Abstract:
A method for fabricating an OLED by preparing phosphorescent metal complexes in situ is provided. In particular, the method simultaneously synthesizes and deposits copper (I) complexes in an organic light emitting device. Devices comprising such complexes may provide improved photoluminescent and electroluminescent properties.

Description:
[0001]    This application claims priority to U.S. Provisional Application Ser. No. 61/400,505, filed Jul. 29, 2010, the disclosure of which is herein expressly incorporated by reference in its entirety. 
     
    
       [0002]    This invention was made with government support under DE-FC26-08NT01585 and DE-FG02-07ER84809 awarded by the Department of Energy. The government has certain rights in the invention. 
     
    
       [0003]    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, The 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 
       [0004]    The present invention relates to phosphorescent complexes, and their use in organic light emitting devices (OLEDs). More particularly, the invention relates to a method for simultaneously synthesizing and depositing phosphorescent copper (I) complexes for fabrication of an OLED. 
       BACKGROUND 
       [0005]    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. 
         [0006]    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. 
         [0007]    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. 
         [0008]    One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy) 3 , which has the following structure: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0009]    In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line. 
         [0010]    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. 
         [0011]    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. 
         [0012]    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. 
         [0013]    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. 
         [0014]    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. 
         [0015]    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. 
         [0016]    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 
       [0017]    Methods for depositing a phosphorescent complex in situ are provided. The method comprises reacting one or more of a metal complex having the formula MX n  and one or more of a ligand selected from L 1 , L 2 , and L 3  to form a phosphorescent complex having the formula (L 1 ) a (L 2 ) b (L 3 ) c (MX p ) m . The one or more metal complexes having the formula MX n  and the one or more ligands L 1 , L 2 , and L 3  are thermally vacuum deposited in combination over a substrate, wherein the reaction is completed to obtain the phosphorescent complex. 
         [0018]    M is a transition metal or lanthanide. X is alkyl, aryl, F, Cl, Br, I, SCN, OCN, CN, OR, and SR or combinations thereof. R is alkyl or aryl. n is 1-10. Preferably, n is 1-3. p is equal to [n-(a·a′)+(b·b′)+(c·c′)]. m is 1-6. Preferably, m is 2. Each of L 1 , L 2 , and L 3  is independently a mono-, di-, tri- or polydentate ligand. Each of a, b, and c may represent mono, bis or tris ligand coordination. a is 1-10, b is 0-9, and c is 0-9. a′ is the number of coordination sites of L 1 . b′ is the number of coordination sites of L 2 . c′ is the number of coordination sites of L 3 . [p+(a·a′)+(b·b′)+(c·c′)] is equal to n. 
         [0019]    Preferably, the metal complex is copper (I). More preferably, the metal complex is CuI. 
         [0020]    At, least one of the ligands L 1 , L 2 , and L 3  may be a neutral ligand. In one aspect, at least one of L 1 , L 2 , and L 3  is a neutral ligand that is coordinated to the Cu through a C, N, O, P or S atom. Preferably, at least one of L 1 , L 2 , and L 3  is a neutral ligand that is coordinated to the Cu through a N atom. 
         [0021]    In another aspect, each of L 1 , L 2 , and L 3  is a neutral ligand that is coordinated to the Cu through a C, N, O, P or S atom. Preferably, each of L 1 , L 2 , and L 3  is a neutral ligand that is coordinated to the Cu through a N atom. 
         [0022]    In yet another aspect, at least one of L 1 , L 2 , and L 3  is selected from the group consisting of: 
         [0000]    
       
                 
         
             
             
         
       
       
                 
         
             
             
         
       
     
         [0023]    X is S, O, or NR. R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8  and R 9  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, sulfonyl, sulfonyl, phosphino, and combinations thereof. The ligand is coordinated to the metal M via at least atom of the ligand. 
         [0024]    Specific examples of ligands L 1 , L 2 , and L 3  are provided. In one aspect, at least one of L 1 , L 2 , and L 3  is selected from the group consisting of: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0025]    R′ and R″ 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. 
         [0026]    Alternatively, at least one of the ligands L 1 , L 2 , and L 3  may be a charged ligand. In one aspect, at least one of L 1 , L 2 , and L 3  is a charged ligand having the formula: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0027]    Y and Z are independently selected from the group consisting of C, N, O, P and S. 
         [0028]    In another aspect, 
         [0000]    
       
                 
         
             
             
         
       
     
         [0029]    A and B are each independently a 5 or 6-membered aromatic or heteroaromatic ring. A-B represents a bonded pair of aromatic or heteroaromatic rings coordinated to the metal via a nitrogen atom on ring A and an sp 2  hybridized carbon atom on ring B. Each of R A  and R B  may represent mono, di, tri, or tetra substituents. Each of R A  and R B  substituents 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. 
         [0030]    The phosphorescent complex obtained from the method may be homoleptic or heteroleptic. In one aspect, b is 0 and c is 0. In another aspect, at least one of b and c is equal to 1. 
         [0031]    In one aspect, p is 0. 
         [0032]    Specific examples of the phosphorescent complex obtained from the method are provided. In one aspect, the phosphorescent complex is selected from the group consisting of CuI:TPBi, CuI:PBD, or CuI:mCPy. 
         [0033]    In one aspect, the one or more metal complexes having the formula MX n  and the one or more ligands L 1 , L 2 , and L 3  are deposited by solution processing. In another aspect, the one or more metal complexes having the formula MX n  and the one or more ligands L 1 , L 2 , and L 3  are deposited by thermal evaporation. 
         [0034]    In one aspect, the one or more metal complexes MX n  is mixed with an organic solvent to form a first solution and at least one of L 1 , L 2 , and L 3  is mixed with an organic solvent to form a second solution, prior to depositing over the substrate, and then the first solution and the second solution are deposited in combination over the substrate. 
         [0035]    In another aspect, the method further comprises providing a first electrode disposed over the substrate, depositing the one or more metal complexes having the formula MX n  and the ligand L on the first electrode, and depositing a second electrode. Preferably, the first electrode is an anode and the second electrode is a cathode. 
         [0036]    In another aspect, the method further comprises providing a first electrode disposed over the substrate, providing an organic layer disposed over the first electrode, depositing the one or more metal complexes having the formula MX n  and the ligand L on the first electrode, and depositing a second electrode. Preferably, the first electrode is an anode and the second electrode is a cathode. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0037]      FIG. 1  shows an organic light emitting device. 
           [0038]      FIG. 2  shows an inverted organic light emitting device that does not have a separate electron transport layer. 
           [0039]      FIG. 3  shows photoluminescent spectra of spin cast TPBi and CuI:TPBi films at a 1:4 ratio. 
           [0040]      FIG. 4  shows the external quantum efficiency-luminance curve for a device having the structure ITO/NPD (1000 Å)/CuI:TPBi (1:1.7, 100 Å)/TPBi (500 Å)/LiF (10 Å)/Al (1000 Å), where the CuI:TPBi layer was made by co-depositing CuI and TPBi in vacuum chamber. 
           [0041]      FIG. 5  shows the electroluminescent spectra for a device having the structure ITO/NPD (1000 Å)/CuI:TPBi (1:1.7, 100 Å)/TPBi (500 Å)/LiF (10 Å)/Al (1000 Å) under different voltages 
           [0042]      FIG. 6  shows the photoluminescent spectra of spin cast PBD and CuI:PBD films at a 1:4 ratio. 
           [0043]      FIG. 7  shows the external quantum efficiency-luminance curve for a device having the structure ITO/NPD (1000 Å)/CuI:PBD (1:1, 100 Å)/PBD (500 Å)/LiF (10 Å)/Al (1000 Å), where the CuI:PBD layer was made by co-depositing CuI and PBD in vacuum chamber. 
           [0044]      FIG. 8  shows the electroluminescent spectra for a device having the structure ITO/NPD (1000 Å)/CuI:PBD (1:1, 100 Å)/PBD (500 Å)/LiF (10 Å)/Al (1000 Å) under different applied voltages. 
           [0045]      FIG. 9  shows the emission spectra of CuI:mCPy films with different molar ratios made by co-depositing CuI and mCPy in vacuum chamber. 
           [0046]      FIG. 10  shows the electroluminescent spectra of devices 1-4. 
           [0047]      FIG. 11  shows the electroluminescent spectra of devices 1-4 at different voltages. 
           [0048]      FIG. 12  shows the electroluminescent spectra of devices 5 and 6 at 8 V. 
           [0049]      FIG. 13  shows the photoluminescent spectra of CuI:mCP and neat mCP films. 
           [0050]      FIG. 14  shows the photoluminescent spectra of model complex A in solid, neat film, A:mCPy film, and in chamber co-deposited CuI:mCPy film. The former two films were made by spin coating of sample in CH 3 CN+CH 2 Cl 2  solution. 
           [0051]      FIG. 15  shows an ORTEP drawing of the model complex B with ellipsoids at the 30% probability level. Hydrogen and solvents are omitted for clarity. 
       
    
    
     DETAILED DESCRIPTION 
       [0052]    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. 
         [0053]    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. 
         [0054]    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. 
         [0055]      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 , and a cathode  160 . 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. 
         [0056]    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 F.sub.4-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. 
         [0057]      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 . 
         [0058]    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 . 
         [0059]    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. 
         [0060]    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. patent application Ser. No. 10/233,470, 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 processibility 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. 
         [0061]    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, 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, 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.). 
         [0062]    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. 
         [0063]    The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference. 
         [0064]    A wide range of phosphorescent emissive materials for application to OLEDs and other optoelectronic devices have been reported. These materials are typically synthesized and purified as crystalline material, prior to their incorporation into a device via thermal evaporation. While phosphorescent copper complexes can be synthesized and purified as crystalline materials, they decompose on attempts to deposit them by thermal evaporation. Phosphorescent copper complexes may be desirable for use in OLEDs, but their use has been limited because of these sublimation problems. 
         [0065]    Herein, a new method for the fabrication of a phosphorescent complex is provided. Phosphorescent emitters are prepared in situ by co-depositing a ligand and a metal complex to form a film. In particular, the method may involve the co-deposition of CuI and one or more organic ligands to form the phosphorescent complex. Particularly desirable phosphorescent complexes that can be obtained using this method have the general formula (CuI) y L z , with (CuI) y  cluster cores. 
         [0066]    The organic ligands that may be used in this method can include a wide range of materials, provided they are sufficiently Lewis basic enough to coordinate to the metal, and in particular Cu ions. Examples of suitable ligands may include, but are not limited to, 2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), 3,5-di(9H-carbazol-9-yl)pyridine (mCPy), or 1,3-bis(carbazol-9-yl)benzene (mCP).  FIGS. 3-5  show electroluminescent and photoluminescent data for CuI:TPBi.  FIGS. 6-8  show electroluminescent and photoluminescent data for CuI:PBD.  FIGS. 9-12  and  14  show electroluminescent and photoluminescent data for CuI:mCPy.  FIG. 13  shows electroluminescent and photoluminescent data for CuI:mCP.  FIG. 15  shows the structure of Cu 4 I 4 (mCPy 4 ).3CH 2 Cl 2 , or the model complex B. 
         [0067]    Phosphorescent complexes made by the method provided herein are suitable for use in an emissive layer of an OLED. For example, the methods provided herein were used to prepare OLEDs with a phosphorescent copper complex as the emitting center and the devices demonstrated an EQE value of 4.4%. 
         [0068]    Novel methods are provided for in situ formation of phosphorescent compounds, particularly copper (I) complexes, by co-depositing one or more metal complexes and one or more ligands under vacuum. These methods may be used to fabricate OLEDs containing phosphorescent copper (I) complexes. The co-deposition method may also be used for in situ formation of emissive complexes containing other metals or metal halides suitable for use as an emissive layer in OLEDs. 
         [0069]    Over the past ten years, tremendous improvements in phosphorescent organic light emitting diodes (PHOLEDs) have been achieved with the help of emissive iridium-based complexes. Generally, iridium complexes possess good thermal stability, suitable for evaporation under vacuum, and potentially 100% internal quantum efficiency. fac-tris(2-phenylpyridine) iridium [Ir(ppy)3] and bis(2-phenylpyridine)(acetylacetonate)iridium [Ir(ppy) 2 (acac)] are two examples of such iridium complexes. See, Lamansky, S.; Djurovich, P.; Murphy, D.; Abdel-Razzaq, F.; Lee, H. E.; Adachi, C.; Burrows, P. E.; Forrest, S. R.; Thompson, M. E., Journal of the American Chemical Society 2001, 123, (18), 4304-4312; Adachi, C.; Baldo, M. A.; Thompson, M. E.; Forrest, S. R, Journal of Applied Physics 2001, 90, (10),5048-5051. 
         [0070]    However, iridium is low in natural abundance and expensive, prohibiting PHOLEDs from being widely used in applications, such as displays and solid state lighting. As a result, there has been an increasing interest in luminescent copper(I) complexes and their application in PHOLEDs, because copper(I) complexes are the largest class of phosphorescent compounds with a relatively abundant, cheap, and environmentally friendly metal element. See, Arrnaroli, N.; Accorsi, G.; Cardinali, F.; Listorti, A.,  Photochemistry and Photophysics of Coordination Compounds  12007, 280, 69-115. 
         [0071]    Among the luminescent copper(I) complexes, copper(I) iodide based complexes are well known for their rich structure and photophysical behavior. See, Ford, P. C.; Carlati, E.; Bourassa, J., Chemical Reviews 1999, 99, (12), 3625.3647; Kyle, K. R.; Ryu, C. K.; Dibenedetto, J. A.; Ford, P. C.,  Journal of the American Chemical Society  1991, 113, (8), 2954-2965; Manbeck, G. F.; Brennessel, W. W.; Evans, C. M.; Eisenberg, R.,  Inorganic Chemistry  2010, 49, (6), 2834-2843; Tard, C.; Perruchas, S.; Maron, S.; Le Goff, X. F.; Guillen, F.; Garcia, A.; Vigneron, J.; Elcheberry, A.; Gacoin, T.; Boilot, J. P.,  Chemistry of Materials  2008, 20, (22), 7010-7016; Vitale, M.; Ford, P. C.,  Coordination Chemistry Reviews  2001, 219, 3-16; Ford, P. C.,  Coordination Chemistry Reviews  1994, 132, 129-140; Ryu, C. K.; Vitale, M.; Ford, P. C.,  Inorganic Chemistry  1993, 32, (6), 869-874. For example, structures ranging from the mononuclear CuI(3-Mepy) 3  to polynuclear [CuIpy] ∞  have been prepared by combining copper(I) iodide and pyridine-based ligands at different ratios. See, Raslon, C. L.; White, A. H.,  Journal of the Chemical Society - Dalton Transactions  1976, (21), 2153-2156; Rath, N. P.; Maxwell, 1. L.; Holl, E. M.,  Journal of the Chemical Society - Dallon Transactions  1986, (II), 2449-2453; Dyason, J. C.; Healy, P. C.; Pakawatchai, C.; Patrick, V. A.; While, A. H.,  Inorganic Chemistry  1985, 24, (12), 1957-1960; Eitel, E.; Oelkrug, D.; Hiller, W.; Strahle, J.,  Zeitschrijt Fur Naturforschung Section B - a Journal of Chemical Sciences  1980, 35, (10), 1247-1253. Excited states in these complexes have been proposed to be halide-to-ligand charge transfer (XLCT), metal-to-ligand charge transfer (MLCT), and/or halide-to-metal charge transfer (XMCT) based on experimental and computational work. See, De Angelis, F.; Fantacci, S.; Sgamellotti, A.; Cariati, E.; Ugo, R.; Ford, P. C.,  Inorganic Chemistry  2006, 45, (26), 10576-10584. Generally, copper(I) iodide based complexes, especially those with a pyridine derivative as ligand, are highly emissive at room temperature regardless of structure and nature of excited state. 
         [0072]    To date, a number of copper complexes with high photoluminescence quantum yield (PLQY) have been reported. However, studies on their application in OLEDs is limited. Most copper complexes are not sublimable, and, hence, are incapacitated from standard vacuum thermal evaporation based OLED fabrication methods. See, Zhang, Q. S.; Zhou, Q. G.; Cheng, Y. X.; Wang, L. x.; Ma, D. G.; Jing, X. B.; Wang, F. S.,  Advanced Materials  2004, 16, (5), 432-+; Che, G. B.; Su, Z. S.; Li, W. L.; Chu, B.; Li, M. T.; Hu, Z. Z.; Zhang, Z. Q.,  Applied Physics Letters  2006, 89, (10); Su, Z. S.; Che, G. B.; Li, W. L.; Su, W. M.; Li, M. T.; Chu, B.; Li, B.; Zhang, Z. Q.; Hu, Z. Z.,  Applied Physics Letters  2006, 88, (21); Tsuboyama, A.; Kuge, K.; Furugori, M.; Okada, S.; Hoshino, M.; Veno, K.,  Inorganic Chemistry  2007, 46, (6), 1992-2001. 
         [0073]    Methods for depositing a phosphorescent complex in situ are provided. The method comprises reacting one or more metal complexes having the formula MX n  and one or more of a ligand selected from L 1 , L 2 , and L 3  to form a phosphorescent complex having the formula (L 1 ) a (L 2 ) b (L 3 ) c (MX p ) m . The one or more metal complexes having the formula MX n  and the one or more ligands L 1 , L 2 , and L 3  are thermally vacuum deposited in combination over a substrate, wherein the reaction is completed to obtain the phosphorescent complex. 
         [0074]    M is a transition metal or lanthanide. X is alkyl, aryl, F, Cl, Br, I, SCN, OCN, CN, OR, and SR or combinations thereof. R is alkyl or aryl. m is 1-6. Preferably, m is 2. n is 1-10. Preferably, n is 1-3. p is equal to [n-(a·a′)+(b·b′)+(c·c′)]. Each of L 1 , L 2 , and L 3  is independently a mono-, di-, tri- or polydentate ligand. Each of a, b, and c may represent mono, bis or tris ligand coordination. a is 1-10, b is 0-9, and c is 0-9. a′ is the number of coordination sites of L 1 . b′ is the number of coordination sites of L 2 . c′ is the number of coordination sites of L 3 . The total number of coordination sites in the phosphorescent complex (L 1 ) a (L 2 ) b (L 3 ) c (MX p ) m  is the sum of the denticity of each ligand bound to each metal complex MX p  multiplied by the number of coordination sites of the ligand, i.e, (a·a′)+(b·b′)+(c·c′). [p+(a·a′)+(b·b′)+(c·c′)] is equal to n. 
         [0075]    If the phosphorescent complex contains more than one metal complex, then each metal complex MX n  may have the same or different formulas. For example, the phosphorescent complex may comprise two metal complexes MX n , i.e., m is 2, and each metal complex MX n  is CuI, such that the complex has the formula Cu 2 I 2 (L 1 ) a (L 2 ) b (L 3 ) c . Alternatively, the phosphorescent complex may comprise two metal complexes MX n  and one metal complex MX n , is CuI while the other metal complex has a different formula. 
         [0076]    As used herein, the term “depositing over” includes depositing directly onto a substrate as well as depositing onto other layers that are themselves already deposited over the substrate. In particular, as used herein, the term “depositing over” refers to depositing one or more metal complexes having the formula MX n  and one or more ligands L 1 , L 2 , and L 3  directly onto a substrate. In addition, the term “depositing over” also refers to depositing one or more metal complexes having the formula MX n  and one or more ligands L 1 , L 2 , and L 3  onto another layer, e.g., an organic layer of an OLED, which is already deposited over the substrate. 
         [0077]    Preferably, the metal complex is copper (I). More preferably, the metal complex is CuI. 
         [0078]    At least one of the ligands L 1 , L 2 , and L 3  may be a neutral ligand. In one aspect, at least one of L 1 , L 2 , and L 3  is a neutral ligand that is coordinated to the Cu through a C, N, O, P or S atom. Preferably, at least one of L 1 , L 2 , and L 3  is a neutral ligand that is coordinated to the Cu through a N atom. 
         [0079]    In another aspect, each of L 1 , L 2 , and L 3  is a neutral ligand that is coordinated to the Cu through a C, N, O, P or S atom. Preferably, each of L 1 , L 2 , and L 3  is a neutral ligand that is coordinated to the Cu through a N atom. 
         [0080]    In yet another aspect, at least one of L 1 , L 2 , and L 3  is selected from the group consisting of: 
         [0000]    
       
                 
         
             
             
         
       
       
                 
         
             
             
         
       
     
         [0081]    X is S, O, or NR. R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8  and R 9  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, sulfonyl, sulfonyl, phosphino, and combinations thereof. The ligand is coordinated to the metal M via at least atom of the ligand. 
         [0082]    Specific examples of ligands L 1 , L 2 , and L 3  are provided. In one aspect, at least one of L 1 , L 2 , and L 3  is selected from the group consisting of: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0083]    R′ and R″ 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. 
         [0084]    Alternatively, at least one of the ligands L 1 , L 2 , and L 3  may be a charged ligand. In one aspect, at least one of L 1 , L 2 , and L 3  is a charged ligand having the formula: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0085]    Y and Z are independently selected from the group consisting of C, N, O, P and S. 
         [0086]    In another aspect, 
         [0000]    
       
                 
         
             
             
         
       
     
         [0087]    A and B are each independently a 5 or 6-membered aromatic or heteroaromatic ring. A-B represents a bonded pair of aromatic or heteroaromatic rings coordinated to the metal via a nitrogen atom on ring A and an sp 2  hybridized carbon atom on ring B. Each of R A  and R B  may represent mono, di, tri, or tetra substituents. Each of R A  and R B  substituents 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. 
         [0088]    The phosphorescent complex obtained from the method may be homoleptic or heteroleptic. In one aspect, b is 0 and c is 0, i.e., homoleptic. In another aspect, at least one of b and c is equal to 1, i.e., heteroleptic. 
         [0089]    The phosphorescent complex obtained using the methods provided may or may not contain one or more halides after the metal complex has been reacted with at least one of the ligands. In one aspect, p is 0, i.e., the phosphorescent complex (L 1 ) a (L 2 ) b (L 3 ) c (MX p ) m  does not contain any halide because all of the halides present in the one or more metal complexes MX n  have been removed after the metal complex was reacted with at least one of L 1 , L 2  and L 3 . 
         [0090]    Specific examples of the phosphorescent complex obtained from the method are provided. In one aspect, the phosphorescent complex is selected from the group consisting of: 
         [0000]    
       
                 
         
             
             
         
       
       
                 
         
             
             
         
       
     
         [0091]    In one aspect, the one or more metal complexes having the formula MX n  and the one or more ligands L 1 , L 2 , and L 3  are deposited by solution processing. In another aspect, the one or more metal complexes having the formula MX n  and the one or more ligands L 1 , L 2 , and L 3  are deposited by thermal evaporation. 
         [0092]    In one aspect, the one or more metal complexes MX n  is mixed with an organic solvent to form a first solution and at least one of L 1 , L 2 , and L 3  is mixed with an organic solvent to form a second solution, prior to depositing over the substrate, and then the first solution and the second solution are deposited in combination over the substrate. 
         [0093]    In another aspect, the method further comprises providing a first electrode disposed over the substrate, depositing the one or more metal complexes having the formula MX n  and the ligand L on the first electrode, and depositing a second electrode. Preferably, the first electrode is an anode and the second electrode is a cathode. 
         [0094]    In another aspect, the method further comprises providing a first electrode disposed over the substrate, providing an organic layer disposed over the first electrode, depositing the one or more metal complexes having the formula MX n  and the ligand L on the first electrode, and depositing a second electrode. Preferably, the first electrode is an anode and the second electrode is a cathode. 
         [0000]    Combination with Other Materials 
         [0095]    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: 
       [0096]    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 porphryin 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 sliane derivatives; a metal oxide derivative, such as MoO x ; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal phosphorescent complex, and a cross-linkable compounds. 
         [0097]    Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0098]    Each of Ar 1  to Ar 9  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. 
         [0099]    In one aspect, Ar 1  to Ar 9  is independently selected from the group consisting of: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0100]    k is an integer from 1 to 20; X 1  to X 8  is C (including CH) or N; Ar 1  has the same group defined above. 
         [0101]    Examples of metal phosphorescent complexes used in HIL or HTL include, but not limit to the following general formula: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0102]    M′ is a metal, having an atomic weight greater than 40; (Y 1 —Y 2 ) is a bidentate ligand, Y 1  and Y 2  are independently selected from C, N, O, P, and S; L′ is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m′+n′ is the maximum number of ligands that may be attached to the metal. 
         [0103]    In one aspect, (Y 1 —Y 2 ) is a 2-phenylpyridine derivative. 
         [0104]    In another aspect, (Y 1 —Y 2 ) is a carbene ligand. 
         [0105]    In another aspect, M′ is selected from Ir, Pt, Os, and Zn. 
         [0106]    In a further aspect, the metal phosphorescent complex has a smallest oxidation potential in solution vs. Fc + /Fc couple less than about 0.6 V. 
       Host: 
       [0107]    The light emitting layer of the organic EL device of the present invention preferably contains at least a metal phosphorescent complex as light emitting material, and may contain a host material using the metal phosphorescent complex as a dopant material. Examples of the host material are not particularly limited, and any metal phosphorescent complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. 
         [0108]    Examples of metal phosphorescent complexes used as host are preferred to have the following general formula: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0109]    M′ is a metal; (Y 3 —Y 4 ) is a bidentate ligand, Y 3  and Y 4  are independently selected from C, N, O, P, and S; L′ is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m′+n′ is the maximum number of ligands that may be attached to the metal. 
         [0110]    In one aspect, the metal phosphorescent complexes are: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0111]    (O—N) is a bidentate ligand, having metal coordinated to atoms O and N. 
         [0112]    In another aspect, M′ is selected from Ir and Pt. 
         [0113]    In a further aspect, (Y 3 —Y 4 ) is a carbene ligand. 
         [0114]    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, oxadiazole, 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 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. 
         [0115]    In one aspect, host compound contains at least one of the following groups in the molecule: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0116]    R 1  to R 7  is independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, arylalkyl, heteroalkyl, aryl and heteroaryl, when it is aryl or heteroaryl, it has the similar definition as Ar&#39;s mentioned above. 
         [0117]    k is an integer from 0 to 20. 
         [0118]    X 1  to X 8  is selected from C (including CH) or N. 
       HBL: 
       [0119]    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. 
         [0120]    In one aspect, compound used in HBL contains the same molecule used as host described above. 
         [0121]    In another aspect, compound used in HBL contains at least one of the following groups in the molecule: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0122]    k is an integer from 0 to 20; L is an ancillary ligand, m is an integer from 1 to 3. 
       ETL: 
       [0123]    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 phosphorescent complexes or organic compounds may be used as long as they are typically used to transport electrons. 
         [0124]    In one aspect, compound used in ETL contains at least one of the following groups in the molecule: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0125]    R 1  is selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, arylalkyl, heteroalkyl, aryl and heteroaryl, when it is aryl or heteroaryl, it has the similar definition as Ar&#39;s mentioned above. 
         [0126]    Ar 1  to Ar 3  has the similar definition as Ar&#39;s mentioned above. 
         [0127]    k is an integer from 0 to 20. 
         [0128]    X 1  to X 8  is selected from C (including CH) or N. 
         [0129]    In another aspect, the metal phosphorescent complexes used in ETL contains, but not limit to the following general formula: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0130]    (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L′ is an ancillary ligand; m′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal. 
         [0131]    In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. 
         [0132]    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. 
         [0000]    
       
         
               
               
               
             
               
             
               
               
               
             
               
             
               
               
               
             
               
             
               
               
               
             
               
             
               
               
               
             
               
             
               
               
               
             
               
             
               
               
               
             
               
             
               
               
               
             
               
             
               
               
               
             
               
             
               
               
               
             
               
             
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 MATERIAL 
                 EXAMPLES OF MATERIAL 
                 PUBLICATIONS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Hole injection materials 
               
             
          
           
               
                 Phthalocyanine and porphryin compounds 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Appl. Phys. Lett. 69, 2160 (1996) 
               
               
                   
               
               
                 Starburst triarylamines 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 J. Lumin. 72-74, 985 (1997) 
               
               
                   
               
               
                 CF x   Fluorohydrocarbon polymer 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Appl. Phys. Lett. 78, 673 (2001) 
               
               
                   
               
               
                 Conducting polymers (e.g., PEDOT: PSS, polyaniline, polypthiophene) 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Synth. Met. 87, 171 (1997) WO2007002683 
               
               
                   
               
               
                 Phosphonic acid and sliane SAMs 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 US20030162053 
               
               
                   
               
               
                 Triarylamine or polythiophene polymers with conductivity dopants 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 EP1725079A1 
               
               
                   
               
               
                   
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
               
               
                   
               
               
                   
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
               
               
                   
               
               
                 Arylamines phosphorescent complexed with  metal oxides such as molybdenum and tungsten oxides 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 SID Symposium Digest, 37, 923 (2006) WO2009018009 
               
               
                   
               
               
                 p-type semiconducting organic phosphorescent complexes 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 US20020158242 
               
               
                   
               
               
                 Metal organometallic phosphorescent complexes 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 US20060240279 
               
               
                   
               
               
                 Cross-linkable compounds 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 US20080220265 
               
               
                   
               
             
          
           
               
                 Hole transporting materials 
               
             
          
           
               
                 Triarylamines (e.g., TPD, α-NPD) 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Appl. Phys. Lett. 51, 913 (1987) 
               
               
                   
               
               
                   
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 US5061569 
               
               
                   
               
               
                   
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 EP650955 
               
               
                   
               
               
                   
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 J. Mater. Chem. 3, 319 (1993) 
               
               
                   
               
               
                   
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Appl. Phys. Lett. 90, 183503 (2007) 
               
               
                   
               
               
                   
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Appl. Phys. Lett. 90, 183503 (2007) 
               
               
                   
               
               
                 Triaylamine on spirofluorene core 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Synth. Met. 91, 209 (1997) 
               
               
                   
               
               
                 Arylamine carbazole compounds 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Adv. Mater. 6, 677 (1994), US20080124572 
               
               
                   
               
               
                 Triarylamine with (di)benzo- thiophene/ (di)benzofuran 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 US20070278938, US20080106190 
               
               
                   
               
               
                 Indolocarbazoles 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Synth. Met. 111, 421 (2000) 
               
               
                   
               
               
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       EXPERIMENTAL 
       [0133]    Three organic molecules (TPBi, PBD, and mCPy) were used to demonstrate the methods provided. In particular, the photophysical properties of the co-deposited film and the performance of an OLEDs comprising the film were studied. Additionally, luminescent species in the co-deposited CuI:mCPy film were studied. 
       Example 1 
     Co-deposition of CuI and TPBi for OLEDs 
       [0134]    
       
                 
         
             
             
         
       
     
         [0135]    A series of CuI:TPBi films with different molar ratios were made by spin coating at room temperature. Table 2 provides the PLQY and lifetime data of spin cast CuI:TPBi films with different ratios. In details, 19.1 mg (0.1 mmol) CuI was dissolved in 5 mL CH 3 CN, 65.5 mg (0.1 mmol) TPBi was dissolved in 25 mL CH 3 CN. Films were then obtained by spin coating mixed solutions with different amount of CuI and TPBi, i.e. mixture of 200 μL CuI solution and 1000 μL TPBi solution was used to make 1:1 film. The photoluminescent spectra, lifetime, and photoluminescence quantum yield (PLQY) were examined under N 2 . 
         [0000]    
       
         
               
               
               
             
               
               
               
             
           
               
                 TABLE 2 
               
               
                   
               
               
                 CuI:TPBi (molar ratio) 
                 PLQY (%) 
                 Lifetime (lls) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1:1 
                 2.1 
                 0.78 
               
               
                 1:2 
                 10.6 
                 1.87 
               
               
                 1:3 
                 12.7 
                 2.30 
               
               
                 1:4 
                 16.3 
                 2.66 
               
               
                 1:5 
                 16.4 
                 2.53 
               
               
                 1:7 
                 16.6 
                 2.68 
               
               
                  1:10 
                 16.8 
                 2.66 
               
               
                   
               
             
          
         
       
     
         [0136]      FIG. 3  shows photoluminescent spectra of CuI:TPBi (molar ratio 1:4) film and neat TPBi film. The CuI:TPBi film has two emission peaks, with CuI:TPBi ratio varied from 1:1 to 1:10. One emission around 390 nm is likely due to TPBi, which consist with the emission of neat TPBi film. The other emission around 550 nm with decay lifetime of several microseconds is assigned to CuI:TPBi complex. By varying the molar ratio, it is found that the CuI:TPBi film shows maximum PLQY around 17% (Table 2). 
         [0137]    Since CuI can react with TPBi to form luminescent film easily, a device ITO/NPD (1000 Å)/CuI:TPBi (1:1.7, 100 Å)/TPBi (500 Å)/LiF (10 Å)/Al (1000 Å) was fabricated. The device was fabricated under standard OLEDs process, except the CuI:TPBi layer was made by co-depositing CuI and TPBi in vacuum chamber from different heating resources. Maximum external quantum efficiency (EQE) around 0.5% ( FIG. 4 ) was examined in this device. As shown in  FIG. 5 , the device shows electroluminescence around 560 nm, which is originated from CuI:TPBi complex based on the photoluminescent study of CuI:TPBi mm mentioned above. Though there is emission around 430 nm that may due to TPBi, the device fabricated here demonstrate that the co-deposited CuI:TPBi layer can be used as emission layer in OLEDs. 
       Example 2 
     Co-deposition of CuI and PBD for OLEDs 
       [0138]    Similar to the CuI:TPBi system, a series of CuI:PBD films with different molar ratio were made by spin coating at room temperature prior to OLEDs fabrication. The photoluminescent spectra, lifetime, and PLQYs of these films were examined, and the data is provided in Table 3. 
         [0000]    
       
         
               
               
               
             
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                 CuI:TPBi (molar ratio) 
                 PLQY (%) 
                 Lifetime (lls) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 2:1 
                 2.5 
                 1.12, 0.31 
               
               
                 1:1 
                 7.2 
                 1.56, 0.63 
               
               
                 1:2 
                 13.9 
                 2.33 
               
               
                 1:3 
                 14.1 
                 2.31 
               
               
                 1:4 
                 14.3 
                 2.97 
               
               
                 1:5 
                 14.3 
                 3.62 
               
               
                 1:7 
                 12.2 
                 4.07 
               
               
                  1:10 
                 12.6 
                 4.42 
               
               
                   
               
             
          
         
       
     
         [0139]    The CuI:PBD film has also two emission peaks with different CuI:PBD ratio, one peak around 390 nm originates from PBD and another peak around 570 nm with decay lifetime of several microseconds that from CuI:PBD complex. By varying the molar ratio of CuI and PBD, it is found that the CuI:PBD film shows maximum PLQY around 14% (Table 3). To apply CuI:PBD complex in OLEDs, a device ITO/NPD (1000 Å)/CuI:PBD (1:1, 100 Å)/PBD (500 Å)/LiF (10 Å)/Al (1000 Å) was fabricated, where the CuI:PBD layer was made by co-depositing CuI and PBD in vacuum chamber from different heating resources. The device shows maximum external quantum efficiency around 1.2% at low luminance (around 0.1 cd/m2) ( FIG. 7 ). As shown in  FIG. 8 , the device has pure CuI:PBD complex emission at very low luminance, while show also emission that may from PBD at higher luminance around 430 nm. Though the electroluminescence is not pure, the device shows mainly emission from CuI:PBD complex, demonstrated that co-deposited CuI:PBD layer can be used as emission layer in OLEDs. 
       Example 3 
     Co-deposition of CuI and mCPy for OLEDs 
       [0140]    As shown above, both TPBi and PBD can be used to co-deposit with CuI to form luminescent film as emission layer in OLEDs. However, the CuI:TPBi and CuI:PBD films have moderate PLQYs (17% and 14%) and impure electroluminescence. To improve OLEDs performance, it is critical to explore ligand that can coordinate to CuI and form highly efficient luminescent film. It is well known that copper iodide and pyridine based complexes are highly emissive at room temperature. [Ford, P. C.; Carlati, E.; Bourassa, J.,  Chemical Reviews  1999, 99, (12), 3625.3647.]Herein, mCPy was designed to co-deposit with CuI to explore efficient OLEDs. 
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         [0141]    The ligand mCPy was synthesized by Ullmann reaction of carbazole and bromopyridine in the presence of Cu as catalyst. A mixture of carbazole (3.67 g, 22 mmol), 3,5-dibromopyridine (2.36 g, 10 mmol), potassium carbonate (3.04 g, 22 mmol), copper powder (0.6 g) and nitrobenzene (30 mL) was refluxed overnight. The mixture was then distillated at reduced pressure. The obtained residue was extracted with CH 2 Cl 2  and purified by column chromatography on silica gel with hexane/CH 2 Cl 2 . The product was further purified by twice sublimation at low pressure (10 −5  ton). Total yield: 46%.  1 H-NMR (500 MHZ, CDCl 3 ): 15 9.13 (br, 2H), 8.19 (s, 1H), 8.18 (d, J=8.0 Hz, 4H), 7.54 (d, J=8.5 Hz, 4H), 7.48 (t, J=7.5 Hz, 4H), 7.36 (t, J=7.5 Hz, 4H). Anal. Calcd. for C 29 H 19 N 3 ): C, 85.06; H, 4.68; N, 10.26. Found: C, 85.54; H, 4.52; N, 10.31. MS m/z: 4 
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                 TABLE 4 
               
             
             
               
                   
               
               
                 PLQYs and lifetimes of CuI:mCPy films with different ratios 
               
             
          
           
               
                 CuI:mCPy (molar ratio) 
                 PLQY (%) 
                 Lifetime (μS) 
               
               
                   
               
             
          
           
               
                 1.75:1     
                 0 
                 — 
               
               
                 1.2:1    
                 7.9 
                 0.49, 3.0  
               
               
                 1:2.3 
                 48.2 
                 3.1, 10.1 
               
               
                 1:2.6 
                 61.5 
                 4.4, 12.8 
               
               
                 1:3.7 
                 63.3 
                 3.4, 11.5 
               
               
                 1:4.1 
                 60.4 
                 3.3, 11.0 
               
               
                 1:5.5 
                 63.9 
                 3.5, 11.6 
               
               
                   
               
             
          
         
       
     
         [0142]      FIG. 9  shows photoluminescent spectra of a series of CuI:mCPy films with different molar ratios made by co-depositing CuI and mCPy in vacuum chamber with two separate heating sources. By comparing the spectra of CuI:mCPy film and neat mCPy film, it is found that the CuI:mCPy film has almost pure emission from CuI:mCPy complex, which is different to CuI:TPBi and CuI:PBD films. Moreover, the maximum PLQY of the co-deposited CuI:mCPy film is up to 64%, indicating a promising candidate for OLEDs. 
         [0143]    To apply CuI:mCPy in OLEDs, four devices ITO/NPD (250 Å)/CuI:mCPy (200 Å)/BCP (400 Å)/LiF (10 Å)/Al (1000 Å) were fabricated, where the molar ratio of CuI:mCPy films varies between 0:1 (device 1), 1:4 (device 2), 1:6 (device 3), and 1:10 (device 4). Table 5 provides device data.  FIG. 10  shows electroluminescent spectra of the four devices at 8 V. The devices with CuI:mCPy complex have significantly different emission to that with neat mCPy, indicating the emission arises from CuI:mCPy complex, which consists with photoluminescent study. Moreover, identical pure CuI:mCPy complex emission was observed in the device  2  under different applied voltage ( FIG. 11 ), which is different from devices with CuI:TPBi or CuI:PBO film as emission layer. The pure copper complex based electroluminescence demonstrated here suggests that the emission color of the co-deposited OLEDs could tuned by varying ligands. 
         [0144]    Among the OLEDs with different molar ratios of CuI and mCPy, the device  4  shows the best EQE of 3.2%, and the maximum power efficiency (PE) and current efficiency (CE) are 3.2 μm/W and 5.9 cd/A, respectively. To get more information about OLEDs based on the co-deposited CuI:mCPy emission layer, another two devices ITO/NPD (250 Å)/CuI:mCPy (1:5, 200 Å)/BCPI Alq) (300 Å)/LiF (10 Å)/Al (1000 Å) were fabricated, where the thickness of BCP layer is 100 (device 5) or 0 Å (device 6).  FIG. 12  shows electroluminescent spectra of devices 5 and 6 at 8 V. The two devices have same emission spectra, indicates that hole-electron combination occurs within CuI:mCPy layer and the electroluminescence is mainly come from CuI:mCPy complex. As summarized below in Table 5, the device 6 shows maximum EQE, PE, and CE of 4.4%, 6.9 μm/W and 8.2 cd/A, respectively. It has been improved as compared to those of the device 2, suggests that the device performance with co-deposited CuI:mCPy emission layer could be further improved by modifying device configuration. 
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                 TABLE 5 
               
               
                   
               
               
                   
                   
                   
                 EQE max   
                 PE max   
                   
               
               
                 Device 
                 V on   a  (V) 
                 L max   b  (cd/m 2 ) 
                 (%) 
                 (lm/W) 
                 CE max  (cd/A) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 6.3 
                 2785 
                 0.52 
                 0.45 
                 0.97 
               
               
                 2 
                 3.7 
                 5257 
                 2.4 
                 2.6 
                 4.4 
               
               
                 3 
                 3.6 
                 5778 
                 3.0 
                 3.0 
                 5.6 
               
               
                 4 
                 3.8 
                 5501 
                 3.2 
                 3.2 
                 5.9 
               
               
                 5 
                 3.6 
                 5706 
                 3.9 
                 7.1 
                 7.3 
               
               
                 6 
                 3.7 
                 5802 
                 4.4 
                 6.9 
                 8.2 
               
               
                   
               
             
          
         
       
     
         [0145]    To understand the luminescent species in CuI:mCPy film we firstly co-deposited CuI and 1,3-bis(carbazol-9-yl)benzene (mCP) using the same technique to make CuI: mCPy films.  FIG. 13  shows photoluminescent spectra of CuI:mCP film and neat mCP film. The CuI:mCP has identical emission spectrum to that of mCP, indicating that the pyridine-nitrogen is response for the emission species in CuI:mCPy film. Thus the luminescent species in CuI:mCPy film might be viewed as reaction products of CuI and pyridine ring. It should be noted that there are mainly three products [CuIpy] ∞ , Cu 2 I 2 (py) 4 , and Cu 4 I 4 (py) 4  for the reaction of CuI and pyridine. They show blue, green, and orange emissions with maximum wavelength at 437, 517, and 580 nm in solid state at room temperature, respectively. [Kyle, K. R.; Ryu, C. K.; Dibenedetto, J. A.; Ford, P. C.,  Journal of the American Chemical Society  1991, 113, (8), 2954-2965.] 
         [0146]    Secondly, a model complex A was synthesized by mixing solutions of 102 mg CuI in CH 3 CN and 48 mg mCPy in CH 2 Cl 2  at room temperature. Elemental analysis shows that the complex A has CuI:mCPy ratio of 1:1. The model complex A has blue emission with maximum wavelength around 480 nm ( FIG. 14 ), likely to be [CuImCPy] n . Moreover, the neat film of A and the film made by doping A in mCPy have nearly the same emission spectra to that of the co-deposited CuI:mCPy film. This suggests that the complex A might be responsible for the luminescence observed in CuI:mCPy film. 
         [0147]    Another model complex B was also synthesized by adding small amount of CuI in CH 3 CN to excess of mCPy in CH 2 Cl 2 . The complex B was obtained as white crystals with green emission. Single X-ray diffraction measurement indicates that the model complex B has structure of Cu 4 I 4 (mCPy 4 ).3CH 2 Cl 2  ( FIG. 15 ). This means that even with a cubane structure that mostly reported as yellow to red emitter [Kyle, K. R.; Ryu, C. K.; Dibenedetto, J. A.; Ford, P. C.,  Journal of the American Chemical Society  1991, 113, (8), 2954-2965], the complex Cu 4 I 4 (mCPy 4 ) may be a green emitter and responsible for the luminescent in CuI:mCPy film. 
         [0148]    Although model complex with structure of Cu 2 I 2 (mCPy) 4  has not been synthesized yet, it is possible that there is such structure in co-deposited CuI:mCPy film, since Cu 2 I 2 (mCPy) 4  is well known as a green material and theoretically Cu 2 I 2 (mCPy) 4  may have green emission that similar to the CuI:mCPy film. In support of this assignment for the emitting species is the fact that the thin film PL efficiency is highest for CuI:mCPy ratios of 1:2 or higher (in mCPy), see Table 4. Less than 2 equivalents of mCPy per Cut is not likely to give Cu 2 I 2 (mCPy) 4  efficiently. 
         [0149]    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.