102
LA102
LB1
103
LA103
LB1
104
LA104
LB1
105
LA105
LB1
106
LA106
LB1
107
LA107
LB1
108
LA108
LB1
109
LA109
LB1
110
LA110
LB1
111
LA111
LB1
112
LA112
LB1
113
LA113
LB1
114
LA114
LB1
115
LA115
LB1
116
LA116
LB1
117
LA117
LB1
118
LA118
LB1
119
LA119
LB1
120
LA120
LB1
121
LA121
LB1
122
LA122
LB1
123
LA123
LB1
124
LA124
LB1
125
LA125
LB1
126
LA126
LB1
127
LA127
LB1
128
LA128
LB1
129
LA129
LB1
130
LA130
LB1
131
LA131
LB1
132
LA132
LB1
133
LA133
LB1
134
LA134
LB1
135
LA135
LB1
136
LA136
LB1
137
LA137
LB1
138
LA138
LB1
139
LA139
LB1
140
LA140
LB1
141
LA141
LB1
142
LA142
LB1
143
LA143
LB1
144
LA144
LB1
145
LA145
LB1
146
LA146
LB1
147
LA147
LB1
148
LA148
LB1
149
LA149
LB1
150
LA150
LB1
151
LA151
LB1
152
LA152
LB1
153
LA153
LB1
154
LA154
LB1
155
LA155
LB1
156
LA156
LB1
157
LA157
LB1
158
LA158
LB1
159
LA159
LB1
160
LA160
LB1
161
LA161
LB1
162
LA162
LB1
163
LA163
LB1
164
LA164
LB1
165
LA165
LB1
166
LA166
LB1
167
LA167
LB1
168
LA168
LB1
169
LA169
LB1
170
LA170
LB1
171
LA171
LB1
172
LA172
LB1
173
LA173
LB1
174
LA174
LB1
175
LA175
LB1
176
LA176
LB1
177
LA177
LB1
178
LA178
LB1
179
LA179
LB1
180
LA180
LB1
181
LA181
LB1
182
LA182
LB1
183
LA183
LB1
184
LA184
LB1
185
LA185
LB1
186
LA186
LB1
187
LA187
LB1
188
LA188
LB1
189
LA189
LB1
190
LA190
LB1
191
LA191
LB1
192
LA192
LB1
193
LA193
LB1
194
LA194
LB1
195
LA195
LB1
196
LA196
LB1
197
LA197
LB1
198
LA198
LB1
199
LA199
LB1
200
LA200
LB1
201
LA201
LB1
202
LA202
LB1
203
LA203
LB1
204
LA204
LB1
205
LA205
LB1
206
LA206
LB1
207
LA207
LB1
208
LA208
LB1
209
LA209
LB1
210
LA210
LB1
211
LA211
LB1
212
LA212
LB1
213
LA213
LB1
214
LA214
LB1
215
LA215
LB1
216
LA216
LB1
217
LA217
LB1
218
LA218
LB1
219
LA219
LB1
220
LA220
LB1
221
LA221
LB1
222
LA222
LB1
223
LA223
LB1
224
LA224
LB1
225
LA225
LB1
226
LA226
LB1
227
LA227
LB1
228
LA228
LB1
229
LA229
LB1
230
LA230
LB1
231
LA231
LB1
232
LA232
LB1
233
LA233
LB1
234
LA234
LB1
235
LA235
LB1
236
LA236
LB1
237
LA237
LB1
238
LA238
LB1
239
LA239
LB1
240
LA240
LB1
241
LA241
LB1
242
LA242
LB1
243
LA243
LB1
244
LA244
LB1
245
LA245
LB1
246
LA246
LB1
247
LA247
LB1
248
LA248
LB1
249
LA249
LB1
250
LA250
LB1
251
LA251
LB1
252
LA252
LB1
253
LA253
LB1
254
LA254
LB1
255
LA255
LB1
256
LA256
LB1
257
LA257
LB1
258
LA258
LB1
259
LA259
LB1
260
LA260
LB1
261
LA261
LB1
262
LA262
LB1
263
LA263
LB1
264
LA264
LB1
265
LA265
LB1
266
LA266
LB1
267
LA267
LB1
268
LA268
LB1
269
LA269
LB1
270
LA270
LB1
271
LA1
LB2
272
LA2
LB2
273
LA3
LB2
274
LA4
LB2
275
LA5
LB2
276
LA6
LB2
277
LA7
LB2
278
LA8
LB2
279
LA9
LB2
280
LA10
LB2
281
LA11
LB2
282
LA12
LB2
283
LA13
LB2
284
LA14
LB2
285
LA15
LB2
286
LA16
LB2
287
LA17
LB2
288
LA18
LB2
289
LA19
LB2
290
LA20
LB2
291
LA21
LB2
292
LA22
LB2
293
LA23
LB2
294
LA24
LB2
295
LA25
LB2
296
LA26
LB2
297
LA27
LB2
298
LA28
LB2
299
LA29
LB2
300
LA30
LB2
301
LA31
LB2
302
LA32
LB2
303
LA33
LB2
304
LA34
LB2
305
LA35
LB2
306
LA36
LB2
307
LA37
LB2
308
LA38
LB2
309
LA39
LB2
310
LA40
LB2
311
LA41
LB2
312
LA42
LB2
313
LA43
LB2
314
LA44
LB2
315
LA45
LB2
316
LA46
LB2
317
LA47
LB2
318
LA48
LB2
319
LA49
LB2
320
LA50
LB2
321
LA51
LB2
322
LA52
LB2
323
LA53
LB2
324
LA54
LB2
325
LA55
LB2
326
LA56
LB2
327
LA57
LB2
328
LA58
LB2
329
LA59
LB2
330
LA60
LB2
331
LA61
LB2
332
LA62
LB2
333
LA63
LB2
334
LA64
LB2
335
LA65
LB2
336
LA66
LB2
337
LA67
LB2
338
LA68
LB2
339
LA69
LB2
340
LA70
LB2
341
LA71
LB2
342
LA72
LB2
343
LA73
LB2
344
LA74
LB2
345
LA75
LB2
346
LA76
LB2
347
LA77
LB2
348
LA78
LB2
349
LA79
LB2
350
LA80
LB2
351
LA81
LB2
352
LA82
LB2
353
LA83
LB2
354
LA84
LB2
355
LA85
LB2
356
LA86
LB2
357
LA87
LB2
358
LA88
LB2
359
LA89
LB2
360
LA90
LB2
361
LA91
LB2
362
LA92
LB2
363
LA93
LB2
364
LA94
LB2
365
LA95
LB2
366
LA96
LB2
367
LA97
LB2
368
LA98
LB2
369
LA99
LB2
370
LA100
LB2
371
LA101
LB2
372
LA102
LB2
373
LA103
LB2
374
LA104
LB2
375
LA105
LB2
376
LA106
LB2
377
LA107
LB2
378
LA108
LB2
379
LA109
LB2
380
LA110
LB2
381
LA111
LB2
382
LA112
LB2
383
LA113
LB2
384
LA114
LB2
385
LA115
LB2
386
LA116
LB2
387
LA117
LB2
388
LA118
LB2
389
LA119
LB2
390
LA120
LB2
391
LA121
LB2
392
LA122
LB2
393
LA123
LB2
394
LA124
LB2
395
LA125
LB2
396
LA126
LB2
397
LA127
LB2
398
LA128
LB2
399
LA129
LB2
400
LA130
LB2
401
LA131
LB2
402
LA132
LB2
403
LA133
LB2
404
LA134
LB2
405
LA135
LB2
406
LA136
LB2
407
LA137
LB2
408
LA138
LB2
409
LA139
LB2
410
LA140
LB2
411
LA141
LB2
412
LA142
LB2
413
LA143
LB2
414
LA144
LB2
415
LA145
LB2
416
LA146
LB2
417
LA147
LB2
418
LA148
LB2
419
LA149
LB2
420
LA150
LB2
421
LA151
LB2
422
LA152
LB2
423
LA153
LB2
424
LA154
LB2
425
LA155
LB2
426
LA156
LB2
427
LA157
LB2
428
LA158
LB2
429
LA159
LB2
430
LA160
LB2
431
LA161
LB2
432
LA162
LB2
433
LA163
LB2
434
LA164
LB2
435
LA165
LB2
436
LA166
LB2
437
LA167
LB2
438
LA168
LB2
439
LA169
LB2
440
LA170
LB2
441
LA171
LB2
442
LA172
LB2
443
LA173
LB2
444
LA174
LB2
445
LA175
LB2
446
LA176
LB2
447
LA177
LB2
448
LA178
LB2
449
LA179
LB2
450
LA180
LB2
451
LA181
LB2
452
LA182
LB2
453
LA183
LB2
454
LA184
LB2
455
LA185
LB2
456
LA186
LB2
457
LA187
LB2
458
LA188
LB2
459
LA189
LB2
460
LA190
LB2
461
LA191
LB2
462
LA192
LB2
463
LA193
LB2
464
LA194
LB2
465
LA195
LB2
466
LA196
LB2
467
LA197
LB2
468
LA198
LB2
469
LA199
LB2
470
LA200
LB2
471
LA201
LB2
472
LA202
LB2
473
LA203
LB2
474
LA204
LB2
475
LA205
LB2
476
LA206
LB2
477
LA207
LB2
478
LA208
LB2
479
LA209
LB2
480
LA210
LB2
481
LA211
LB2
482
LA212
LB2
483
LA213
LB2
484
LA214
LB2
485
LA215
LB2
486
LA216
LB2
487
LA217
LB2
488
LA218
LB2
489
LA219
LB2
490
LA220
LB2
491
LA221
LB2
492
LA222
LB2
493
LA223
LB2
494
LA224
LB2
495
LA225
LB2
496
LA226
LB2
497
LA227
LB2
498
LA228
LB2
499
LA229
LB2
500
LA230
LB2
501
LA231
LB2
502
LA232
LB2
503
LA233
LB2
504
LA234
LB2
505
LA235
LB2
506
LA236
LB2
507
LA237
LB2
508
LA238
LB2
509
LA239
LB2
510
LA240
LB2
511
LA241
LB2
512
LA242
LB2
513
LA243
LB2
514
LA244
LB2
515
LA245
LB2
516
LA246
LB2
517
LA247
LB2
518
LA248
LB2
519
LA249
LB2
520
LA250
LB2
521
LA251
LB2
522
LA252
LB2
523
LA253
LB2
524
LA254
LB2
525
LA255
LB2
526
LA256
LB2
527
LA257
LB2
528
LA258
LB2
529
LA259
LB2
530
LA260
LB2
531
LA261
LB2
532
LA262
LB2
533
LA263
LB2
534
LA264
LB2
535
LA265
LB2
536
LA266
LB2
537
LA267
LB2
538
LA268
LB2
539
LA269
LB2
540
LA270
LB2
541
LA1
LB3
542
LA2
LB3
543
LA3
LB3
544
LA4
LB3
545
LA5
LB3
546
LA6
LB3
547
LA7
LB3
548
LA8
LB3
549
LA9
LB3
550
LA10
LB3
551
LA11
LB3
552
LA12
LB3
553
LA13
LB3
554
LA14
LB3
555
LA15
LB3
556
LA16
LB3
557
LA17
LB3
558
LA18
LB3
559
LA19
LB3
560
LA20
LB3
561
LA21
LB3
562
LA22
LB3
563
LA23
LB3
564
LA24
LB3
565
LA25
LB3
566
LA26
LB3
567
LA27
LB3
568
LA28
LB3
569
LA29
LB3
570
LA30
LB3
571
LA31
LB3
572
LA32
LB3
573
LA33
LB3
574
LA34
LB3
575
LA35
LB3
576
LA36
LB3
577
LA37
LB3
578
LA38
LB3
579
LA39
LB3
580
LA40
LB3
581
LA41
LB3
582
LA42
LB3
583
LA43
LB3
584
LA44
LB3
585
LA45
LB3
586
LA46
LB3
587
LA47
LB3
588
LA48
LB3
589
LA49
LB3
590
LA50
LB3
591
LA51
LB3
592
LA52
LB3
593
LA53
LB3
594
LA54
LB3
595
LA55
LB3
596
LA56
LB3
597
LA57
LB3
598
LA58
LB3
599
LA59
LB3
600
LA60
LB3
601
LA61
LB3
602
LA62
LB3
603
LA63
LB3
604
LA64
LB3
605
LA65
LB3
606
LA66
LB3
607
LA67
LB3
608
LA68
LB3
609
LA69
LB3
610
LA70
LB3
611
LA71
LB3
612
LA72
LB3
613
LA73
LB3
614
LA74
LB3
615
LA75
LB3
616
LA76
LB3
617
LA77
LB3
618
LA78
LB3
619
LA79
LB3
620
LA80
LB3
621
LA81
LB3
622
LA82
LB3
623
LA83
LB3
624
LA84
LB3
625
LA85
LB3
626
LA86
LB3
627
LA87
LB3
628
LA88
LB3
629
LA89
LB3
630
LA90
LB3
631
LA91
LB3
632
LA92
LB3
633
LA93
LB3
634
LA94
LB3
635
LA95
LB3
636
LA96
LB3
637
LA97
LB3
638
LA98
LB3
639
LA99
LB3
640
LA100
LB3
641
LA101
LB3
642
LA102
LB3
643
LA103
LB3
644
LA104
LB3
645
LA105
LB3
646
LA106
LB3
647
LA107
LB3
648
LA108
LB3
649
LA109
LB3
650
LA110
LB3
651
LA111
LB3
652
LA112
LB3
653
LA113
LB3
654
LA114
LB3
655
LA115
LB3
656
LA116
LB3
657
LA117
LB3
658
LA118
LB3
659
LA119
LB3
660
LA120
LB3
661
LA121
LB3
662
LA122
LB3
663
LA123
LB3
664
LA124
LB3
665
LA125
LB3
666
LA126
LB3
667
LA127
LB3
668
LA128
LB3
669
LA129
LB3
670
LA130
LB3
671
LA131
LB3
672
LA132
LB3
673
LA133
LB3
674
LA134
LB3
675
LA135
LB3
676
LA136
LB3
677
LA137
LB3
678
LA138
LB3
679
LA139
LB3
680
LA140
LB3
681
LA141
LB3
682
LA142
LB3
683
LA143
LB3
684
LA144
LB3
685
LA145
LB3
686
LA146
LB3
687
LA147
LB3
688
LA148
LB3
689
LA149
LB3
690
LA150
LB3
691
LA151
LB3
692
LA152
LB3
693
LA153
LB3
694
LA154
LB3
695
LA155
LB3
696
LA156
LB3
697
LA157
LB3
698
LA158
LB3
699
LA159
LB3
700
LA160
LB3
701
LA161
LB3
702
LA162
LB3
703
LA163
LB3
704
LA164
LB3
705
LA165
LB3
706
LA166
LB3
707
LA167
LB3
708
LA168
LB3
709
LA169
LB3
710
LA170
LB3
711
LA171
LB3
712
LA172
LB3
713
LA173
LB3
714
LA174
LB3
715
LA175
LB3
716
LA176
LB3
717
LA177
LB3
718
LA178
LB3
719
LA179
LB3
720
LA180
LB3
721
LA181
LB3
722
LA182
LB3
723
LA183
LB3
724
LA184
LB3
725
LA185
LB3
726
LA186
LB3
727
LA187
LB3
728
LA188
LB3
729
LA189
LB3
730
LA190
LB3
731
LA191
LB3
732
LA192
LB3
733
LA193
LB3
734
LA194
LB3
735
LA195
LB3
736
LA196
LB3
737
LA197
LB3
738
LA198
LB3
739
LA199
LB3
740
LA200
LB3
741
LA201
LB3
742
LA202
LB3
743
LA203
LB3
744
LA204
LB3
745
LA205
LB3
746
LA206
LB3
747
LA207
LB3
748
LA208
LB3
749
LA209
LB3
750
LA210
LB3
751
LA211
LB3
752
LA212
LB3
753
LA213
LB3
754
LA214
LB3
755
LA215
LB3
756
LA216
LB3
757
LA217
LB3
758
LA218
LB3
759
LA219
LB3
760
LA220
LB3
761
LA221
LB3
762
LA222
LB3
763
LA223
LB3
764
LA224
LB3
765
LA225
LB3
766
LA226
LB3
767
LA227
LB3
768
LA228
LB3
769
LA229
LB3
770
LA230
LB3
771
LA231
LB3
772
LA232
LB3
773
LA233
LB3
774
LA234
LB3
775
LA235
LB3
776
LA236
LB3
777
LA237
LB3
778
LA238
LB3
779
LA239
LB3
780
LA240
LB3
781
LA241
LB3
782
LA242
LB3
783
LA243
LB3
784
LA244
LB3
785
LA245
LB3
786
LA246
LB3
787
LA247
LB3
788
LA248
LB3
789
LA249
LB3
790
LA250
LB3
791
LA251
LB3
792
LA252
LB3
793
LA253
LB3
794
LA254
LB3
795
LA255
LB3
796
LA256
LB3
797
LA257
LB3
798
LA258
LB3
799
LA259
LB3
800
LA260
LB3
801
LA261
LB3
802
LA262
LB3
803
LA263
LB3
804
LA264
LB3
805
LA265
LB3
806
LA266
LB3
807
LA267
LB3
808
LA268
LB3
809
LA269
LB3
810
LA270
LB3
811
LA1
LB4
812
LA2
LB4
813
LA3
LB4
814
LA4
LB4
815
LA5
LB4
816
LA6
LB4
817
LA7
LB4
818
LA8
LB4
819
LA9
LB4
820
LA10
LB4
821
LA11
LB4
822
LA12
LB4
823
LA13
LB4
824
LA14
LB4
825
LA15
LB4
826
LA16
LB4
827
LA17
LB4
828
LA18
LB4
829
LA19
LB4
830
LA20
LB4
831
LA21
LB4
832
LA22
LB4
833
LA23
LB4
834
LA24
LB4
835
LA25
LB4
836
LA26
LB4
837
LA27
LB4
838
LA28
LB4
839
LA29
LB4
840
LA30
LB4
841
LA31
LB4
842
LA32
LB4
843
LA33
LB4
844
LA34
LB4
845
LA35
LB4
846
LA36
LB4
847
LA37
LB4
848
LA38
LB4
849
LA39
LB4
850
LA40
LB4
851
LA41
LB4
852
LA42
LB4
853
LA43
LB4
854
LA44
LB4
855
LA45
LB4
856
LA46
LB4
857
LA47
LB4
858
LA48
LB4
859
LA49
LB4
860
LA50
LB4
861
LA51
LB4
862
LA52
LB4
863
LA53
LB4
864
LA54
LB4
865
LA55
LB4
866
LA56
LB4
867
LA57
LB4
868
LA58
LB4
869
LA59
LB4
870
LA60
LB4
871
LA61
LB4
872
LA62
LB4
873
LA63
LB4
874
LA64
LB4
875
LA65
LB4
876
LA66
LB4
877
LA67
LB4
878
LA68
LB4
879
LA69
LB4
880
LA70
LB4
881
LA71
LB4
882
LA72
LB4
883
LA73
LB4
884
LA74
LB4
885
LA75
LB4
886
LA76
LB4
887
LA77
LB4
888
LA78
LB4
889
LA79
LB4
890
LA80
LB4
891
LA81
LB4
892
LA82
LB4
893
LA83
LB4
894
LA84
LB4
895
LA85
LB4
896
LA86
LB4
897
LA87
LB4
898
LA88
LB4
899
LA89
LB4
900
LA90
LB4
901
LA91
LB4
902
LA92
LB4
903
LA93
LB4
904
LA94
LB4
905
LA95
LB4
906
LA96
LB4
907
LA97
LB4
908
LA98
LB4
909
LA99
LB4
910
LA100
LB4
911
LA101
LB4
912
LA102
LB4
913
LA103
LB4
914
LA104
LB4
915
LA105
LB4
916
LA106
LB4
917
LA107
LB4
918
LA108
LB4
919
LA109
LB4
920
LA110
LB4
921
LA111
LB4
922
LA112
LB4
923
LA113
LB4
924
LA114
LB4
925
LA115
LB4
926
LA116
LB4
927
LA117
LB4
928
LA118
LB4
929
LA119
LB4
930
LA120
LB4
931
LA121
LB4
932
LA122
LB4
933
LA123
LB4
934
LA124
LB4
935
LA125
LB4
936
LA126
LB4
937
LA127
LB4
938
LA128
LB4
939
LA129
LB4
940
LA130
LB4
941
LA131
LB4
942
LA132
LB4
943
LA133
LB4
944
LA134
LB4
945
LA135
LB4
946
LA136
LB4
947
LA137
LB4
948
LA138
LB4
949
LA139
LB4
950
LA140
LB4
951
LA141
LB4
952
LA142
LB4
953
LA143
LB4
954
LA144
LB4
955
LA145
LB4
956
LA146
LB4
957
LA147
LB4
958
LA148
LB4
959
LA149
LB4
960
LA150
LB4
961
LA151
LB4
962
LA152
LB4
963
LA153
LB4
964
LA154
LB4
965
LA155
LB4
966
LA156
LB4
967
LA157
LB4
968
LA158
LB4
969
LA159
LB4
970
LA160
LB4
971
LA161
LB4
972
LA162
LB4
973
LA163
LB4
974
LA164
LB4
975
LA165
LB4
976
LA166
LB4
977
LA167
LB4
978
LA168
LB4
979
LA169
LB4
980
LA170
LB4
981
LA171
LB4
982
LA172
LB4
983
LA173
LB4
984
LA174
LB4
985
LA175
LB4
986
LA176
LB4
987
LA177
LB4
988
LA178
LB4
989
LA179
LB4
990
LA180
LB4
991
LA181
LB4
992
LA182
LB4
993
LA183
LB4
994
LA184
LB4
995
LA185
LB4
996
LA186
LB4
997
LA187
LB4
998
LA188
LB4
999
LA189
LB4
1000
LA190
LB4
1001
LA191
LB4
1002
LA192
LB4
1003
LA193
LB4
1004
LA194
LB4
1005
LA195
LB4
1006
LA196
LB4
1007
LA197
LB4
1008
LA198
LB4
1009
LA199
LB4
1010
LA200
LB4
1011
LA201
LB4
1012
LA202
LB4
1013
LA203
LB4
1014
LA204
LB4
1015
LA205
LB4
1016
LA206
LB4
1017
LA207
LB4
1018
LA208
LB4
1019
LA209
LB4
1020
LA210
LB4
1021
LA211
LB4
1022
LA212
LB4
1023
LA213
LB4
1024
LA214
LB4
1025
LA215
LB4
1026
LA216
LB4
1027
LA217
LB4
1028
LA218
LB4
1029
LA219
LB4
1030
LA220
LB4
1031
LA221
LB4
1032
LA222
LB4
1033
LA223
LB4
1034
LA224
LB4
1035
LA225
LB4
1036
LA226
LB4
1037
LA227
LB4
1038
LA228
LB4
1039
LA229
LB4
1040
LA230
LB4
1041
LA231
LB4
1042
LA232
LB4
1043
LA233
LB4
1044
LA234
LB4
1045
LA235
LB4
1046
LA236
LB4
1047
LA237
LB4
1048
LA238
LB4
1049
LA239
LB4
1050
LA240
LB4
1051
LA241
LB4
1052
LA242
LB4
1053
LA243
LB4
1054
LA244
LB4
1055
LA245
LB4
1056
LA246
LB4
1057
LA247
LB4
1058
LA248
LB4
1059
LA249
LB4
1060
LA250
LB4
1061
LA251
LB4
1062
LA252
LB4
1063
LA253
LB4
1064
LA254
LB4
1065
LA255
LB4
1066
LA256
LB4
1067
LA257
LB4
1068
LA258
LB4
1069
LA259
LB4
1070
LA260
LB4
1071
LA261
LB4
1072
LA262
LB4
1073
LA263
LB4
1074
LA264
LB4
1075
LA265
LB4
1076
LA266
LB4
1077
LA267
LB4
1078
LA268
LB4
1079
LA269
LB4
1080
LA270
LB4
1081
LA1
LB5
1082
LA2
LB5
1083
LA3
LB5
1084
LA4
LB5
1085
LA5
LB5
1086
LA6
LB5
1087
LA7
LB5
1088
LA8
LB5
1089
LA9
LB5
1090
LA10
LB5
1091
LA11
LB5
1092
LA12
LB5
1093
LA13
LB5
1094
LA14
LB5
1095
LA15
LB5
1096
LA16
LB5
1097
LA17
LB5
1098
LA18
LB5
1099
LA19
LB5
1100
LA20
LB5
1101
LA21
LB5
1102
LA22
LB5
1103
LA23
LB5
1104
LA24
LB5
1105
LA25
LB5
1106
LA26
LB5
1107
LA27
LB5
1108
LA28
LB5
1109
LA29
LB5
1110
LA30
LB5
1111
LA31
LB5
1112
LA32
LB5
1113
LA33
LB5
1114
LA34
LB5
1115
LA35
LB5
1116
LA36
LB5
1117
LA37
LB5
1118
LA38
LB5
1119
LA39
LB5
1120
LA40
LB5
1121
LA41
LB5
1122
LA42
LB5
1123
LA43
LB5
1124
LA44
LB5
1125
LA45
LB5
1126
LA46
LB5
1127
LA47
LB5
1128
LA48
LB5
1129
LA49
LB5
1130
LA50
LB5
1131
LA51
LB5
1132
LA52
LB5
1133
LA53
LB5
1134
LA54
LB5
1135
LA55
LB5
1136
LA56
LB5
1137
LA57
LB5
1138
LA58
LB5
1139
LA59
LB5
1140
LA60
LB5
1141
LA61
LB5
1142
LA62
LB5
1143
LA63
LB5
1144
LA64
LB5
1145
LA65
LB5
1146
LA66
LB5
1147
LA67
LB5
1148
LA68
LB5
1149
LA69
LB5
1150
LA70
LB5
1151
LA71
LB5
1152
LA72
LB5
1153
LA73
LB5
1154
LA74
LB5
1155
LA75
LB5
1156
LA76
LB5
1157
LA77
LB5
1158
LA78
LB5
1159
LA79
LB5
1160
LA80
LB5
1161
LA81
LB5
1162
LA82
LB5
1163
LA83
LB5
1164
LA84
LB5
1165
LA85
LB5
1166
LA86
LB5
1167
LA87
LB5
1168
LA88
LB5
1169
LA89
LB5
1170
LA90
LB5
1171
LA91
LB5
1172
LA92
LB5
1173
LA93
LB5
1174
LA94
LB5
1175
LA95
LB5
1176
LA96
LB5
1177
LA97
LB5
1178
LA98
LB5
1179
LA99
LB5
1180
LA100
LB5
1181
LA101
LB5
1182
LA102
LB5
1183
LA103
LB5
1184
LA104
LB5
1185
LA105
LB5
1186
LA106
LB5
1187
LA107
LB5
1188
LA108
LB5
1189
LA109
LB5
1190
LA110
LB5
1191
LA111
LB5
1192
LA112
LB5
1193
LA113
LB5
1194
LA114
LB5
1195
LA115
LB5
1196
LA116
LB5
1197
LA117
LB5
1198
LA118
LB5
1199
LA119
LB5
1200
LA120
LB5
1201
LA121
LB5
1202
LA122
LB5
1203
LA123
LB5
1204
LA124
LB5
1205
LA125
LB5
1206
LA126
LB5
1207
LA127
LB5
1208
LA128
LB5
1209
LA129
LB5
1210
LA130
LB5
1211
LA131
LB5
1212
LA132
LB5
1213
LA133
LB5
1214
LA134
LB5
1215
LA135
LB5
1216
LA136
LB5
1217
LA137
LB5
1218
LA138
LB5
1219
LA139
LB5
1220
LA140
LB5
1221
LA141
LB5
1222
LA142
LB5
1223
LA143
LB5
1224
LA144
LB5
1225
LA145
LB5
1226
LA146
LB5
1227
LA147
LB5
1228
LA148
LB5
1229
LA149
LB5
1230
LA150
LB5
1231
LA151
LB5
1232
LA152
LB5
1233
LA153
LB5
1234
LA154
LB5
1235
LA155
LB5
1236
LA156
LB5
1237
LA157
LB5
1238
LA158
LB5
1239
LA159
LB5
1240
LA160
LB5
1241
LA161
LB5
1242
LA162
LB5
1243
LA163
LB5
1244
LA164
LB5
1245
LA165
LB5
1246
LA166
LB5
1247
LA167
LB5
1248
LA168
LB5
1249
LA169
LB5
1250
LA170
LB5
1251
LA171
LB5
1252
LA172
LB5
1253
LA173
LB5
1254
LA174
LB5
1255
LA175
LB5
1256
LA176
LB5
1257
LA177
LB5
1258
LA178
LB5
1259
LA179
LB5
1260
LA180
LB5
1261
LA181
LB5
1262
LA182
LB5
1263
LA183
LB5
1264
LA184
LB5
1265
LA185
LB5
1266
LA186
LB5
1267
LA187
LB5
1268
LA188
LB5
1269
LA189
LB5
1270
LA190
LB5
1271
LA191
LB5
1272
LA192
LB5
1273
LA193
LB5
1274
LA194
LB5
1275
LA195
LB5
1276
LA196
LB5
1277
LA197
LB5
1278
LA198
LB5
1279
LA199
LB5
1280
LA200
LB5
1281
LA201
LB5
1282
LA202
LB5
1283
LA203
LB5
1284
LA204
LB5
1285
LA205
LB5
1286
LA206
LB5
1287
LA207
LB5
1288
LA208
LB5
1289
LA209
LB5
1290
LA210
LB5
1291
LA211
LB5
1292
LA212
LB5
1293
LA213
LB5
1294
LA214
LB5
1295
LA215
LB5
1296
LA216
LB5
1297
LA217
LB5
1298
LA218
LB5
1299
LA219
LB5
1300
LA220
LB5
1301
LA221
LB5
1302
LA222
LB5
1303
LA223
LB5
1304
LA224
LB5
1305
LA225
LB5
1306
LA226
LB5
1307
LA227
LB5
1308
LA228
LB5
1309
LA229
LB5
1310
LA230
LB5
1311
LA231
LB5
1312
LA232
LB5
1313
LA233
LB5
1314
LA234
LB5
1315
LA235
LB5
1316
LA236
LB5
1317
LA237
LB5
1318
LA238
LB5
1319
LA239
LB5
1320
LA240
LB5
1321
LA241
LB5
1322
LA242
LB5
1323
LA243
LB5
1324
LA244
LB5
1325
LA245
LB5
1326
LA246
LB5
1327
LA247
LB5
1328
LA248
LB5
1329
LA249
LB5
1330
LA250
LB5
1331
LA251
LB5
1332
LA252
LB5
1333
LA253
LB5
1334
LA254
LB5
1335
LA255
LB5
1336
LA256
LB5
1337
LA257
LB5
1338
LA258
LB5
1339
LA259
LB5
1340
LA260
LB5
1341
LA261
LB5
1342
LA262
LB5
1343
LA263
LB5
1344
LA264
LB5
1345
LA265
LB5
1346
LA266
LB5
1347
LA267
LB5
1348
LA268
LB5
1349
LA269
LB5
1350
LA270
LB5
1351
LA1
LB6
1352
LA2
LB6
1353
LA3
LB6
1354
LA4
LB6
1355
LA5
LB6
1356
LA6
LB6
1357
LA7
LB6
1358
LA8
LB6
1359
LA9
LB6
1360
LA10
LB6
1361
LA11
LB6
1362
LA12
LB6
1363
LA13
LB6
1364
LA14
LB6
1365
LA15
LB6
1366
LA16
LB6
1367
LA17
LB6
1368
LA18
LB6
1369
LA19
LB6
1370
LA20
LB6
1371
LA21
LB6
1372
LA22
LB6
1373
LA23
LB6
1374
LA24
LB6
1375
LA25
LB6
1376
LA26
LB6
1377
LA27
LB6
1378
LA28
LB6
1379
LA29
LB6
1380
LA30
LB6
1381
LA31
LB6
1382
LA32
LB6
1383
LA33
LB6
1384
LA34
LB6
1385
LA35
LB6
1386
LA36
LB6
1387
LA37
LB6
1388
LA38
LB6
1389
LA39
LB6
1390
LA40
LB6
1391
LA41
LB6
1392
LA42
LB6
1393
LA43
LB6
1394
LA44
LB6
1395
LA45
LB6
1396
LA46
LB6
1397
LA47
LB6
1398
LA48
LB6
1399
LA49
LB6
1400
LA50
LB6
1401
LA51
LB6
1402
LA52
LB6
1403
LA53
LB6
1404
LA54
LB6
1405
LA55
LB6
1406
LA56
LB6
1407
LA57
LB6
1408
LA58
LB6
1409
LA59
LB6
1410
LA60
LB6
1411
LA61
LB6
1412
LA62
LB6
1413
LA63
LB6
1414
LA64
LB6
1415
LA65
LB6
1416
LA66
LB6
1417
LA67
LB6
1418
LA68
LB6
1419
LA69
LB6
1420
LA70
LB6
1421
LA71
LB6
1422
LA72
LB6
1423
LA73
LB6
1424
LA74
LB6
1425
LA75
LB6
1426
LA76
LB6
1427
LA77
LB6
1428
LA78
LB6
1429
LA79
LB6
1430
LA80
LB6
1431
LA81
LB6
1432
LA82
LB6
1433
LA83
LB6
1434
LA84
LB6
1435
LA85
LB6
1436
LA86
LB6
1437
LA87
LB6
1438
LA88
LB6
1439
LA89
LB6
1440
LA90
LB6
1441
LA91
LB6
1442
LA92
LB6
1443
LA93
LB6
1444
LA94
LB6
1445
LA95
LB6
1446
LA96
LB6
1447
LA97
LB6
1448
LA98
LB6
1449
LA99
LB6
1450
LA100
LB6
1451
LA101
LB6
1452
LA102
LB6
1453
LA103
LB6
1454
LA104
LB6
1455
LA105
LB6
1456
LA106
LB6
1457
LA107
LB6
1458
LA108
LB6
1459
LA109
LB6
1460
LA110
LB6
1461
LA111
LB6
1462
LA112
LB6
1463
LA113
LB6
1464
LA114
LB6
1465
LA115
LB6
1466
LA116
LB6
1467
LA117
LB6
1468
LA118
LB6
1469
LA119
LB6
1470
LA120
LB6
1471
LA121
LB6
1472
LA122
LB6
1473
LA123
LB6
1474
LA124
LB6
1475
LA125
LB6
1476
LA126
LB6
1477
LA127
LB6
1478
LA128
LB6
1479
LA129
LB6
1480
LA130
LB6
1481
LA131
LB6
1482
LA132
LB6
1483
LA133
LB6
1484
LA134
LB6
1485
LA135
LB6
1486
LA136
LB6
1487
LA137
LB6
1488
LA138
LB6
1489
LA139
LB6
1490
LA140
LB6
1491
LA141
LB6
1492
LA142
LB6
1493
LA143
LB6
1494
LA144
LB6
1495
LA145
LB6
1496
LA146
LB6
1497
LA147
LB6
1498
LA148
LB6
1499
LA149
LB6
1500
LA150
LB6
1501
LA151
LB6
1502
LA152
LB6
1503
LA153
LB6
1504
LA154
LB6
1505
LA155
LB6
1506
LA156
LB6
1507
LA157
LB6
1508
LA158
LB6
1509
LA159
LB6
1510
LA160
LB6
1511
LA161
LB6
1512
LA162
LB6
1513
LA163
LB6
1514
LA164
LB6
1515
LA165
LB6
1516
LA166
LB6
1517
LA167
LB6
1518
LA168
LB6
1519
LA169
LB6
1520
LA170
LB6
1521
LA171
LB6
1522
LA172
LB6
1523
LA173
LB6
1524
LA174
LB6
1525
LA175
LB6
1526
LA176
LB6
1527
LA177
LB6
1528
LA178
LB6
1529
LA179
LB6
1530
LA180
LB6
1531
LA181
LB6
1532
LA182
LB6
1533
LA183
LB6
1534
LA184
LB6
1535
LA185
LB6
1536
LA186
LB6
1537
LA187
LB6
1538
LA188
LB6
1539
LA189
LB6
1540
LA190
LB6
1541
LA191
LB6
1542
LA192
LB6
1543
LA193
LB6
1544
LA194
LB6
1545
LA195
LB6
1546
LA196
LB6
1547
LA197
LB6
1548
LA198
LB6
1549
LA199
LB6
1550
LA200
LB6
1551
LA201
LB6
1552
LA202
LB6
1553
LA203
LB6
1554
LA204
LB6
1555
LA205
LB6
1556
LA206
LB6
1557
LA207
LB6
1558
LA208
LB6
1559
LA209
LB6
1560
LA210
LB6
1561
LA211
LB6
1562
LA212
LB6
1563
LA213
LB6
1564
LA214
LB6
1565
LA215
LB6
1566
LA216
LB6
1567
LA217
LB6
1568
LA218
LB6
1569
LA219
LB6
1570
LA220
LB6
1571
LA221
LB6
1572
LA222
LB6
1573
LA223
LB6
1574
LA224
LB6
1575
LA225
LB6
1576
LA226
LB6
1577
LA227
LB6
1578
LA228
LB6
1579
LA229
LB6
1580
LA230
LB6
1581
LA231
LB6
1582
LA232
LB6
1583
LA233
LB6
1584
LA234
LB6
1585
LA235
LB6
1586
LA236
LB6
1587
LA237
LB6
1588
LA238
LB6
1589
LA239
LB6
1590
LA240
LB6
1591
LA241
LB6
1592
LA242
LB6
1593
LA243
LB6
1594
LA244
LB6
1595
LA245
LB6
1596
LA246
LB6
1597
LA247
LB6
1598
LA248
LB6
1599
LA249
LB6
1600
LA250
LB6
1601
LA251
LB6
1602
LA252
LB6
1603
LA253
LB6
1604
LA254
LB6
1605
LA255
LB6
1606
LA256
LB6
1607
LA257
LB6
1608
LA258
LB6
1609
LA259
LB6
1610
LA260
LB6
1611
LA261
LB6
1612
LA262
LB6
1613
LA263
LB6
1614
LA264
LB6
1615
LA265
LB6
1616
LA266
LB6
1617
LA267
LB6
1618
LA268
LB6
1619
LA269
LB6
1620
LA270
LB6
1621
LA1
LB7
1622
LA2
LB7
1623
LA3
LB7
1624
LA4
LB7
1625
LA5
LB7
1626
LA6
LB7
1627
LA7
LB7
1628
LA8
LB7
1629
LA9
LB7
1630
LA10
LB7
1631
LA11
LB7
1632
LA12
LB7
1633
LA13
LB7
1634
LA14
LB7
1635
LA15
LB7
1636
LA16
LB7
1637
LA17
LB7
1638
LA18
LB7
1639
LA19
LB7
1640
LA20
LB7
1641
LA21
LB7
1642
LA22
LB7
1643
LA23
LB7
1644
LA24
LB7
1645
LA25
LB7
1646
LA26
LB7
1647
LA27
LB7
1648
LA28
LB7
1649
LA29
LB7
1650
LA30
LB7
1651
LA31
LB7
1652
LA32
LB7
1653
LA33
LB7
1654
LA34
LB7
1655
LA35
LB7
1656
LA36
LB7
1657
LA37
LB7
1658
LA38
LB7
1659
LA39
LB7
1660
LA40
LB7
1661
LA41
LB7
1662
LA42
LB7
1663
LA43
LB7
1664
LA44
LB7
1665
LA45
LB7
1666
LA46
LB7
1667
LA47
LB7
1668
LA48
LB7
1669
LA49
LB7
1670
LA50
LB7
1671
LA51
LB7
1672
LA52
LB7
1673
LA53
LB7
1674
LA54
LB7
1675
LA55
LB7
1676
LA56
LB7
1677
LA57
LB7
1678
LA58
LB7
1679
LA59
LB7
1680
LA60
LB7
1681
LA61
LB7
1682
LA62
LB7
1683
LA63
LB7
1684
LA64
LB7
1685
LA65
LB7
1686
LA66
LB7
1687
LA67
LB7
1688
LA68
LB7
1689
LA69
LB7
1690
LA70
LB7
1691
LA71
LB7
1692
LA72
LB7
1693
LA73
LB7
1694
LA74
LB7
1695
LA75
LB7
1696
LA76
LB7
1697
LA77
LB7
1698
LA78
LB7
1699
LA79
LB7
1700
LA80
LB7
1701
LA81
LB7
1702
LA82
LB7
1703
LA83
LB7
1704
LA84
LB7
1705
LA85
LB7
1706
LA86
LB7
1707
LA87
LB7
1708
LA88
LB7
1709
LA89
LB7
1710
LA90
LB7
1711
LA91
LB7
1712
LA92
LB7
1713
LA93
LB7
1714
LA94
LB7
1715
LA95
LB7
1716
LA96
LB7
1717
LA97
LB7
1718
LA98
LB7
1719
LA99
LB7
1720
LA100
LB7
1721
LA101
LB7
1722
LA102
LB7
1723
LA103
LB7
1724
LA104
LB7
1725
LA105
LB7
1726
LA106
LB7
1727
LA107
LB7
1728
LA108
LB7
1729
LA109
LB7
1730
LA110
LB7
1731
LA111
LB7
1732
LA112
LB7
1733
LA113
LB7
1734
LA114
LB7
1735
LA115
LB7
1736
LA116
LB7
1737
LA117
LB7
1738
LA118
LB7
1739
LA119
LB7
1740
LA120
LB7
1741
LA121
LB7
1742
LA122
LB7
1743
LA123
LB7
1744
LA124
LB7
1745
LA125
LB7
1746
LA126
LB7
1747
LA127
LB7
1748
LA128
LB7
1749
LA129
LB7
1750
LA130
LB7
1751
LA131
LB7
1752
LA132
LB7
1753
LA133
LB7
1754
LA134
LB7
1755
LA135
LB7
1756
LA136
LB7
1757
LA137
LB7
1758
LA138
LB7
1759
LA139
LB7
1760
LA140
LB7
1761
LA141
LB7
1762
LA142
LB7
1763
LA143
LB7
1764
LA144
LB7
1765
LA145
LB7
1766
LA146
LB7
1767
LA147
LB7
1768
LA148
LB7
1769
LA149
LB7
1770
LA150
LB7
1771
LA151
LB7
1772
LA152
LB7
1773
LA153
LB7
1774
LA154
LB7
1775
LA155
LB7
1776
LA156
LB7
1777
LA157
LB7
1778
LA158
LB7
1779
LA159
LB7
1780
LA160
LB7
1781
LA161
LB7
1782
LA162
LB7
1783
LA163
LB7
1784
LA164
LB7
1785
LA165
LB7
1786
LA166
LB7
1787
LA167
LB7
1788
LA168
LB7
1789
LA169
LB7
1790
LA170
LB7
1791
LA171
LB7
1792
LA172
LB7
1793
LA173
LB7
1794
LA174
LB7
1795
LA175
LB7
1796
LA176
LB7
1797
LA177
LB7
1798
LA178
LB7
1799
LA179
LB7
1800
LA180
LB7
1801
LA181
LB7
1802
LA182
LB7
1803
LA183
LB7
1804
LA184
LB7
1805
LA185
LB7
1806
LA186
LB7
1807
LA187
LB7
1808
LA188
LB7
1809
LA189
LB7
1810
LA190
LB7
1811
LA191
LB7
1812
LA192
LB7
1813
LA193
LB7
1814
LA194
LB7
1815
LA195
LB7
1816
LA196
LB7
1817
LA197
LB7
1818
LA198
LB7
1819
LA199
LB7
1820
LA200
LB7
1821
LA201
LB7
1822
LA202
LB7
1823
LA203
LB7
1824
LA204
LB7
1825
LA205
LB7
1826
LA206
LB7
1827
LA207
LB7
1828
LA208
LB7
1829
LA209
LB7
1830
LA210
LB7
1831
LA211
LB7
1832
LA212
LB7
1833
LA213
LB7
1834
LA214
LB7
1835
LA215
LB7
1836
LA216
LB7
1837
LA217
LB7
1838
LA218
LB7
1839
LA219
LB7
1840
LA220
LB7
1841
LA221
LB7
1842
LA222
LB7
1843
LA223
LB7
1844
LA224
LB7
1845
LA225
LB7
1846
LA226
LB7
1847
LA227
LB7
1848
LA228
LB7
1849
LA229
LB7
1850
LA230
LB7
1851
LA231
LB7
1852
LA232
LB7
1853
LA233
LB7
1854
LA234
LB7
1855
LA235
LB7
1856
LA236
LB7
1857
LA237
LB7
1858
LA238
LB7
1859
LA239
LB7
1860
LA240
LB7
1861
LA241
LB7
1862
LA242
LB7
1863
LA243
LB7
1864
LA244
LB7
1865
LA245
LB7
1866
LA246
LB7
1867
LA247
LB7
1868
LA248
LB7
1869
LA249
LB7
1870
LA250
LB7
1871
LA251
LB7
1872
LA252
LB7
1873
LA253
LB7
1874
LA254
LB7
1875
LA255
LB7
1876
LA256
LB7
1877
LA257
LB7
1878
LA258
LB7
1879
LA259
LB7
1880
LA260
LB7
1881
LA261
LB7
1882
LA262
LB7
1883
LA263
LB7
1884
LA264
LB7
1885
LA265
LB7
1886
LA266
LB7
1887
LA267
LB7
1888
LA268
LB7
1889
LA269
LB7
1890
LA270
LB7
1891
LA1
LB8
1892
LA2
LB8
1893
LA3
LB8
1894
LA4
LB8
1895
LA5
LB8
1896
LA6
LB8
1897
LA7
LB8
1898
LA8
LB8
1899
LA9
LB8
1900
LA10
LB8
1901
LA11
LB8
1902
LA12
LB8
1903
LA13
LB8
1904
LA14
LB8
1905
LA15
LB8
1906
LA16
LB8
1907
LA17
LB8
1908
LA18
LB8
1909
LA19
LB8
1910
LA20
LB8
1911
LA21
LB8
1912
LA22
LB8
1913
LA23
LB8
1914
LA24
LB8
1915
LA25
LB8
1916
LA26
LB8
1917
LA27
LB8
1918
LA28
LB8
1919
LA29
LB8
1920
LA30
LB8
1921
LA31
LB8
1922
LA32
LB8
1923
LA33
LB8
1924
LA34
LB8
1925
LA35
LB8
1926
LA36
LB8
1927
LA37
LB8
1928
LA38
LB8
1929
LA39
LB8
1930
LA40
LB8
1931
LA41
LB8
1932
LA42
LB8
1933
LA43
LB8
1934
LA44
LB8
1935
LA45
LB8
1936
LA46
LB8
1937
LA47
LB8
1938
LA48
LB8
1939
LA49
LB8
1940
LA50
LB8
1941
LA51
LB8
1942
LA52
LB8
1943
LA53
LB8
1944
LA54
LB8
1945
LA55
LB8
1946
LA56
LB8
1947
LA57
LB8
1948
LA58
LB8
1949
LA59
LB8
1950
LA60
LB8
1951
LA61
LB8
1952
LA62
LB8
1953
LA63
LB8
1954
LA64
LB8
1955
LA65
LB8
1956
LA66
LB8
1957
LA67
LB8
1958
LA68
LB8
1959
LA69
LB8
1960
LA70
LB8
1961
LA71
LB8
1962
LA72
LB8
1963
LA73
LB8
1964
LA74
LB8
1965
LA75
LB8
1966
LA76
LB8
1967
LA77
LB8
1968
LA78
LB8
1969
LA79
LB8
1970
LA80
LB8
1971
LA81
LB8
1972
LA82
LB8
1973
LA83
LB8
1974
LA84
LB8
1975
LA85
LB8
1976
LA86
LB8
1977
LA87
LB8
1978
LA88
LB8
1979
LA89
LB8
1980
LA90
LB8
1981
LA91
LB8
1982
LA92
LB8
1983
LA93
LB8
1984
LA94
LB8
1985
LA95
LB8
1986
LA96
LB8
1987
LA97
LB8
1988
LA98
LB8
1989
LA99
LB8
1990
LA100
LB8
1991
LA101
LB8
1992
LA102
LB8
1993
LA103
LB8
1994
LA104
LB8
1995
LA105
LB8
1996
LA106
LB8
1997
LA107
LB8
1998
LA108
LB8
1999
LA109
LB8
2000
LA110
LB8
2001
LA111
LB8
2002
LA112
LB8
2003
LA113
LB8
2004
LA114
LB8
2005
LA115
LB8
2006
LA116
LB8
2007
LA117
LB8
2008
LA118
LB8
2009
LA119
LB8
2010
LA120
LB8
2011
LA121
LB8
2012
LA122
LB8
2013
LA123
LB8
2014
LA124
LB8
2015
LA125
LB8
2016
LA126
LB8
2017
LA127
LB8
2018
LA128
LB8
2019
LA129
LB8
2020
LA130
LB8
2021
LA131
LB8
2022
LA132
LB8
2023
LA133
LB8
2024
LA134
LB8
2025
LA135
LB8
2026
LA136
LB8
2027
LA137
LB8
2028
LA138
LB8
2029
LA139
LB8
2030
LA140
LB8
2031
LA141
LB8
2032
LA142
LB8
2033
LA143
LB8
2034
LA144
LB8
2035
LA145
LB8
2036
LA146
LB8
2037
LA147
LB8
2038
LA148
LB8
2039
LA149
LB8
2040
LA150
LB8
2041
LA151
LB8
2042
LA152
LB8
2043
LA153
LB8
2044
LA154
LB8
2045
LA155
LB8
2046
LA156
LB8
2047
LA157
LB8
2048
LA158
LB8
2049
LA159
LB8
2050
LA160
LB8
2051
LA161
LB8
2052
LA162
LB8
2053
LA163
LB8
2054
LA164
LB8
2055
LA165
LB8
2056
LA166
LB8
2057
LA167
LB8
2058
LA168
LB8
2059
LA169
LB8
2060
LA170
LB8
2061
LA171
LB8
2062
LA172
LB8
2063
LA173
LB8
2064
LA174
LB8
2065
LA175
LB8
2066
LA176
LB8
2067
LA177
LB8
2068
LA178
LB8
2069
LA179
LB8
2070
LA180
LB8
2071
LA181
LB8
2072
LA182
LB8
2073
LA183
LB8
2074
LA184
LB8
2075
LA185
LB8
2076
LA186
LB8
2077
LA187
LB8
2078
LA188
LB8
2079
LA189
LB8
2080
LA190
LB8
2081
LA191
LB8
2082
LA192
LB8
2083
LA193
LB8
2084
LA194
LB8
2085
LA195
LB8
2086
LA196
LB8
2087
LA197
LB8
2088
LA198
LB8
2089
LA199
LB8
2090
LA200
LB8
2091
LA201
LB8
2092
LA202
LB8
2093
LA203
LB8
2094
LA204
LB8
2095
LA205
LB8
2096
LA206
LB8
2097
LA207
LB8
2098
LA208
LB8
2099
LA209
LB8
2100
LA210
LB8
2101
LA211
LB8
2102
LA212
LB8
2103
LA213
LB8
2104
LA214
LB8
2105
LA215
LB8
2106
LA216
LB8
2107
LA217
LB8
2108
LA218
LB8
2109
LA219
LB8
2110
LA220
LB8
2111
LA221
LB8
2112
LA222
LB8
2113
LA223
LB8
2114
LA224
LB8
2115
LA225
LB8
2116
LA226
LB8
2117
LA227
LB8
2118
LA228
LB8
2119
LA229
LB8
2120
LA230
LB8
2121
LA231
LB8
2122
LA232
LB8
2123
LA233
LB8
2124
LA234
LB8
2125
LA235
LB8
2126
LA236
LB8
2127
LA237
LB8
2128
LA238
LB8
2129
LA239
LB8
2130
LA240
LB8
2131
LA241
LB8
2132
LA242
LB8
2133
LA243
LB8
2134
LA244
LB8
2135
LA245
LB8
2136
LA246
LB8
2137
LA247
LB8
2138
LA248
LB8
2139
LA249
LB8
2140
LA250
LB8
2141
LA251
LB8
2142
LA252
LB8
2143
LA253
LB8
2144
LA254
LB8
2145
LA255
LB8
2146
LA256
LB8
2147
LA257
LB8
2148
LA258
LB8
2149
LA259
LB8
2150
LA260
LB8
2151
LA261
LB8
2152
LA262
LB8
2153
LA263
LB8
2154
LA264
LB8
2155
LA265
LB8
2156
LA266
LB8
2157
LA267
LB8
2158
LA268
LB8
2159
LA269
LB8
2160
LA270
LB8
2161
LA1
LB9
2162
LA2
LB9
2163
LA3
LB9
2164
LA4
LB9
2165
LA5
LB9
2166
LA6
LB9
2167
LA7
LB9
2168
LA8
LB9
2169
LA9
LB9
2170
LA10
LB9
2171
LA11
LB9
2172
LA12
LB9
2173
LA13
LB9
2174
LA14
LB9
2175
LA15
LB9
2176
LA16
LB9
2177
LA17
LB9
2178
LA18
LB9
2179
LA19
LB9
2180
LA20
LB9
2181
LA21
LB9
2182
LA22
LB9
2183
LA23
LB9
2184
LA24
LB9
2185
LA25
LB9
2186
LA26
LB9
2187
LA27
LB9
2188
LA28
LB9
2189
LA29
LB9
2190
LA30
LB9
2191
LA31
LB9
2192
LA32
LB9
2193
LA33
LB9
2194
LA34
LB9
2195
LA35
LB9
2196
LA36
LB9
2197
LA37
LB9
2198
LA38
LB9
2199
LA39
LB9
2200
LA40
LB9
2201
LA41
LB9
2202
LA42
LB9
2203
LA43
LB9
2204
LA44
LB9
2205
LA45
LB9
2206
LA46
LB9
2207
LA47
LB9
2208
LA48
LB9
2209
LA49
LB9
2210
LA50
LB9
2211
LA51
LB9
2212
LA52
LB9
2213
LA53
LB9
2214
LA54
LB9
2215
LA55
LB9
2216
LA56
LB9
2217
LA57
LB9
2218
LA58
LB9
2219
LA59
LB9
2220
LA60
LB9
2221
LA61
LB9
2222
LA62
LB9
2223
LA63
LB9
2224
LA64
LB9
2225
LA65
LB9
2226
LA66
LB9
2227
LA67
LB9
2228
LA68
LB9
2229
LA69
LB9
2230
LA70
LB9
2231
LA71
LB9
2232
LA72
LB9
2233
LA73
LB9
2234
LA74
LB9
2235
LA75
LB9
2236
LA76
LB9
2237
LA77
LB9
2238
LA78
LB9
2239
LA79
LB9
2240
LA80
LB9
2241
LA81
LB9
2242
LA82
LB9
2243
LA83
LB9
2244
LA84
LB9
2245
LA85
LB9
2246
LA86
LB9
2247
LA87
LB9
2248
LA88
LB9
2249
LA89
LB9
2250
LA90
LB9
2251
LA91
LB9
2252
LA92
LB9
2253
LA93
LB9
2254
LA94
LB9
2255
LA95
LB9
2256
LA96
LB9
2257
LA97
LB9
2258
LA98
LB9
2259
LA99
LB9
2260
LA100
LB9
2261
LA101
LB9
2262
LA102
LB9
2263
LA103
LB9
2264
LA104
LB9
2265
LA105
LB9
2266
LA106
LB9
2267
LA107
LB9
2268
LA108
LB9
2269
LA109
LB9
2270
LA110
LB9
2271
LA111
LB9
2272
LA112
LB9
2273
LA113
LB9
2274
LA114
LB9
2275
LA115
LB9
2276
LA116
LB9
2277
LA117
LB9
2278
LA118
LB9
2279
LA119
LB9
2280
LA120
LB9
2281
LA121
LB9
2282
LA122
LB9
2283
LA123
LB9
2284
LA124
LB9
2285
LA125
LB9
2286
LA126
LB9
2287
LA127
LB9
2288
LA128
LB9
2289
LA129
LB9
2290
LA130
LB9
2291
LA131
LB9
2292
LA132
LB9
2293
LA133
LB9
2294
LA134
LB9
2295
LA135
LB9
2296
LA136
LB9
2297
LA137
LB9
2298
LA138
LB9
2299
LA139
LB9
2300
LA140
LB9
2301
LA141
LB9
2302
LA142
LB9
2303
LA143
LB9
2304
LA144
LB9
2305
LA145
LB9
2306
LA146
LB9
2307
LA147
LB9
2308
LA148
LB9
2309
LA149
LB9
2310
LA150
LB9
2311
LA151
LB9
2312
LA152
LB9
2313
LA153
LB9
2314
LA154
LB9
2315
LA155
LB9
2316
LA156
LB9
2317
LA157
LB9
2318
LA158
LB9
2319
LA159
LB9
2320
LA160
LB9
2321
LA161
LB9
2322
LA162
LB9
2323
LA163
LB9
2324
LA164
LB9
2325
LA165
LB9
2326
LA166
LB9
2327
LA167
LB9
2328
LA168
LB9
2329
LA169
LB9
2330
LA170
LB9
2331
LA171
LB9
2332
LA172
LB9
2333
LA173
LB9
2334
LA174
LB9
2335
LA175
LB9
2336
LA176
LB9
2337
LA177
LB9
2338
LA178
LB9
2339
LA179
LB9
2340
LA180
LB9
2341
LA181
LB9
2342
LA182
LB9
2343
LA183
LB9
2344
LA184
LB9
2345
LA185
LB9
2346
LA186
LB9
2347
LA187
LB9
2348
LA188
LB9
2349
LA189
LB9
2350
LA190
LB9
2351
LA191
LB9
2352
LA192
LB9
2353
LA193
LB9
2354
LA194
LB9
2355
LA195
LB9
2356
LA196
LB9
2357
LA197
LB9
2358
LA198
LB9
2359
LA199
LB9
2360
LA200
LB9
2361
LA201
LB9
2362
LA202
LB9
2363
LA203
LB9
2364
LA204
LB9
2365
LA205
LB9
2366
LA206
LB9
2367
LA207
LB9
2368
LA208
LB9
2369
LA209
LB9
2370
LA210
LB9
2371
LA211
LB9
2372
LA212
LB9
2373
LA213
LB9
2374
LA214
LB9
2375
LA215
LB9
2376
LA216
LB9
2377
LA217
LB9
2378
LA218
LB9
2379
LA219
LB9
2380
LA220
LB9
2381
LA221
LB9
2382
LA222
LB9
2383
LA223
LB9
2384
LA224
LB9
2385
LA225
LB9
2386
LA226
LB9
2387
LA227
LB9
2388
LA228
LB9
2389
LA229
LB9
2390
LA230
LB9
2391
LA231
LB9
2392
LA232
LB9
2393
LA233
LB9
2394
LA234
LB9
2395
LA235
LB9
2396
LA236
LB9
2397
LA237
LB9
2398
LA238
LB9
2399
LA239
LB9
2400
LA240
LB9
2401
LA241
LB9
2402
LA242
LB9
2403
LA243
LB9
2404
LA244
LB9
2405
LA245
LB9
2406
LA246
LB9
2407
LA247
LB9
2408
LA248
LB9
2409
LA249
LB9
2410
LA250
LB9
2411
LA251
LB9
2412
LA252
LB9
2413
LA253
LB9
2414
LA254
LB9
2415
LA255
LB9
2416
LA256
LB9
2417
LA257
LB9
2418
LA258
LB9
2419
LA259
LB9
2420
LA260
LB9
2421
LA261
LB9
2422
LA262
LB9
2423
LA263
LB9
2424
LA264
LB9
2425
LA265
LB9
2426
LA266
LB9
2427
LA267
LB9
2428
LA268
LB9
2429
LA269
LB9
2430
LA270
LB9
2431
LA1
LB10
2432
LA2
LB10
2433
LA3
LB10
2434
LA4
LB10
2435
LA5
LB10
2436
LA6
LB10
2437
LA7
LB10
2438
LA8
LB10
2439
LA9
LB10
2440
LA10
LB10
2441
LA11
LB10
2442
LA12
LB10
2443
LA13
LB10
2444
LA14
LB10
2445
LA15
LB10
2446
LA16
LB10
2447
LA17
LB10
2448
LA18
LB10
2449
LA19
LB10
2450
LA20
LB10
2451
LA21
LB10
2452
LA22
LB10
2453
LA23
LB10
2454
LA24
LB10
2455
LA25
LB10
2456
LA26
LB10
2457
LA27
LB10
2458
LA28
LB10
2459
LA29
LB10
2460
LA30
LB10
2461
LA31
LB10
2462
LA32
LB10
2463
LA33
LB10
2464
LA34
LB10
2465
LA35
LB10
2466
LA36
LB10
2467
LA37
LB10
2468
LA38
LB10
2469
LA39
LB10
2470
LA40
LB10
2471
LA41
LB10
2472
LA42
LB10
2473
LA43
LB10
2474
LA44
LB10
2475
LA45
LB10
2476
LA46
LB10
2477
LA47
LB10
2478
LA48
LB10
2479
LA49
LB10
2480
LA50
LB10
2481
LA51
LB10
2482
LA52
LB10
2483
LA53
LB10
2484
LA54
LB10
2485
LA55
LB10
2486
LA56
LB10
2487
LA57
LB10
2488
LA58
LB10
2489
LA59
LB10
2490
LA60
LB10
2491
LA61
LB10
2492
LA62
LB10
2493
LA63
LB10
2494
LA64
LB10
2495
LA65
LB10
2496
LA66
LB10
2497
LA67
LB10
2498
LA68
LB10
2499
LA69
LB10
2500
LA70
LB10
2501
LA71
LB10
2502
LA72
LB10
2503
LA73
LB10
2504
LA74
LB10
2505
LA75
LB10
2506
LA76
LB10
2507
LA77
LB10
2508
LA78
LB10
2509
LA79
LB10
2510
LA80
LB10
2511
LA81
LB10
2512
LA82
LB10
2513
LA83
LB10
2514
LA84
LB10
2515
LA85
LB10
2516
LA86
LB10
2517
LA87
LB10
2518
LA88
LB10
2519
LA89
LB10
2520
LA90
LB10
2521
LA91
LB10
2522
LA92
LB10
2523
LA93
LB10
2524
LA94
LB10
2525
LA95
LB10
2526
LA96
LB10
2527
LA97
LB10
2528
LA98
LB10
2529
LA99
LB10
2530
LA100
LB10
2531
LA101
LB10
2532
LA102
LB10
2533
LA103
LB10
2534
LA104
LB10
2535
LA105
LB10
2536
LA106
LB10
2537
LA107
LB10
2538
LA108
LB10
2539
LA109
LB10
2540
LA110
LB10
2541
LA111
LB10
2542
LA112
LB10
2543
LA113
LB10
2544
LA114
LB10
2545
LA115
LB10
2546
LA116
LB10
2547
LA117
LB10
2548
LA118
LB10
2549
LA119
LB10
2550
LA120
LB10
2551
LA121
LB10
2552
LA122
LB10
2553
LA123
LB10
2554
LA124
LB10
2555
LA125
LB10
2556
LA126
LB10
2557
LA127
LB10
2558
LA128
LB10
2559
LA129
LB10
2560
LA130
LB10
2561
LA131
LB10
2562
LA132
LB10
2563
LA133
LB10
2564
LA134
LB10
2565
LA135
LB10
2566
LA136
LB10
2567
LA137
LB10
2568
LA138
LB10
2569
LA139
LB10
2570
LA140
LB10
2571
LA141
LB10
2572
LA142
LB10
2573
LA143
LB10
2574
LA144
LB10
2575
LA145
LB10
2576
LA146
LB10
2577
LA147
LB10
2578
LA148
LB10
2579
LA149
LB10
2580
LA150
LB10
2581
LA151
LB10
2582
LA152
LB10
2583
LA153
LB10
2584
LA154
LB10
2585
LA155
LB10
2586
LA156
LB10
2587
LA157
LB10
2588
LA158
LB10
2589
LA159
LB10
2590
LA160
LB10
2591
LA161
LB10
2592
LA162
LB10
2593
LA163
LB10
2594
LA164
LB10
2595
LA165
LB10
2596
LA166
LB10
2597
LA167
LB10
2598
LA168
LB10
2599
LA169
LB10
2600
LA170
LB10
2601
LA171
LB10
2602
LA172
LB10
2603
LA173
LB10
2604
LA174
LB10
2605
LA175
LB10
2606
LA176
LB10
2607
LA177
LB10
2608
LA178
LB10
2609
LA179
LB10
2610
LA180
LB10
2611
LA181
LB10
2612
LA182
LB10
2613
LA183
LB10
2614
LA184
LB10
2615
LA185
LB10
2616
LA186
LB10
2617
LA187
LB10
2618
LA188
LB10
2619
LA189
LB10
2620
LA190
LB10
2621
LA191
LB10
2622
LA192
LB10
2623
LA193
LB10
2624
LA194
LB10
2625
LA195
LB10
2626
LA196
LB10
2627
LA197
LB10
2628
LA198
LB10
2629
LA199
LB10
2630
LA200
LB10
2631
LA201
LB10
2632
LA202
LB10
2633
LA203
LB10
2634
LA204
LB10
2635
LA205
LB10
2636
LA206
LB10
2637
LA207
LB10
2638
LA208
LB10
2639
LA209
LB10
2640
LA210
LB10
2641
LA211
LB10
2642
LA212
LB10
2643
LA213
LB10
2644
LA214
LB10
2645
LA215
LB10
2646
LA216
LB10
2647
LA217
LB10
2648
LA218
LB10
2649
LA219
LB10
2650
LA220
LB10
2651
LA221
LB10
2652
LA222
LB10
2653
LA223
LB10
2654
LA224
LB10
2655
LA225
LB10
2656
LA226
LB10
2657
LA227
LB10
2658
LA228
LB10
2659
LA229
LB10
2660
LA230
LB10
2661
LA231
LB10
2662
LA232
LB10
2663
LA233
LB10
2664
LA234
LB10
2665
LA235
LB10
2666
LA236
LB10
2667
LA237
LB10
2668
LA238
LB10
2669
LA239
LB10
2670
LA240
LB10
2671
LA241
LB10
2672
LA242
LB10
2673
LA243
LB10
2674
LA244
LB10
2675
LA245
LB10
2676
LA246
LB10
2677
LA247
LB10
2678
LA248
LB10
2679
LA249
LB10
2680
LA250
LB10
2681
LA251
LB10
2682
LA252
LB10
2683
LA253
LB10
2684
LA254
LB10
2685
LA255
LB10
2686
LA256
LB10
2687
LA257
LB10
2688
LA258
LB10
2689
LA259
LB10
2690
LA260
LB10
2691
LA261
LB10
2692
LA262
LB10
2693
LA263
LB10
2694
LA264
LB10
2695
LA265
LB10
2696
LA266
LB10
2697
LA267
LB10
2698
LA268
LB10
2699
LA269
LB10
2700
LA270
LB10
2701
LA1
LB11
2702
LA2
LB11
2703
LA3
LB11
2704
LA4
LB11
2705
LA5
LB11
2706
LA6
LB11
2707
LA7
LB11
2708
LA8
LB11
2709
LA9
LB11
2710
LA10
LB11
2711
LA11
LB11
2712
LA12
LB11
2713
LA13
LB11
2714
LA14
LB11
2715
LA15
LB11
2716
LA16
LB11
2717
LA17
LB11
2718
LA18
LB11
2719
LA19
LB11
2720
LA20
LB11
2721
LA21
LB11
2722
LA22
LB11
2723
LA23
LB11
2724
LA24
LB11
2725
LA25
LB11
2726
LA26
LB11
2727
LA27
LB11
2728
LA28
LB11
2729
LA29
LB11
2730
LA30
LB11
2731
LA31
LB11
2732
LA32
LB11
2733
LA33
LB11
2734
LA34
LB11
2735
LA35
LB11
2736
LA36
LB11
2737
LA37
LB11
2738
LA38
LB11
2739
LA39
LB11
2740
LA40
LB11
2741
LA41
LB11
2742
LA42
LB11
2743
LA43
LB11
2744
LA44
LB11
2745
LA45
LB11
2746
LA46
LB11
2747
LA47
LB11
2748
LA48
LB11
2749
LA49
LB11
2750
LA50
LB11
2751
LA51
LB11
2752
LA52
LB11
2753
LA53
LB11
2754
LA54
LB11
2755
LA55
LB11
2756
LA56
LB11
2757
LA57
LB11
2758
LA58
LB11
2759
LA59
LB11
2760
LA60
LB11
2761
LA61
LB11
2762
LA62
LB11
2763
LA63
LB11
2764
LA64
LB11
2765
LA65
LB11
2766
LA66
LB11
2767
LA67
LB11
2768
LA68
LB11
2769
LA69
LB11
2770
LA70
LB11
2771
LA71
LB11
2772
LA72
LB11
2773
LA73
LB11
2774
LA74
LB11
2775
LA75
LB11
2776
LA76
LB11
2777
LA77
LB11
2778
LA78
LB11
2779
LA79
LB11
2780
LA80
LB11
2781
LA81
LB11
2782
LA82
LB11
2783
LA83
LB11
2784
LA84
LB11
2785
LA85
LB11
2786
LA86
LB11
2787
LA87
LB11
2788
LA88
LB11
2789
LA89
LB11
2790
LA90
LB11
2791
LA91
LB11
2792
LA92
LB11
2793
LA93
LB11
2794
LA94
LB11
2795
LA95
LB11
2796
LA96
LB11
2797
LA97
LB11
2798
LA98
LB11
2799
LA99
LB11
2800
LA100
LB11
2801
LA101
LB11
2802
LA102
LB11
2803
LA103
LB11
2804
LA104
LB11
2805
LA105
LB11
2806
LA106
LB11
2807
LA107
LB11
2808
LA108
LB11
2809
LA109
LB11
2810
LA110
LB11
2811
LA111
LB11
2812
LA112
LB11
2813
LA113
LB11
2814
LA114
LB11
2815
LA115
LB11
2816
LA116
LB11
2817
LA117
LB11
2818
LA118
LB11
2819
LA119
LB11
2820
LA120
LB11
2821
LA121
LB11
2822
LA122
LB11
2823
LA123
LB11
2824
LA124
LB11
2825
LA125
LB11
2826
LA126
LB11
2827
LA127
LB11
2828
LA128
LB11
2829
LA129
LB11
2830
LA130
LB11
2831
LA131
LB11
2832
LA132
LB11
2833
LA133
LB11
2834
LA134
LB11
2835
LA135
LB11
2836
LA136
LB11
2837
LA137
LB11
2838
LA138
LB11
2839
LA139
LB11
2840
LA140
LB11
2841
LA141
LB11
2842
LA142
LB11
2843
LA143
LB11
2844
LA144
LB11
2845
LA145
LB11
2846
LA146
LB11
2847
LA147
LB11
2848
LA148
LB11
2849
LA149
LB11
2850
LA150
LB11
2851
LA151
LB11
2852
LA152
LB11
2853
LA153
LB11
2854
LA154
LB11
2855
LA155
LB11
2856
LA156
LB11
2857
LA157
LB11
2858
LA158
LB11
2859
LA159
LB11
2860
LA160
LB11
2861
LA161
LB11
2862
LA162
LB11
2863
LA163
LB11
2864
LA164
LB11
2865
LA165
LB11
2866
LA166
LB11
2867
LA167
LB11
2868
LA168
LB11
2869
LA169
LB11
2870
LA170
LB11
2871
LA171
LB11
2872
LA172
LB11
2873
LA173
LB11
2874
LA174
LB11
2875
LA175
LB11
2876
LA176
LB11
2877
LA177
LB11
2878
LA178
LB11
2879
LA179
LB11
2880
LA180
LB11
2881
LA181
LB11
2882
LA182
LB11
2883
LA183
LB11
2884
LA184
LB11
2885
LA185
LB11
2886
LA186
LB11
2887
LA187
LB11
2888
LA188
LB11
2889
LA189
LB11
2890
LA190
LB11
2891
LA191
LB11
2892
LA192
LB11
2893
LA193
LB11
2894
LA194
LB11
2895
LA195
LB11
2896
LA196
LB11
2897
LA197
LB11
2898
LA198
LB11
2899
LA199
LB11
2900
LA200
LB11
2901
LA201
LB11
2902
LA202
LB11
2903
LA203
LB11
2904
LA204
LB11
2905
LA205
LB11
2906
LA206
LB11
2907
LA207
LB11
2908
LA208
LB11
2909
LA209
LB11
2910
LA210
LB11
2911
LA211
LB11
2912
LA212
LB11
2913
LA213
LB11
2914
LA214
LB11
2915
LA215
LB11
2916
LA216
LB11
2917
LA217
LB11
2918
LA218
LB11
2919
LA219
LB11
2920
LA220
LB11
2921
LA221
LB11
2922
LA222
LB11
2923
LA223
LB11
2924
LA224
LB11
2925
LA225
LB11
2926
LA226
LB11
2927
LA227
LB11
2928
LA228
LB11
2929
LA229
LB11
2930
LA230
LB11
2931
LA231
LB11
2932
LA232
LB11
2933
LA233
LB11
2934
LA234
LB11
2935
LA235
LB11
2936
LA236
LB11
2937
LA237
LB11
2938
LA238
LB11
2939
LA239
LB11
2940
LA240
LB11
2941
LA241
LB11
2942
LA242
LB11
2943
LA243
LB11
2944
LA244
LB11
2945
LA245
LB11
2946
LA246
LB11
2947
LA247
LB11
2948
LA248
LB11
2949
LA249
LB11
2950
LA250
LB11
2951
LA251
LB11
2952
LA252
LB11
2953
LA253
LB11
2954
LA254
LB11
2955
LA255
LB11
2956
LA256
LB11
2957
LA257
LB11
2958
LA258
LB11
2959
LA259
LB11
2960
LA260
LB11
2961
LA261
LB11
2962
LA262
LB11
2963
LA263
LB11
2964
LA264
LB11
2965
LA265
LB11
2966
LA266
LB11
2967
LA267
LB11
2968
LA268
LB11
2969
LA269
LB11
2970
LA270
LB11
2971
LA1
LB12
2972
LA2
LB12
2973
LA3
LB12
2974
LA4
LB12
2975
LA5
LB12
2976
LA6
LB12
2977
LA7
LB12
2978
LA8
LB12
2979
LA9
LB12
2980
LA10
LB12
2981
LA11
LB12
2982
LA12
LB12
2983
LA13
LB12
2984
LA14
LB12
2985
LA15
LB12
2986
LA16
LB12
2987
LA17
LB12
2988
LA18
LB12
2989
LA19
LB12
2990
LA20
LB12
2991
LA21
LB12
2992
LA22
LB12
2993
LA23
LB12
2994
LA24
LB12
2995
LA25
LB12
2996
LA26
LB12
2997
LA27
LB12
2998
LA28
LB12
2999
LA29
LB12
3000
LA30
LB12
3001
LA31
LB12
3002
LA32
LB12
3003
LA33
LB12
3004
LA34
LB12
3005
LA35
LB12
3006
LA36
LB12
3007
LA37
LB12
3008
LA38
LB12
3009
LA39
LB12
3010
LA40
LB12
3011
LA41
LB12
3012
LA42
LB12
3013
LA43
LB12
3014
LA44
LB12
3015
LA45
LB12
3016
LA46
LB12
3017
LA47
LB12
3018
LA48
LB12
3019
LA49
LB12
3020
LA50
LB12
3021
LA51
LB12
3022
LA52
LB12
3023
LA53
LB12
3024
LA54
LB12
3025
LA55
LB12
3026
LA56
LB12
3027
LA57
LB12
3028
LA58
LB12
3029
LA59
LB12
3030
LA60
LB12
3031
LA61
LB12
3032
LA62
LB12
3033
LA63
LB12
3034
LA64
LB12
3035
LA65
LB12
3036
LA66
LB12
3037
LA67
LB12
3038
LA68
LB12
3039
LA69
LB12
3040
LA70
LB12
3041
LA71
LB12
3042
LA72
LB12
3043
LA73
LB12
3044
LA74
LB12
3045
LA75
LB12
3046
LA76
LB12
3047
LA77
LB12
3048
LA78
LB12
3049
LA79
LB12
3050
LA80
LB12
3051
LA81
LB12
3052
LA82
LB12
3053
LA83
LB12
3054
LA84
LB12
3055
LA85
LB12
3056
LA86
LB12
3057
LA87
LB12
3058
LA88
LB12
3059
LA89
LB12
3060
LA90
LB12
3061
LA91
LB12
3062
LA92
LB12
3063
LA93
LB12
3064
LA94
LB12
3065
LA95
LB12
3066
LA96
LB12
3067
LA97
LB12
3068
LA98
LB12
3069
LA99
LB12
3070
LA100
LB12
3071
LA101
LB12
3072
LA102
LB12
3073
LA103
LB12
3074
LA104
LB12
3075
LA105
LB12
3076
LA106
LB12
3077
LA107
LB12
3078
LA108
LB12
3079
LA109
LB12
3080
LA110
LB12
3081
LA111
LB12
3082
LA112
LB12
3083
LA113
LB12
3084
LA114
LB12
3085
LA115
LB12
3086
LA116
LB12
3087
LA117
LB12
3088
LA118
LB12
3089
LA119
LB12
3090
LA120
LB12
3091
LA121
LB12
3092
LA122
LB12
3093
LA123
LB12
3094
LA124
LB12
3095
LA125
LB12
3096
LA126
LB12
3097
LA127
LB12
3098
LA128
LB12
3099
LA129
LB12
3100
LA130
LB12
3101
LA131
LB12
3102
LA132
LB12
3103
LA133
LB12
3104
LA134
LB12
3105
LA135
LB12
3106
LA136
LB12
3107
LA137
LB12
3108
LA138
LB12
3109
LA139
LB12
3110
LA140
LB12
3111
LA141
LB12
3112
LA142
LB12
3113
LA143
LB12
3114
LA144
LB12
3115
LA145
LB12
3116
LA146
LB12
3117
LA147
LB12
3118
LA148
LB12
3119
LA149
LB12
3120
LA150
LB12
3121
LA151
LB12
3122
LA152
LB12
3123
LA153
LB12
3124
LA154
LB12
3125
LA155
LB12
3126
LA156
LB12
3127
LA157
LB12
3128
LA158
LB12
3129
LA159
LB12
3130
LA160
LB12
3131
LA161
LB12
3132
LA162
LB12
3133
LA163
LB12
3134
LA164
LB12
3135
LA165
LB12
3136
LA166
LB12
3137
LA167
LB12
3138
LA168
LB12
3139
LA169
LB12
3140
LA170
LB12
3141
LA171
LB12
3142
LA172
LB12
3143
LA173
LB12
3144
LA174
LB12
3145
LA175
LB12
3146
LA176
LB12
3147
LA177
LB12
3148
LA178
LB12
3149
LA179
LB12
3150
LA180
LB12
3151
LA181
LB12
3152
LA182
LB12
3153
LA183
LB12
3154
LA184
LB12
3155
LA185
LB12
3156
LA186
LB12
3157
LA187
LB12
3158
LA188
LB12
3159
LA189
LB12
3160
LA190
LB12
3161
LA191
LB12
3162
LA192
LB12
3163
LA193
LB12
3164
LA194
LB12
3165
LA195
LB12
3166
LA196
LB12
3167
LA197
LB12
3168
LA198
LB12
3169
LA199
LB12
3170
LA200
LB12
3171
LA201
LB12
3172
LA202
LB12
3173
LA203
LB12
3174
LA204
LB12
3175
LA205
LB12
3176
LA206
LB12
3177
LA207
LB12
3178
LA208
LB12
3179
LA209
LB12
3180
LA210
LB12
3181
LA211
LB12
3182
LA212
LB12
3183
LA213
LB12
3184
LA214
LB12
3185
LA215
LB12
3186
LA216
LB12
3187
LA217
LB12
3188
LA218
LB12
3189
LA219
LB12
3190
LA220
LB12
3191
LA221
LB12
3192
LA222
LB12
3193
LA223
LB12
3194
LA224
LB12
3195
LA225
LB12
3196
LA226
LB12
3197
LA227
LB12
3198
LA228
LB12
3199
LA229
LB12
3200
LA230
LB12
3201
LA231
LB12
3202
LA232
LB12
3203
LA233
LB12
3204
LA234
LB12
3205
LA235
LB12
3206
LA236
LB12
3207
LA237
LB12
3208
LA238
LB12
3209
LA239
LB12
3210
LA240
LB12
3211
LA241
LB12
3212
LA242
LB12
3213
LA243
LB12
3214
LA244
LB12
3215
LA245
LB12
3216
LA246
LB12
3217
LA247
LB12
3218
LA248
LB12
3219
LA249
LB12
3220
LA250
LB12
3221
LA251
LB12
3222
LA252
LB12
3223
LA253
LB12
3224
LA254
LB12
3225
LA255
LB12
3226
LA256
LB12
3227
LA257
LB12
3228
LA258
LB12
3229
LA259
LB12
3230
LA260
LB12
3231
LA261
LB12
3232
LA262
LB12
3233
LA263
LB12
3234
LA264
LB12
3235
LA265
LB12
3236
LA266
LB12
3237
LA267
LB12
3238
LA268
LB12
3239
LA269
LB12
3240
LA270
LB12
3241
LA1
LB13
3242
LA2
LB13
3243
LA3
LB13
3244
LA4
LB13
3245
LA5
LB13
3246
LA6
LB13
3247
LA7
LB13
3248
LA8
LB13
3249
LA9
LB13
3250
LA10
LB13
3251
LA11
LB13
3252
LA12
LB13
3253
LA13
LB13
3254
LA14
LB13
3255
LA15
LB13
3256
LA16
LB13
3257
LA17
LB13
3258
LA18
LB13
3259
LA19
LB13
3260
LA20
LB13
3261
LA21
LB13
3262
LA22
LB13
3263
LA23
LB13
3264
LA24
LB13
3265
LA25
LB13
3266
LA26
LB13
3267
LA27
LB13
3268
LA28
LB13
3269
LA29
LB13
3270
LA30
LB13
3271
LA31
LB13
3272
LA32
LB13
3273
LA33
LB13
3274
LA34
LB13
3275
LA35
LB13
3276
LA36
LB13
3277
LA37
LB13
3278
LA38
LB13
3279
LA39
LB13
3280
LA40
LB13
3281
LA41
LB13
3282
LA42
LB13
3283
LA43
LB13
3284
LA44
LB13
3285
LA45
LB13
3286
LA46
LB13
3287
LA47
LB13
3288
LA48
LB13
3289
LA49
LB13
3290
LA50
LB13
3291
LA51
LB13
3292
LA52
LB13
3293
LA53
LB13
3294
LA54
LB13
3295
LA55
LB13
3296
LA56
LB13
3297
LA57
LB13
3298
LA58
LB13
3299
LA59
LB13
3300
LA60
LB13
3301
LA61
LB13
3302
LA62
LB13
3303
LA63
LB13
3304
LA64
LB13
3305
LA65
LB13
3306
LA66
LB13
3307
LA67
LB13
3308
LA68
LB13
3309
LA69
LB13
3310
LA70
LB13
3311
LA71
LB13
3312
LA72
LB13
3313
LA73
LB13
3314
LA74
LB13
3315
LA75
LB13
3316
LA76
LB13
3317
LA77
LB13
3318
LA78
LB13
3319
LA79
LB13
3320
LA80
LB13
3321
LA81
LB13
3322
LA82
LB13
3323
LA83
LB13
3324
LA84
LB13
3325
LA85
LB13
3326
LA86
LB13
3327
LA87
LB13
3328
LA88
LB13
3329
LA89
LB13
3330
LA90
LB13
3331
LA91
LB13
3332
LA92
LB13
3333
LA93
LB13
3334
LA94
LB13
3335
LA95
LB13
3336
LA96
LB13
3337
LA97
LB13
3338
LA98
LB13
3339
LA99
LB13
3340
LA100
LB13
3341
LA101
LB13
3342
LA102
LB13
3343
LA103
LB13
3344
LA104
LB13
3345
LA105
LB13
3346
LA106
LB13
3347
LA107
LB13
3348
LA108
LB13
3349
LA109
LB13
3350
LA110
LB13
3351
LA111
LB13
3352
LA112
LB13
3353
LA113
LB13
3354
LA114
LB13
3355
LA115
LB13
3356
LA116
LB13
3357
LA117
LB13
3358
LA118
LB13
3359
LA119
LB13
3360
LA120
LB13
3361
LA121
LB13
3362
LA122
LB13
3363
LA123
LB13
3364
LA124
LB13
3365
LA125
LB13
3366
LA126
LB13
3367
LA127
LB13
3368
LA128
LB13
3369
LA129
LB13
3370
LA130
LB13
3371
LA131
LB13
3372
LA132
LB13
3373
LA133
LB13
3374
LA134
LB13
3375
LA135
LB13
3376
LA136
LB13
3377
LA137
LB13
3378
LA138
LB13
3379
LA139
LB13
3380
LA140
LB13
3381
LA141
LB13
3382
LA142
LB13
3383
LA143
LB13
3384
LA144
LB13
3385
LA145
LB13
3386
LA146
LB13
3387
LA147
LB13
3388
LA148
LB13
3389
LA149
LB13
3390
LA150
LB13
3391
LA151
LB13
3392
LA152
LB13
3393
LA153
LB13
3394
LA154
LB13
3395
LA155
LB13
3396
LA156
LB13
3397
LA157
LB13
3398
LA158
LB13
3399
LA159
LB13
3400
LA160
LB13
3401
LA161
LB13
3402
LA162
LB13
3403
LA163
LB13
3404
LA164
LB13
3405
LA165
LB13
3406
LA166
LB13
3407
LA167
LB13
3408
LA168
LB13
3409
LA169
LB13
3410
LA170
LB13
3411
LA171
LB13
3412
LA172
LB13
3413
LA173
LB13
3414
LA174
LB13
3415
LA175
LB13
3416
LA176
LB13
3417
LA177
LB13
3418
LA178
LB13
3419
LA179
LB13
3420
LA180
LB13
3421
LA181
LB13
3422
LA182
LB13
3423
LA183
LB13
3424
LA184
LB13
3425
LA185
LB13
3426
LA186
LB13
3427
LA187
LB13
3428
LA188
LB13
3429
LA189
LB13
3430
LA190
LB13
3431
LA191
LB13
3432
LA192
LB13
3433
LA193
LB13
3434
LA194
LB13
3435
LA195
LB13
3436
LA196
LB13
3437
LA197
LB13
3438
LA198
LB13
3439
LA199
LB13
3440
LA200
LB13
3441
LA201
LB13
3442
LA202
LB13
3443
LA203
LB13
3444
LA204
LB13
3445
LA205
LB13
3446
LA206
LB13
3447
LA207
LB13
3448
LA208
LB13
3449
LA209
LB13
3450
LA210
LB13
3451
LA211
LB13
3452
LA212
LB13
3453
LA213
LB13
3454
LA214
LB13
3455
LA215
LB13
3456
LA216
LB13
3457
LA217
LB13
3458
LA218
LB13
3459
LA219
LB13
3460
LA220
LB13
3461
LA221
LB13
3462
LA222
LB13
3463
LA223
LB13
3464
LA224
LB13
3465
LA225
LB13
3466
LA226
LB13
3467
LA227
LB13
3468
LA228
LB13
3469
LA229
LB13
3470
LA230
LB13
3471
LA231
LB13
3472
LA232
LB13
3473
LA233
LB13
3474
LA234
LB13
3475
LA235
LB13
3476
LA236
LB13
3477
LA237
LB13
3478
LA238
LB13
3479
LA239
LB13
3480
LA240
LB13
3481
LA241
LB13
3482
LA242
LB13
3483
LA243
LB13
3484
LA244
LB13
3485
LA245
LB13
3486
LA246
LB13
3487
LA247
LB13
3488
LA248
LB13
3489
LA249
LB13
3490
LA250
LB13
3491
LA251
LB13
3492
LA252
LB13
3493
LA253
LB13
3494
LA254
LB13
3495
LA255
LB13
3496
LA256
LB13
3497
LA257
LB13
3498
LA258
LB13
3499
LA259
LB13
3500
LA260
LB13
3501
LA261
LB13
3502
LA262
LB13
3503
LA263
LB13
3504
LA264
LB13
3505
LA265
LB13
3506
LA266
LB13
3507
LA267
LB13
3508
LA268
LB13
3509
LA269
LB13
3510
LA270
LB13

In some embodiments, the compound is selected from the group consisting of:

According to another aspect of the present disclosure, a first device is also provided. The first device includes a first organic light emitting device, that includes an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer can include a compound according to the formula M(LA)x(LB)y(LC)z, and its variations as described herein.

The first device can be one or more of a consumer product, an organic light-emitting device and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.

The organic layer can also include a host. In some embodiments, the host can include a metal complex. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡C—CnH2n+1, Ar1, Ar1-Ar2, CnH2n—Ar1, or no substitution. In the preceding substituents n can range from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

The host can be a compound selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The host can include a metal complex. The host can be a specific compound selected from the group consisting of:

and combinations thereof.

In yet another aspect of the present disclosure, a formulation that comprises a compound according to the formula M(LA)x(LB)y(LC)z is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein.

Combination with Other Materials

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

HIL/HTL:

A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:

Each of Ar1 to Ar9 is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:

wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y101-Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.

Host:

The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have the following general formula:

wherein Met is a metal; (Y103-Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.

Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzosclenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, host compound contains at least one of the following groups in the molecule:

wherein R101 to R107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. X101 to X108 is selected from C (including CH) or N. Z101 and Z102 is selected from NR101, O, or S.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.

In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of the following groups in the molecule:

wherein k is an integer from 1 to 20; L101 is an another ligand, k′ is an integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

In one aspect, compound used in ETL contains at least one of the following groups in the molecule:

wherein R101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20, X101 to X108 is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.

In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 1 below. Table 1 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.


TABLE 1
MATERIAL
EXAMPLES OF MATERIAL
PUBLICATIONS
Hole injection materials
Phthalocyanine and porphyin compounds
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Synth. Met. 87, 171 (1997) WO2007002683
Phosphonic acid and silane SAMs
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Triarylamine or polythiophene polymers with conductivity dopants
EP1725079A1
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US20050123751 SID Symposium Digest, 37, 923 (2006) WO2009018009
n-type semiconducting organic complexes
US20020158242
Metal organometallic complexes
US20060240279
Cross-linkable compounds
US20080220265
Polythiophene based polymers and copolymers
WO 2011075644 EP2350216
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Triarylamines (e.g., TPD, α-NPD)
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U.S. Pat. No. 5,061,569
EP650955
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Appl. Phys. Lett. 90, 183503 (2007)
Appl. Phys. Lett. 90, 183503 (2007)
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Synth. Met. 91, 209 (1997)
Arylamine carbazole compounds
Adv. Mater. 6, 677 (1994), US20080124572
Triarylamine with (di)benzothiophenei/(di) zofuran
US20070278938, US20080106190 US20110163302
Indolocarbazoles
Synth. Met. 111, 421 (2000)
Isoindole compounds
Chem. Mater. 15, 3148 (2003)
Metal carbene complexes
US2008008221
Phosphorescent OLED host materials
Red hosts
Arylcarbazoles
Appl. Phys. Lett. 78, 1622 (2001)
Metal 8-hydroxyquinolates (e.g., Alq3, BAlq)
Nature 395, 151 (1998)
US20060202194
WO2005014551
WO2006072002
Metal phenoxybenzothiazole compounds
Appl. Phys. Lett. 90, 123509 (2007)
Conjugated oligomers and polymers (e.g., polyfluorene)
Org. Electron. 1, 15 (2000)
Aromatic fused rings
WO2009066779, WO2009066778, WO2009063833, US20090045731, US20090045730, WO2009008311, US20090008605, US20090009065
Zinc complexes
WO2010056066
Chrysene based compounds
WO2011086863
Green hosts
Arylcarbozoles
Appl. Phys. Lett. 78, 1622 (2001)
US20030175553
WO2001039234
Aryltriphenylene compounds
US20060280965
US20060280965
WO2009021126
Poly-fused heteroaryl compounds
US20090309488 US20090302743 US20100012931
Donor acceptor type molecules
WO2008056746
WO2010107244
Aza-carbazole/DBT/DBF
JP2008074939
US20100187984
Polymers (e.g., PVK)
Appl. Phys. Lett. 77, 2280 (2000)
Spirofluorene compounds
WO2004093207
Metal phenoxybenzooxazole compounds
WO2005089025
WO2006132173
JP200511610
Spirofluorene-carbazole compounds
JP2007254297
JP2007254297
Indolocarbazoles
WO2007063796
WO2007063754
5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole)
J. Appl. Phys. 90, 5048 (2001)
WO2004107822
Tetraphenylene complexes
US20050112407
Metal phenoxypyridine compounds
WO2005030900
Metal coordination complexes (e,g., Zn, Al with N{circumflex over ( )}N ligands)
US20040137268, US20040137267
Blue hosts
Arylcarbazoles
Appl. Phys. Lett, 82, 2422 (2003)
US20070190359
Dibenzothiophene/ Dibenzofuran-carbazole compounds
WO2006114966, US20090167162
US20090167162
WO2009086028
US20090030202, US20090017330
US20100084966
Silicon aryl compounds
US20050238919
WO2009003898
Silicon/Germanium aryl compounds
EP2034538A
Aryl benzoyl ester
WO2006100298
Carbazole linked by non- conjugated groups
US20040115476
Aza-carbazoles
US20060121308
High triplet metal organometallic complex
U.S. Pat. No. 7,154,114
Phosphorescent dopants
Red dopants
Heavy metal porphyrins (e.g., PtOEP)
Nature 395, 151 (1998)
Iridium(III) organometallic complexes
Appl. Phys. Lett. 78, 1622 (2001)
US2006835469
US2006835469
US20060202194
US20060202194
US20070087321
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US20070087321
Adv. Mater. 19, 739 (2007)
WO2009100991
WO2008101842
U.S. Pat. No. 7,232,618
Platinum(II) organornetallic complexes
WO2003040257
US20070103060
Osminum(III) complexes
Chem. Mater. 17, 3532 (2005)
Ruthenium(II) complexes
Adv. Mater. 17, 1059 (2005)
Rhenium (I), (II), and (III) complexes
US20050244673
Green dopants
Iridium(III) organometallic complexes
Inorg. Chem. 40, 1704 (2001)
US20020034656
U.S Pat. No. 7,332,232
US20090108737
WO2010028151
EP1841834B
US20060127696
US20090039776
U.S. Pat. No. 6,921,915
US20100244004
U.S. Pat. No. 6,687,266
Chem. Mater. 16 2480 (2004)
US20070190359
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Adv. Mater 16, 2003 (2004)
Angew. Chem. Int Ed. 2006, 45, 7800
WO2009050290
US20090165846
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US20010015432
US20100295032
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Pt(11) organometallic complexes, including polydentated ligands
Appl. Phys. Lett. 86, 153505 (2005)
Appl. Phys. Lett. 86, 153505 (2005)
Chem. Lett. 34, 592 (2005)
WO2002015645
US20060263635
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Cu complexes
WO2009000673
US20070111026
Gold complexes
Chem. Commun. 2906 (2005)
Rhenium(III) complexes
Inorg. Chem. 42, 1248 (2003)
Osmium(II) complexes
U.S. Pat. No. 7,279,704
Deuterated organometalli ccomplexes
US20030138657
Organometallic complexes with two or more metal centers
US20030152802
U.S. Pat. No. 7,090,928
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U.S. Pat. No. 7,534,505
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WO2005123873
WO2005123873
WO2007004380
WO2006082742
Osminium(II) complexes
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Organometallics 23, 3745 (2004)
Gold complexes
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Platinum (II) complexes
WO2006098120, WO2006103874
Pt tetradentate complexes with at least one metal- carbene bond
U.S. Pat. No. 7,655,323
Exciton/hole blocking layer materials
Bathocuprine compounds (e.g., BCP, BPhen)
Appl. Phys. Lett. 75, 4 (1999)
Appl. Phys. Lett. 79, 449 (2001)
Metal 8-hydroxyquinolates (e.g., BAlq)
Appl. Phys. Lett. 81, 162 (2002)
5-member ring electron deficient heterocycles such as triazole, oxadiazole, imidazole, benzoimidazole
Appl. Phys. Lett. 81, 162 (2002)
Triphenylene compounds
US20050025993
Fluorinated aromatic compounds
Appl. Phys. Lett. 79, 156 (2001)
Phenothiazine-S-oxide
WO2008132085
Silylated five-membered nitrogen, oxygen, sulfur or phosphorus dibenzoheterocycles
WO20110079051
Aza-carbazoles
US20060121308
Electron transporting materials
Anthracene-benzoimidazole compounds
WO2003060956
US20090179554
Aza triphenylene derivatives
US20090115316
Anthracene-benzothiazole compounds
Appl. Phys. Lett. 89, 063504 (2006)
Metal 8-hydroxyquinolates (e.g., Alq3, Zrq4)
Appl. Phys. Lett. 51, 913 (1987) U.S. Pat. No. 7,230,107
Metal hydroxybenoquinolates
Chem. Lett. 5, 905 (1993)
Bathocuprine compounds such as BCP, BPhen, etc
Appl. Phys. Lett. 91, 263503 (2007)
Appl. Phys. Lett. 79, 449 (2001)
5-member ring electron deficient heterocycles (e.g.,triazole, oxadiazole, imidazole, benzoimidazole)
Appl. Phys. Lett. 74, 865 (1999)
Appl. Phys. Lett. 55, 1489 (1989)
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Silole compounds
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Arylborane compounds
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Fluorinated aromatic compounds
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Fullerene (e.g., C60)
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Experimental

All reactions were carried out under nitrogen protections unless specified otherwise. All solvents for reactions are anhydrous and used as received from commercial sources.

Synthesis of Compound 81

Synthesis of 4-(3,5-dimethylphenyl)quinazoline

(3,5-Dimethylphenyl)boronic acid (5.75 g, 38.4 mmol), 4-chloroquinazoline (5.05 g, 30.7 mmol), and K2CO3 (8.48 g, 61.4 mmol) were dissolved in toluene (150 mL) and water (30 mL). The mixture was degassed by bubbling it with nitrogen for 30 minutes and adding tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (1.78 g, 1.53 mmol). The mixture was then held at 100° C. overnight. Upon completion of the reaction, the mixture was cooled to room temperature, extracted with toluene, and washed with brine and water. The organic solution was filtered and evaporated. The crude product was purified by column chromatography using a gradient mixture of ethyl acetate (EA) (from 20 to 65%) in heptanes. The white powder product was recrystallized three times from heptanes to give colorless crystals (5.0 g, 70% yield).

Synthesis of Ir(III) Dimer

The 4-(3,5-Dimethylphenyl)quinazoline (2.50 g, 10.7 mmol) was solubilized in ethoxyethanol (30 mL) and water (10 mL) and degassed by bubbling with nitrogen for 30 minutes. Iridium chloride (1.32 g, 3.56 mmol) was then added to the mixture and the reaction was refluxed under nitrogen for 24 h. After cooling down to room temperature, the solid product was filtered, washed with methanol, and dried to give the Ir(II) dimer (2.40 g, 97% yield).

Synthesis of Compound 81

Ir(III) Dimer (2.00 g, 1.15 mmol) and 3,7-diethylnonane-4,6-dione (1.84 g, 8.64 mmol) were suspended in 2-ethoxyethanol (35 mL) and degassed by bubbling nitrogen. Potassium carbonate (1.19 g, 8.64 mmol) was then added, and the mixture was stirred at room temperature for 48 h. The solvent was evaporated under vacuum, methanol was added and the solid was filtered. The crude red solid was purified by column chromatography starting with 100% heptanes and slowly adding 15% of dichloromethane in heptanes. The solid obtained were recrystallized from dichloromethane and methanol. The target compound is obtained as a red solid (0.45 g, 22% yield).

Synthesis of Comparative Compound 1

The Ir(III) Dimer (2.50 g, 1.44 mmol)(see above) and pentane-2,4-dione (1.48 g, 14.4 mmol) were diluted in 2-ethoxyethanol (48 mL) and degassed by bubbling nitrogen. Potassium carbonate (1.99 g, 14.4 mmol) was then added to the mixture, which was then stirred at room temperature for 24 h. The solvent was evaporated under vacuum. The crude oil was dissolved in DCM and filtered through a plug of triethylamine-treated silica. The solvent was then evaporated. Methanol (25 mL) was added to the solid and the product was recrystallized in a freezer. The target compound was obtained as a dark red solid (0.52 g, 22% yield).

Device Examples

All example devices were fabricated by high vacuum (<10−7 Torr) thermal evaporation. The anode electrode was 1200 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1,000 Å of Al. All devices are encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after fabrication, and a moisture getter was incorporated inside the package.

The organic stack of the device examples consisted of sequentially, from the ITO surface, 100 Å of LG101 (purchased from LG Chem) as a hole injection layer (HIL), 400 Å of 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD) as a hole transporting layer (HTL), 400 Å of the inventive compound or comparative compound doped in BAlq as a host and compound H as a stability dopant (SD) with as an emissive layer (EML), 100 Å of BAlq as a blocking layer (BL), and 450 Å of Alq3 (tris-8-hydroxyquinoline aluminum) as an electron transport layer (ETL).

The device results and data are summarized in Tables 2 and 3 from those devices. As used herein, NPD, Alq3, BAlq, SD have the following structures:disclosure


TABLE 2
Device structures of inventive compounds
HIL
HTL
EML (400 Å, doping %)
BL
ETL
Device
LG101 100 Å
NPD 400 Å
BAlq
Compound H
Compound 81
BAlq 100 Å
Alq 450 Å
Example
9%
3%
Comparative
LG101 100 Å
NPD 400 Å
BAlq
Compound H
Comparative
BAlq 100 Å
Alq 450 Å
Example
9%
compound 1
3%


TABLE 3
VTE device results
1931 CIE
At 1,000 nits
CIE
CIE
λ max
FWHM
Voltage
LE
EQE
x
y
[nm]
[nm]
[%]
[%]
[%]
Device
0.71
0.29
668
62
99
129
119
Example
Comparative
0.71
0.29
672
72
100
100
100
Example

Table 3 summarizes the performance of the devices. The driving voltage (V), luminous efficiency (LE), and external quantum efficiency (EQE) were measured at 1000 nits. The EL spectra were measured at 10 mA/cm2. Both device example and comparative example devices showed very deep red color with a CIE of (0.71, 0.29). Example device and comparative example one has 668 nm and 672 nm of peak wavelength, respectively and the example device has 10 nm narrower full width at half maximum (FWHM) than the comparative example. Example device has 29% higher LE and 19% higher EQE than comparative example.

It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

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Citation

Patents Cited in This Cited by
Title Current Assignee Application Date Publication Date
含芳基联喹唑啉类金属铱配合物红色有机电致磷光材料及其有机电致发光器件 西安瑞联近代电子材料有限责任公司 13 July 2010 01 December 2010
Composition for charge-transporting film and ion compound, charge-transporting film and organic electroluminescent device using same, and method for manufacturing organic electroluminescent device and method for producing charge-transporting film MITSUBISHI CHEMICAL CORPORATION 07 March 2005 22 November 2006
Amine compound and electro-luminescence device comprising same HODOGAYA CHEMICAL CO., LTD.,MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD. 31 October 1994 03 May 1995
磷光材料 通用显示公司 16 September 2009 29 January 2014
红色磷光化合物和使用它的有机电致发光器件 LG电子株式会社 13 May 2005 09 April 2008
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