CN113801148A - Europium-doped macrocyclic complex and application thereof as electroluminescent material - Google Patents
Europium-doped macrocyclic complex and application thereof as electroluminescent material Download PDFInfo
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- CN113801148A CN113801148A CN202010544031.9A CN202010544031A CN113801148A CN 113801148 A CN113801148 A CN 113801148A CN 202010544031 A CN202010544031 A CN 202010544031A CN 113801148 A CN113801148 A CN 113801148A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
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Abstract
An electroluminescent material comprises a complex EuX2‑N8It has the following structure:
wherein X is F, Cl, Br, I, OCN, SCN, CN, CF3SO3、BF4Or PF6Each R is independently selected from H, C1‑C18Alkyl, halogen atom, aryl, substituted aryl, phenyl, substituted phenyl; alternatively, the electroluminescent material comprises a complex EuX2‑N4It has the following structure:
wherein X is F, Cl, Br, I, OCN, SCN, CN, CF3SO3、BF4Or PF6Each R is independently selected from H, C1‑C18Alkyl groups, halogen atoms, aryl groups, substituted aryl groups, phenyl groups, substituted phenyl groups.
Description
Technical Field
The invention belongs to the field of electroluminescent materials. In particular to a europium-doped macrocyclic complex and application thereof as an electroluminescent material.
Background
The 5d-4f transition of lanthanides (Ln) has been studied for decades in the mechanism of luminescence and in potential applications in various fields. For lanthanide ion luminescence, only the f-f transition is observed under normal ambient conditions, while the 5d-4f transition is generally absent, since it is shifted from 4fn-15d1To 4fnQuenching by rapid intersystem crossing. Among the divalent lanthanides, the 5d-4f transition is more prominent due to its spin-permitting property and stability of the 5d orbital.
In all Ln2+In ion, Eu2+The ions show strong 5d-4f transitions and good utility for two reasons: (1)5d energy is close to or lower than 6P7/2Multiphoton relaxation is reduced; (2) eu (Eu)3+/Eu2+The reduction potential is not too high. Eu (Eu)2+The study of the properties of ion luminescence can be roughly divided into two categories: eu in inorganic matrix2+Doped and molecular Eu2+And (3) a complex. The first category has been extensively studied, while the latter has not been explored in many respects. Eu reported in literature2+The complexes are mainly cyclopentadienyl, tri (pyrazolyl) borate, silyl amide and derivatives thereof. Recently, Allen et al reported a series of novel Eu-containing compounds2+The attractive luminescence, photoredox catalysis and magnetic resonance imaging of azamacrocyclic complexes of formula (I) are of increasing interest.
The uniqueness of the 5d-4f luminescence mechanism makes Eu2+Complexes in high performance Organic Light Emitting Diodes (OLEDs)Has great potential. OLEDs have been successfully commercialized as a new technology in sophisticated displays and are being developed in solid state lighting. To achieve a theoretical Exciton Utilization Efficiency (EUE) of 100%, phosphorescence, Thermally Activated Delayed Fluorescence (TADF) and organic free-radical materials were successively discovered and used as OLED light emitting materials. Eu in contrast to conventional f-f transitions and other currently used luminescent materials2+The compound has the following remarkable advantages: i) short excited state lifetime: f-f transitions are spin-forbidden, with lifetimes as long as a few milliseconds, greatly limiting the maximum brightness of their devices; while the 5d-4f transition is allowed with typical nanosecond lifetimes, significantly reducing excited state quenching, leading to higher brightness and lower efficiency roll-off; ii) the luminescent color can be easily adjusted by changing the coordination environment: the 5d orbital is sensitive to the ligand field, although the 4f orbital is not sensitive to the ligand field because it is effectively shielded by 5s5 p; iii) high abundance: the abundance of europium in the earth crust is 10-6wt%, much higher than the noble metals (Ir, Pt) of current commercial OLED light emitting materials. Therefore, the present inventors believe that Eu is used as Eu2+The 5d-4f transition material represented by the complex is the next unexplored but extremely potential field in the OLED luminescent material.
Disclosure of Invention
Despite the above advantages, Eu2+The use of the complexes is limited by their poor air stability. To the best of the inventors' knowledge, only one part so far has been based on Eu2+The OLED of the complex was reported to have an External Quantum Efficiency (EQE) of only 0.01% and a maximum luminance of only 10cd · m in consideration of a high photoluminescence quantum yield (PLQY) of 85%, which is unsatisfactory in performance of the External Quantum Efficiency (EQE)-2. Further, Eu2+5d-4f transition of ion is open shell electron at 4f65d1And 4f7The transition between orbitals, which the present inventors theoretically predict can utilize 100% of exciton energy when applied to OLEDs; therefore, more effort must be made to apply Eu2+The complex is reasonably designed, and the electroluminescent mechanism of the complex is deeply understood to improve the efficiency and brightness of the device. The inventors of the present invention believe that the steric effect and coordination interaction of macrocyclic ligands are exploitedCan increase Eu2+Stability of the complex. Thus, in a particular embodiment of the invention, the inventors have selected three ligands, 1,4,7, 10-tetraazadodecane (N)4) 1,4,7,10,13,16,21, 24-octaazabicyclo [8.8.8 ] s]Hexaalkane (N)8) And 4,7,13,16,21, 24-hexamethyl-1, 4,7,10,13,16,21, 24-octaazabicyclo [8.8.8]Hexacosane (N)8M6) For designing six names EuX2-NnAnd EuX2-N8M6Containing Eu2+The azamacrocycle complex of (X ═ Br, I; n ═ 4, 8). A series of crystal analyses, spectra, stabilities and theoretical studies were carried out to reveal these Eu2+Photophysical properties of the complex. Then, due to EuX2-N8The high efficiency and good thermal/air stability of the complexes, which are exemplarily selected as the light emitting layer material of the OLED for optimum device performance. Using EuI2-N8The optimized device has excellent performance, the maximum EQE is 17.7 percent, and the maximum brightness is 25470 cd.m-2The organic electroluminescent device can perform as well as the most advanced OLED device which takes a phosphorescent metal complex or TADF molecule as a luminescent material.
Embodiments of the present invention provide an electroluminescent material comprising a complex EuX2-N8It has the following structure:
alternatively, the electroluminescent material comprises a complex EuX2-N4It has the following structure:
wherein X is F, Cl, Br, I, OCN, SCN, CN, CF3SO3、BF4Or PF6Each R is independently selected from H, C1-C18Alkyl groups, halogen atoms, aryl groups, substituted aryl groups, phenyl groups, substituted phenyl groups.
According to one embodiment of the invention, for example, the luminescent material comprises (a) EuI2-N8，(b)EuBr2-N8，(c)EuI2-N8M6，(d)EuBr2-N8M6，(e)EuI2-N4，(f)EuBr2-N4The corresponding structural formula of the complex is shown as follows:
embodiments of the present invention also provide an electroluminescent device comprising a cathode, an anode, and a light-emitting layer located between the cathode and the anode, wherein the light-emitting layer comprises an electroluminescent material as described above.
According to one embodiment of the present invention, for example, the light emitting layer is a mixture of a guest material and a host material, wherein the guest material comprises an electroluminescent material as described above, and the host material comprises m-MTDATA and/or TAPC, with a doping concentration of 5 wt% to 12 wt%, preferably 7 wt% to 10 wt%, and most preferably 10 wt%, the doping concentration being the mass of the guest material as a percentage of the total mass of the guest material and the host material.
According to an embodiment of the present invention, for example, the electroluminescent device further comprises an electron transport layer between the cathode and the light-emitting layer, the electron transport layer comprising TmPyPB, DPEPO, Bphen and/or TPBi.
According to an embodiment of the present invention, for example, the electroluminescent device further includes a hole transport layer between the anode and the light emitting layer; preferably, the hole transport layer comprises m-MTDATA, TCTA and/or TAPC.
According to an embodiment of the present invention, for example, the electroluminescent device further includes an electron transport layer between the cathode and the light emitting layer and a hole transport layer between the anode and the light emitting layer;
preferably, the hole transport layer comprises TAPC and the electron transport layer comprises Bphen.
According to one embodiment of the invention, the thickness of the light emitting layer is, for example, 10-40nm, preferably 15-30nm, preferably 20-25nm, most preferably 25 nm.
According to an embodiment of the present invention, for example, the electroluminescent device further includes a hole blocking layer between the light emitting layer and the electron transport layer; preferably, the material of the hole blocking layer is TSPO 1;
preferably, the electroluminescent device further comprises a second hole transport layer located between the anode and the hole transport layer; preferably, the material of the second hole transport layer is NPB.
According to one embodiment of the present invention, for example, the electroluminescent device has a structure in which: ITO/MoO3(2nm)/N, N ' -bis (1-naphthyl) -N, N ' -bis-phenyl- (1,1' -biphenyl) -4,4' -diamine (NPB, 50 nm)/cyclohexylidenebis [ N, N ' -bis (p-tolyl) aniline](TAPC，10nm)/EuX2-N8: 4,4' -tris [ phenyl (m-tolyl) amino group]Triphenylamine (m-MTDATA, 25 nm)/diphenyl [4- (triphenylsilyl) phenyl]Phosphine oxide (TSPO1, 10nm)/4, 7-diphenyl-1, 10-phenanthroline (Bphen 30nm)/LiF (0.7 nm)/Al.
Drawings
FIG. 1 is a chemical structural formula of a complex, wherein (a) EuI2-N8，(b)EuBr2-N8，(c)EuI2-N8M6，(d)EuBr2-N8M6，(e)EuI2-N4，(f)EuBr2-N4(g) general structure EuX2-N8(h) general structure EuX2-N4。
FIG. 2 is an embodiment of the present inventionSchematic representation of the coordination structure of the complex in the example, wherein (a) EuBr2-N4，(b)EuI2-N4，(c)EuBr2-N8And (d) EuI2-N8. (e) Coordinating polyhedra (from top to bottom): eux2-N4Square inverse prism of (1), EuX2-N4Distorted cube of (1), EuBr2-N8And EuI2-N8In (1) a "hula hoop" configuration. Corresponding to the data in Table 1, the nitrogen atoms are labeled from N1-N8. For clarity, the solvent methanol (in EuBr) was omitted2-N4And EuI2-N8Middle) and all hydrogen atoms. The atom located at the most central position is an Eu atom.
FIG. 3 is a schematic representation of the crystal structure of a complex in an example of the present invention, wherein (a) EuBr2-N4，(b)EuI2-N4. Bipyramid representation is composed of two N4Ligand coordinated Eu2+. As shown, there are two groups [ Eu (N) in the crystal4)2]2+With different orientations. The direction is represented by a unit vector from Eu2+To the upper N4The midpoint of the ligand. Then, the angle θ between the two vectors is calculated for comparison. For EuBr2-N4：v1＝(-0.79,-0.085,0.60)，v2(-0.79,0.085,0.60), θ is 9.7 °. For EuI2-N4：v1＝(0,0.82,0.56)，v2＝(0,-0.83,0.53)，θ＝111.0°。
Detailed Description
The europium-doped macrocyclic complexes of the invention and their use as electroluminescent materials are described in more detail below with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Abbreviations the corresponding compounds are full names:
m-MTDATA 4,4' -tris [ phenyl (m-tolyl) amino ] triphenylamine
TAPC 4,4' -Cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ]
TmPyPB 1,3, 5-tris [ (3-pyridyl) -3-phenyl ] benzene
DPEPO bis [2- ((oxo) diphenylphosphino) phenyl ] ether
Bphen 4, 7-diphenyl-1, 10-phenanthroline
TPBi 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene
TSPO1 Diphenyl [4- (triphenylsilyl) phenyl ] phosphine oxide
TCTA Tris (4- (9 carbazolyl) phenyl) amine
NPB N, N '-di (1-naphthyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine
PEDOT PSS Poly (ethylenedioxythiophene) -poly (styrenesulfonate)
Preparation method and test method.
Unless otherwise indicated, all chemicals used in the synthesis were commercially available and used as received.1H-NMR was measured on Bruker-400 MHz NMR. Tetramethylsilane (TMS) was used as an internal reference for chemical shift correction, where δTMSEqual to 0. Elemental analysis was performed on a VARIO EL analyzer. Eu (Eu)2+All syntheses of the complexes were carried out in a glove box. Solid Eu2+All spectral tests of the complexes were carried out after paraffin encapsulation between two quartz plates, the solution being in N2The test was carried out under an atmosphere using a cuvette with a stopcock. By using KMnO4Commercial paraffins were purified by oxidation and column chromatography to remove optical brighteners. N is a radical of4The ligand (1,4,7, 10-tetraazadodecane) is commercially available.
N8Ligand (1,4,7,10,13,16,21, 24-octaazabicyclo [8.8.8 ]]Hexaalkane) was performed by a modified version of the reported method: tris (2-aminoethyl) amine (4.9g, 33.5mmol), NEt32-necked 1-L round-bottom flask (12mL) and 2-propanol (250mL) were charged, equipped with mechanical stirring and a dropping funnel, containing a dilute glyoxal solution (7.5 g). The flask was cooled to-78 ℃ and glyoxal solution (1 drop/1 s) was slowly added. After the addition was complete, the yellow solution was stirred at room temperature overnight. Then removing the solvent at 40 deg.C under vacuum to obtain yellowA colored solid, which was dispersed in 300mL CHCl3In (1), stirring was carried out for 2h, resulting in a large amount of yellow translucent gel. The gel was removed by filtration and the resulting CHCl was removed under vacuum at 40 deg.C3. The crude intermediate was dissolved in 300mL MeOH and cooled with ice water. Gradually adding excess NaBH4(14g) Slowly added to the solution to prevent vigorous reaction. The cloudy solution was stirred for 4 hours and the solvent was removed under vacuum to give a white solid which was treated with CH2Cl2(200 mL. times.3) was extracted. Removal of CH2Cl2Obtaining a crude product N8. Further purification was performed by thermal gradient sublimation (160 ℃ C. -80 ℃ C.) at low pressure (. about.5 Pa).1H-NMR(400MHz,D2O):δ2.79(s,12H),2.75(m,12H),2.58(m,12H)。
N8M6Ligand (4,7,13,16,21, 24-hexamethyl-1, 4,7,10,13,16,21, 24-octaazabicyclo [8.8.8 ]]Hexacosane) was synthesized by the following method: heating and refluxing N under the protection of nitrogen8Ligand (1.9g, 5.0mmol), formic acid (50mL, large excess) and paraformaldehyde (14g, large excess) are reacted for 4 days, the solvent is removed by rotary evaporation, the pH value is adjusted to 13 by 2M NaOH (aq.), dichloromethane is extracted (100mL multiplied by 3), anhydrous sodium sulfate is dried and is dried to obtain brown oily substance, the oily substance is dried in vacuum at 70 ℃ for 12h and then is sublimated and purified to obtain yellow white waxy solid 1.850g, the yield of the crude product is 81 percent, the crude product is recrystallized by n-pentane to obtain colorless crystals 1.170g, and the yield is 51 percent.1H NMR(400MHz,CDCl3,δ):2.68(s,12H,MeNCH2CH2NMe),2.56(s,24H,NCH2CH2NMe),2.29(s,18H,NCH3)。
EuBr2-N4The preparation method comprises the following steps: in a clean glass bottle, EuBr2(78mg, 0.29mmol) was dissolved in 6mL MeOH. Will N4(85mg, 0.50mmol) was dissolved in 3.5mL MeOH, which was slowly added to EuBr2In the solution, the solution was colorless and changed to orange-red without stirring. As the solvent evaporated, red crystals suitable for SCXRD analysis were formed (85% yield based on Eu). Elemental analysis C16H40Br2EuN8: c, 29.28%; h, 6.14%; and N, 17.07%. Fruit of Chinese wolfberryAnd (3) measurement: c, 29.05%; h, 6.05%; n,16.69 percent.
EuI2-N4The preparation method comprises the following steps: in a clean glass bottle, EuI2(55mg, 0.14mmol) was dissolved in 6mL MeOH. Will N4(50mg, 0.29mmol) was dissolved in 3.5mL MeOH and slowly added to EuI2In solution, the pale yellow solution turned orange-red without stirring. Shortly after mixing was complete, red crystals formed (70% yield based on Eu) suitable for SCXRD analysis. Elemental analysis C16H40EuI2N8: c, 25.61%; h, 5.37%; n,14.93 percent. Actually measuring: c, 25.84%; h, 5.54%; n,14.42 percent.
EuBr2-N8The preparation method comprises the following steps: EuBr was added under magnetic stirring2(0.156g, 0.500mmol) was dissolved in 10mL MeOH in a 50mL round bottom flask. Will N8(0.185g, 0.500mmol) was dissolved in 10mL MeOH and slowly added to EuBr2In solution. The colorless solution turned orange. The solvent was removed under reduced pressure to give a crude product (86% yield based on Eu). By applying a low pressure (10)-5Pa) for further purification by thermal gradient sublimation (320-250-60 ℃). By slowly volatilizing MeOH as solvent, green crystals suitable for SCXRD analysis were obtained. Elemental analysis C18H42Br2EuN8: c, 31.68%; h, 6.20%; n,16.42 percent. Actually measuring: c, 31.75%; h, 6.18%; n,16.39 percent.
EuI2-N8The preparation method comprises the following steps: EuI was added under magnetic stirring2(0.260g, 0.64mmol) was dissolved in 10mL MeOH in a 50mL round bottom flask. Will N8(0.260g, 0.70mmol) was dissolved in 10mL MeOH and slowly added to EuI2Of the solutions, the pale yellow solution turned orange. Green crystals suitable for SCXRD analysis were formed and the solvent was evaporated without evaporation (yield 72% based on Eu). Elemental analysis C18H42I2EuN8: c, 27.85%; h, 5.45%; n,14.43 percent. Actually measuring: c, 28.04%; h, 5.41%; n,14.28 percent.
EuBr2-N8M6And EuI2-N8M6The preparation method comprises the following steps: mixing the ligand solution and the rare earth salt solution according to a metering ratio in an anhydrous oxygen-free glove box for reaction. When the ultra-dry methanol is used as a solvent, the solvent is pumped to obtain a complex; and (4) when tetrahydrofuran is redistilled as a solvent, filtering to obtain the complex.
EuBr2-N8M6: the ultra-dry methanol is used as a solvent, and the product is a yellow-green solid. Elemental analysis C24H54Br2EuN8·H2O, C,36.74 percent; h, 7.20%; n,14.28 percent. Actually measuring: c, 36.71%; h, 6.92%; n,14.22 percent.
EuI2-N8M6: the tetrahydrofuran was redistilled as a solvent and the product was a pale yellow solid. Elemental analysis C24H54EuI2N833.50 percent of C; h, 6.33%; and N,13.02 percent. Actually measuring: c, 33.27%; h, 6.35%; n,12.72 percent.
And (3) photo-physical measurement: the UV-visible absorption spectrum was obtained using a UV-3100 spectrometer from Shimadzu, Japan. Steady state/transient PL spectra were recorded on an edinburg analysis instrument FLS980 spectrophotometer (edinburg ltd) equipped with a pulsed laser. The photoluminescence quantum yield (PLQY) of the crystalline powder was measured by an absolute PLQY measurement system on C9920-02 of Hamamatsu corporation.
Thermal stability analysis: use of Q600SDT Instrument at fixed N2Thermogravimetric analysis was recorded at a ramp rate of 15 °/min from room temperature to 700 ℃.
Quantum chemical computation: all calculations were performed using the ORCA package. To optimize the ground state geometry, a mixed B3LYP3-6 density functional that is not symmetrically constrained is used. The Def2-ECP pseudo potential with the base set of Def2-TZVP valency is for Eu (28 core electrons). The remaining elements in these compounds all adopt an all-electron-triplet zeta mass Def2-TZVP group. We included atomic pair dispersion correction using Becke-Johnson damping (D3BJ) to account for van der waals interactions. In the single-point time-varying DFT (TD-DFT) calculation, the PBE function is applied, and the base number of Def2-SV (P) is (the Def2-ECP pseudo potential is also applicable to Eu) for all elements. RI plus sphere chain (RIJCOSX) approximation all calculations were accelerated by the Weigned's "general purpose" Coulomb fit auxiliary basis set def 2/J.15.
Preparation and testing of OLEDs: indium Tin Oxide (ITO) anodes are commercially available with a sheet resistance of 14 Ω/gauge (Ω square)-1) And the thickness is 80 nm. Before preparation, the ITO substrate was cleaned with deionized water, acetone and ethanol. The organic layer and the metal layer are deposited in different vacuum chambers at a pressure of less than 1X 10-4Pa. The thickness of each layer and the evaporation rate of all materials were monitored using a quartz crystal monitor. For organic materials, the deposition rates are respectively maintained at
For the cathode, the deposition rates were kept at
The effective area of each device is 4mm2. All electrical and optical measurements were performed under ambient conditions and the equipment was enclosed in a glove box. The EL spectra, current density-voltage-luminance (J-V-L) and EQE characteristics were measured by a computer controlled Keithley 2400 source meter, absolute EQE measurement system (C9920-12) and photon multichannel analyzer (PMA-12, Hamamatsu Photonics).
Example 1 Structure of the Complex
By mixing EuX in methanol or tetrahydrofuran2And corresponding ligands, six complexes EuX were synthesized in a glove box2-NnAnd EuX2-N8M6(X ═ Br, I, n ═ 4,8), and the product was confirmed by elemental analysis. Part of Eu in the study was examined by single crystal X-ray diffraction (SCXRD)2+Coordination geometry of the macrocyclic complex (FIG. 2). Eubr2-N4Space group is P21/n, one unit cell comprises two complex positive ions, four bromine ions outside and four methanol. N is a radical of4The ligand has two possible conformations, each of which accounts for 50%. Thus, Eu2+The center is coordinated by eight nitrogen atoms from two ligands, using an unusual geometry, with an average of 50% being tetragonal inverse prisms and 50% being distorted cubic structures. In EuI2-N4A similar coordination structure is found in (a) of,the crystal has a higher symmetry Cmca. Two groups [ Eu (N) in unit cell4)2]2+They are oriented differently and are located at the face center, the edge center and the body center, respectively, and eight iodide ions are dispersed therein (fig. 3). Eux2-N8The crystal structure of (b) shows that the central Eu2+Coordination was performed with eight nitrogen atoms and one halide as a distorted "hula-hoop" geometry, and another halide in the outer sphere as a counterion, consistent with the reported structure. As shown in Table 1, EuX2-N4The bond length of medium Eu-N is relatively shorter than that of EuX2-N8Indicates N4The complex is in Eu2+And the ligand has stronger coordination interaction. Considering charge separation in crystals, EuX2-N4More like ionic crystals of the compound, in the counter ion and [ Eu (N)4)2]2+There is a relatively strong electrostatic attraction between the ions.
TABLE 1 EuX2-NnIn various bond lengths (or distances, units)
)
Note that:a EuX2-N4the structure has only one Eu-X distance; eux2-N8One halide ion is connected to the central metal (inner boundary) and the other is outside;b EuX2-N4two in N4The nitrogen atoms of the ligands are labelled 1-4 and 5-8, EuX2-N8The reference numerals are as shown in fig. 2.
Example 2 photophysical Properties of the Complex
In order to systematically study Eu2+The photophysical properties of the complex, the inventors determined its steady state and transient spectra. Eux2-N4The crystalline powder of (A) shows an orange-red emission, maximum wavelength (. lamda.)max) Are each 605nm (X ═ Br) and613nm (X ═ I). From N4Is changed to N8Ligand due to N8The weaker crystal field of the ligand results in a significant blue shift, EuX2-N8Lambda of the Complexmax510nm (X ═ Br) and 515nm (X ═ I). When N is to be8After methylation of the ligand, the resulting complex EuX2-N8M6Further blue-shifted of the emission wavelength of (a)max469nm (X ═ Br) and 466nm (X ═ I), respectively. The lifetime of these complexes is in the hundreds of nanoseconds (Table 2), within the expected range of 5d-4f transitions. The full width at half maximum (FWHM) of these complexes in solid powders is relatively narrow (only 32nm at the narrowest) compared to luminescent materials characterized by a Charge Transfer (CT) mechanism. The excitation bandwidths of these complexes are uncharacterized and range from 230nm to 500nm (EuX)2-N8And EuX2-N8M6) And 230nm-600nm (EuX)2-N4) In the meantime. According to the above photo-physical studies, and considering that the ligand in the complex system is a saturated organic compound having an extremely high energy level, the possibility of ligand-metal charge transfer (LMCT) is excluded. Thus, the excitation and emission process can be regarded as Eu2+Electron transition in ion, where ground state is 4f7[8S7/2]Excited state of 4f6[7F0]5s1。
Due to EuX2-N4Insoluble in common solvents, the inventors of the present invention studied only EuX2-N8And EuX2-N8M6Photophysical properties in methanol solution (1.5mM) and under nitrogen atmosphere. Eux2-N8The solution showed a bright yellow emission, lambdamaxAt 579nm, the emission spectra of the two complexes are almost identical. The emission was red-shifted by about 70nm compared to the solid sample, probably due to the N in the solid8The conformational differences of the ligands and the effects of the solution outweigh the effects of the halogens. The excitation bands of the two compounds are at 280nm and 410nm, respectively, from 4fz 3To 5dz 2And from 4fz 3To 5dxyIs detected. Ultraviolet visible spectrum shows EuX2-N8The complex is inHigh energy absorption at 250nm (. epsilon.)>1000L·mol-1·cm-1) Has a low-energy absorption peak (epsilon 644L. mol) at 404nm-1·cm-1X ═ Br) and 405nm (e ═ 512L · mol-1·cm-1X ═ I), consistent with their excitation band. Since the f-d transition is Laporte and spin allowed, the molar absorption rate will be larger, which is consistent with the reported Eu2+The complex is equivalent. For EuX2-N8And EuBr2-N4Time-lapse DFT (TD-DFT) calculations were performed. Eux2-N8The calculated predictions of (a) are very close to the experimental data. For N4Complex, EuBr2-N4With two possible conformations (high symmetry: cubic conformation, low symmetry: tetragonal antiprism conformation), calculations show that different conformations show different absorption bands. Eubr2-N8M6Lambda of the solutionmax449nm, FWHM 33nm only, and EuI2–N8M6The solution was almost identical, with only 1nm broadening and 2nm red-shift. Eubr2–N8M6The excitation of the solution is bimodal, with maximum wavelengths of 369nm and 285nm, corresponding to EuI2-N8M6The solution ratio was red-shifted by 20nm and 14nm, respectively. Eubr2-N8M6The absorption of the solution is bimodal, with maximum wavelengths of 347nm and 260nm, corresponding to EuI2-N8M6The solution ratio is red-shifted by 2nm and blue-shifted by 1 nm. Eubr2-N8M6The molar absorption coefficient of the solution at 260nm of the maximum absorption peak thereof was 2.1X 103M-1·cm–1And EuI2-N8M6The solution is increased by two times compared with the prior solution, but still is positioned at thousands of M-1·cm–1Of order of magnitude, Eu2+The 4f-5d transition of (1) absorbs.
Interestingly, EuI2-N8The fluorescent material shows mechanical color change property, and the fluorescent color changes from green to yellow after moderate mechanical grinding. The emission spectrum shows that a new peak appears in the longer wavelength region after milling. To explore possible causes, excitation and transient spectra at 515nm and 580nm were collected in the ground samples.Similar excitation characteristics and slightly longer excited state lifetime of the new peak at 580nm both indicate that the longer wavelength emission still comes from Eu2+In the center, there may be slightly different coordination environments. We temporarily attributed the mechanical discoloration properties to EuI2-N8The relatively weak lattice can lead to a change in the conformation of the ligand after milling. The reversible process is essentially recrystallization in some solvent atmosphere (e.g., methanol). Furthermore, EuI was obtained by rapid precipitation in an antisolvent (tetrahydrofuran)2-N8Amorphous powder, can significantly enhance emission of long wavelengths. The 560nm emission is greatly enhanced and the lifetime of the excited state is increased from the crystalline state to the amorphous state. However, in EuBr2-N8No similar phenomenon was observed, indicating EuBr2-N8Have a high lattice energy and thus are difficult to change the ligand conformation by such a small mechanical stimulus.
TABLE 2 summary of photophysical properties of six europium-ene complexes
EXAMPLE 3 thermal and air stability of the Complex
Eux was studied by thermogravimetric analysis (TGA)2-NnThermal properties of the four compounds. Eubr2-N4，EuI2-N4，EuBr2-N8And EuI2-N8Decomposition temperature (T)dCorresponding to a weight loss of 5%) were 270 ℃, 265 ℃, 393 ℃ and 436 ℃, respectively, the residual weight percentage of these compounds at 550 ℃ was unchanged, theoretically the mass percentage of the metal halide with respect to the total mass, since the decomposition process was temporarily due to the breakage of coordination bonds and the volatilization of organic ligands. The relative error in residue weight (RE) was then calculated to verify the guesswork. Eux2-N4RE of (D) is quite low (-3%), whereas EuX2RE of-N8 is too high (I is-6% and-10% for X ═ Br, respectively). Exclusion of EuX by elemental analysis2-N8The possibility of impurities. Therefore, we consider these EuX' s2-N8The compound is at TdNearby undergoes decomposition and sublimation, which will result in a large deviation of the final weight percentage.
Then at 10-5These compounds were tested for sublimation characteristics under high vacuum at Pa and gradient heating. Discovery of EuBr2-N8Complete sublimation in the small range of 50mg was possible around 320 ℃ (tube temperature, different from sample temperature). It is noteworthy that significant decomposition occurs in the bulk sublimation, which may be due to uneven heating in the sublimation boat. For EuI with a higher sublimation temperature (350 ℃ C.)2-N8Similar properties were also found.
Considering N8The complex has excellent thermal stability, can be used for preparing OLED devices by using a traditional thermal evaporation method, and has poor thermal stability to N4And N8M6The complex can be used as a light-emitting material in an OLED in a solution film-forming mode. However, Eu is conventionally known2+The ion is easily O2Oxidized to Eu3+Air stability is therefore a key parameter for further applications. In order to reveal its air stability at room temperature, the inventors of the present invention measured EuX2-N8As a function of time, wherein the changes in the PLQY values reflect their respective air stability, EuBr2-N8Has not changed after being exposed to air for more than 450 hours, and EuI2-N8Metastable to air. To the best knowledge of the inventors, these two complexes are the most stable molecular type Eu2+And (3) a complex. To explain Eu2+Differences in the stability of the complexes, buried volumes (% V) were calculatedbur) Analysis to estimate N8Steric protection of the ligands, both complexes show a high% VburValues (for X ═ Br, I77% and 75.1%, respectively). Since Eu is used2+And Br-Closer distance therebetween, EuBr2-N8% V ofburSlightly higher than EuI2-Nn. Thus, consider similar% VburTwo of these N8Difference in air stability between complexesRelated to the lattice energy. Eui2-N8Lattice energy ratio of (E) EuBr2-N8Small because of their weak static interactions and the presence of the solvent methanol in the crystals, which can also be used to explain their different mechanical discolouration behaviour.
Example 4 electroluminescent device-screening host materials
Photophysics according to example 2 and stability study of example 3, EuX2-N8The complexes are good candidates for luminescent materials for OLEDs. Due to the lack of Eu for OLED2+Complex device experience and therefore efforts are made to optimize device structures. First, EuBr was selected2-N8Device optimization, including screening of host materials in subsequent examples, finding the best combination of Hole Transport Layer (HTL) and Electron Transport Layer (ETL), adjusting the emissive layer thickness, and then further following the optimization conditions, adjusting the EuI2-N8Doping concentration of the device and thickness of the emitting layer, material used.
A1, A2 devices were designed and fabricated, and different host materials m-MTDATA and TAPC were tested in A1-A2 devices. The EQE for a1 was found to be the highest at 7.6%, with a small drop in efficiency. Therefore m-MTDATA was chosen for further optimization. The following table lists the device structure (modified and emissive materials shown in bold):
A1:ITO/MoO3(2nm)/m-MTDATA(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/TmPyPB(40nm)/LiF(0.7nm)/Al(100nm)
A2:ITO/MoO3(2nm)/m-MTDATA(40nm)/EuBr2-N8:TAPC(10wt％,20nm)/TmPyPB(40nm)/LiF(0.7nm)/Al(100nm)
TABLE 3 Main device parameters of devices A1 and A2
a)A starting voltage of 1cd m-2A corresponding voltage;b)a maximum EQE;c)100cd m-2EQE value corresponding to brightness;d)1000cd m-2EQE value corresponding to brightness;e)maximum current efficiency;f)the maximum brightness.g)Since the maximum luminance does not reach 1000cd m-2So there is no data.
Example 5 electroluminescent device-screening Electron Transport Layer (ETL) and Hole Transport Layer (HTL) materials
Different ETL materials were designed in the A3-a12 device, including TmPyPB, DPEPO, Bphen, TPBi and combinations thereof. The EQE of a10 was found to be the highest at 12.4%, but unfortunately, the efficiency drop of a10 was very severe and efficiency could be effectively increased by the introduction of TSPO 1. As for HTL materials, m-MTDATA, TCTA, TAPC, etc. were also tested in this example. The a12 with TAPC showed the best performance with little drop in efficiency and the highest brightness. The combination of TAPC and Bphen was tentatively chosen considering that a simple structure would help simplify further optimization. The device structures of A3-A12 are as follows:
A3:ITO/MoO3(2nm)/m-MTDATA(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/DPEPO(10nm)/TmPyPB(30nm)/LiF(0.7nm)/Al(100nm)
A4:ITO/MoO3(2nm)/m-MTDATA(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/DPEPO(40nm)/LiF(0.7nm)/Al(100nm)
A5:ITO/MoO3(2nm)/m-MTDATA(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/DPEPO(10nm)/TPBi(30nm)/LiF(0.7nm)/Al(100nm)
A6:ITO/MoO3(2nm)/m-MTDATA(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/TPBi(40nm)/LiF(0.7nm)/Al(100nm)
A7:ITO/MoO3(2nm)/m-MTDATA(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/TSPO1(40nm)/LiF(0.7nm)/Al(100nm)
A8:ITO/MoO3(2nm)/m-MTDATA(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/TSPO1(10nm)/Bphen(30nm)/LiF(0.7nm)/Al(100nm)
A9:ITO/MoO3(2nm)/m-MTDATA(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/TSPO1(10nm)/TPBi(30nm)/LiF(0.7nm)/Al(100nm)
A10:ITO/MoO3(2nm)/m-MTDATA(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/Bphen(40nm)/LiF(0.7nm)/Al(100nm)
A11:ITO/MoO3(2nm)/TCTA(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/Bphen(40nm)/LiF(0.7nm)/Al(100nm)
A12:ITO/MoO3(2nm)/TAPC(40nm)/EuBr2-N8:m-MTDATA(10wt％,20nm)/Bphen(40nm)/LiF(0.7nm)/Al(100nm)
TABLE 4 Main device parameters of A3-A12
EXAMPLE 6 electroluminescent device-light-emitting layer thickness
The thickness of the light emitting layer (EML) was tested in devices a13-a15, varying between 15nm, 25nm and 30 nm. As the EML thickness increases, the lighting voltage increases significantly. Taken together, an optimum thickness of 25nm was found in A14.
The device structures of A13-A15 are as follows:
A13:ITO/MoO3(2nm)/TAPC(40nm)/EuBr2-N8:m-MTDATA(～10wt％,15nm)/Bphen(40nm)/LiF(0.7nm)/Al(100nm)
A14:ITO/MoO3(2nm)/TAPC(40nm)/EuBr2-N8:m-MTDATA(～10wt％,25nm)/Bphen(40nm)/LiF(0.7nm)/Al(100nm)
A15:ITO/MoO3(2nm)/TAPC(40nm)/EuBr2-N8:m-MTDATA(～10wt％,30nm)/Bphen(40nm)/LiF(0.7nm)/Al(100nm)
TABLE 5 Main device parameters of A13-A15
Example 7 electroluminescent device-EuBr2-N8Device final trimming
This example is for EuBr2-N8With some minor adjustments to the device, the maximum EQE and brightness were further improved with less efficiency drop after the NPB and TSPO1 layers were inserted compared to a1-a 15. The device structure of a16 is as follows:
A16:ITO/MoO3(2nm)/NPB(50nm)/TAPC(10nm)/EuBr2-N8:m-MTDATA(～10wt％,25nm)/TSPO1(10nm)/Bphen(30nm)/LiF(0.7nm)/Al(100nm)
TABLE 6 Main device parameters of A16
Example 8 electroluminescent device-optimized EuI2-N8Device doping ratio
From the test results shown in Table 7, this example 8 selects 7 wt% as EuI in consideration of the maximum EQE, luminance, turn-on voltage and efficiency degradation of these devices2-N8The optimum doping concentration of the device. The device structures of B1-B4 are as follows:
B1:ITO/MoO3(2nm)/NPB(50nm)/TAPC(10nm)/EuI2-N8:m-MTDATA(5wt％,25nm)/TSPO1(10nm)/Bphen(30nm)/LiF(0.7nm)/Al(100nm)
B2:ITO/MoO3(2nm)/NPB(50nm)/TAPC(10nm)/EuI2-N8:m-MTDATA(7wt％,25nm)/TSPO1(10nm)/Bphen(30nm)/LiF(0.7nm)/Al(100nm)
B3:ITO/MoO3(2nm)/NPB(50nm)/TAPC(10nm)/EuI2-N8:m-MTDATA(10wt％,25nm)/TSPO1(10nm)/Bphen(30nm)/LiF(0.7nm)/Al(100nm)
B4:ITO/MoO3(2nm)/NPB(50nm)/TAPC(10nm)/EuI2-N8:m-MTDATA(12wt％,25nm)/TSPO1(10nm)/Bphen(30nm)/LiF(0.7nm)/Al(100nm)
TABLE 7 main device parameters of B1-B4
Example 9 electroluminescent device-optimization of light emitting layer thickness
From the test results shown in table 8, the optimum thickness of the light emitting layer is 25nm in consideration of the maximum EQE, luminance and efficiency degradation of the device in combination. The device structures of B5-B8 are as follows:
B5:ITO/MoO3(2nm)/NPB(50nm)/TAPC(10nm)/EuI2-N8:m-MTDATA(7wt％,15nm)/TSPO1(10nm)/Bphen(30nm)/LiF(0.7nm)/Al(100nm)
B6:ITO/MoO3(2nm)/NPB(50nm)/TAPC(10nm)/EuI2-N8:m-MTDATA(7wt％,20nm)/TSPO1(10nm)/Bphen(30nm)/LiF(0.7nm)/Al(100nm)
B7:ITO/MoO3(2nm)/NPB(50nm)/TAPC(10nm)/EuI2-N8:m-MTDATA(7wt％,25nm)/TSPO1(10nm)/Bphen(30nm)/LiF(0.7nm)/Al(100nm)
B8:ITO/MoO3(2nm)/NPB(50nm)/TAPC(10nm)/EuI2-N8:m-MTDATA(7wt％,30nm)/TSPO1(10nm)/Bphen(30nm)/LiF(0.7nm)/Al(100nm)
TABLE 8 Main device parameters of B1-B4
On the basis of the results of the above embodiment, the OLED structure obtained by final optimization is ITO/MoO3(2nm)/N, N ' -bis (1-naphthyl) -N, N ' -bis-phenyl- (1,1' -biphenyl) -4,4' -diamine (NPB, 50 nm)/cyclohexylidenebis [ N, N ' -bis (p-tolyl) aniline](TAPC，10nm)/EuX2-N8: 4,4' -tris [ phenyl (m-tolyl) amino group]Triphenylamine (m-MTDATA, 25 nm)/diphenyl [4- (triphenylsilyl) phenyl]Phosphine oxide (TSPO1, 10nm)/4, 7-diphenyl-1, 10-phenanthroline (Bphen 30nm)/LiF (0.7 nm)/Al. The best EuBr2-N8The device has a starting voltage (V) of 6.2Von)，10200cd·m-2Maximum luminance (L)max)，52.8cd·A-1Maximum Current Efficiency (CE)max) And excellent performance with a maximum EQE of 15.5%. By using EuI2-N8Obtaining optimal device performance as a luminescent material, Von，Lmax，CEmaxAnd EQE increased to 6.5V, 25470 cd.m-2、62.4cd·A-1And 17.7%. These results far exceed the only one previously reported case based on Eu2+The maximum EQE of the OLED device of (1) is 0.01%, LmaxIs 10 cd.m-2The lighting voltage is 20V. The device results of the embodiments of the present invention are comparable to most mainstream OLEDs (phosphorescent metal complexes or TADF molecules as light emitting materials).
It is noteworthy that, considering the bandgap of the host material is about 3eV (400 nm), there is a rather high VonValue (>6V). To understand this phenomenon, we studied the vacuum by working at high vacuum (10)-5Pa) on a quartz substrate2Photophysical properties of the films produced in N-doped m-MTDATA (10% by weight). Also make EuX2-N8For reference. The emission of the doped thin film is mainly located in two wave bands, wherein the 400-470nm wave band (tau-1.2 ns) is attributed to the fluorescence of the host material, and the 500-650nm wave band (tau-10 ns)2ns) from EuX2-N8. Excitation spectroscopy shows that the two main excitation bands are located near 320nm and 390nm in pure films, which is similar to solution and solid state studies. Both doped films have almost the same excitation band at 350nm, indicating that the light energy first excites the host material and then transfers to the doped Eu2+Complex, and energy is not completely transferred during photoluminescence. Interestingly, the electroluminescence spectrum shows only Eu2+The emission of the complex, with a doping concentration (7 wt%) lower than that in the photoluminescence study. Thus, the above results indicate that carrier binding occurs primarily in the dopant material rather than the host material.
EXAMPLE 10 electroluminescent device-solution method for preparing OLED
In view of EuX2-N4And EuX2-N8M6The thermal stability of the series europium-doped europium complexes is not good enough, and the OLED device adopting the compounds as the light-emitting layer is prepared by a solution method in the embodiment, and the structure of the device is ITO/PEDOT: PSS (20nm)/EuX2-N4Or EuX2-N8M6(20nm)/TPBi (60nm)/LiF (0.7nm)/Al (100 nm). Although the performance of these devices is not good enough at present, it is expected that the performance of the devices is expected to be significantly improved when the film forming process is improved and appropriate charge transport materials and host materials are selected.
TABLE 9 EuX-based solution method of preparation2-NnAnd EuX2-N8M6Device parameters of light-emitting OLEDs
The embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An electroluminescent material, characterized in that the electroluminescent material comprises a complex EuX2-N8It has the following structure:
alternatively, the electroluminescent material comprises a complex EuX2-N4It has the following structure:
wherein X is F, Cl, Br, I, OCN, SCN, CN, CF3SO3、BF4Or PF6Each R is independently selected from H, C1-C18Alkyl groups, halogen atoms, aryl groups, substituted aryl groups, phenyl groups, substituted phenyl groups.
2. The electroluminescent material of claim 1, wherein the luminescent material comprises (a) EuI2-N8，(b)EuBr2-N8，(c)EuI2-N8M6，(d)EuBr2-N8M6，(e)EuI2-N4，(f)EuBr2-N4The corresponding structural formula of the complex is shown as follows:
3. an electroluminescent device comprising a cathode, an anode, and a light-emitting layer between the cathode and the anode, wherein the light-emitting layer comprises an electroluminescent material as claimed in claim 1 or 2.
4. An electroluminescent device according to claim 3, wherein the light-emitting layer is a mixture of a guest material and a host material, wherein the guest material comprises an electroluminescent material according to claim 1 or 2, and the host material comprises m-MTDATA and/or TAPC, with a doping concentration of 5 wt% to 12 wt%, preferably 7 wt% to 10 wt%, most preferably 10 wt%, the doping concentration being the mass of the guest material as a percentage of the total mass of the guest material and the host material.
5. An electroluminescent device according to claim 3 or 4, characterized in that the electroluminescent device further comprises an electron transport layer between the cathode and the light-emitting layer, the electron transport layer comprising TmPyPB, DPEPO, Bphen and/or TPBi.
6. An electroluminescent device according to claim 3 or 4, characterized in that it further comprises a hole transport layer between the anode and the light-emitting layer; preferably, the hole transport layer comprises m-MTDATA, TCTA and/or TAPC.
7. An electroluminescent device according to claim 5 or 6, characterized in that it further comprises an electron transport layer between the cathode and the light-emitting layer and a hole transport layer between the anode and the light-emitting layer;
preferably, the hole transport layer comprises TAPC and the electron transport layer comprises Bphen.
8. An electroluminescent device according to any of claims 3 to 7, characterized in that the thickness of the light-emitting layer is 10-40nm, preferably 15-30nm, preferably 20-25nm, most preferably 25 nm.
9. The electroluminescent device of claim 5, further comprising a hole blocking layer between the light-emitting layer and the electron transport layer; preferably, the material of the hole blocking layer is TSPO 1;
preferably, the electroluminescent device further comprises a second hole transport layer located between the anode and the hole transport layer; preferably, the material of the second hole transport layer is NPB.
10. An electroluminescent device as claimed in claim 3, characterized in that the electroluminescent device has the structure: ITO/MoO3(2nm)/N, N ' -bis (1-naphthyl) -N, N ' -bis-phenyl- (1,1' -biphenyl) -4,4'-diamine (NPB, 50 nm)/cyclohexylidenebis [ N, N' -bis (p-tolyl) aniline](TAPC，10nm)/EuX2-N8: 4,4' -tris [ phenyl (m-tolyl) amino group]Triphenylamine (m-MTDATA, 25 nm)/diphenyl [4- (triphenylsilyl) phenyl]Phosphine oxide (TSPO1, 10nm)/4, 7-diphenyl-1, 10-phenanthroline (Bphen 30nm)/LiF (0.7 nm)/Al.
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