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org/acsaelm Article

Highly Efficient Multifunctional Luminogens for Near UV/Deep Blue

(CIEy ∼0.02) and Hybrid White OLEDs (CIE ∼0.33, 0.37) with Superior
Color Stability
Jaipal Devesing Girase,§ Mangey Ram Nagar,§ Shahnawaz, Abhijeet Choudhury, Jwo-Huei Jou,
and Sivakumar Vaidyanathan*
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ABSTRACT: Near-ultraviolet (NUV) light-emitting pure organic

fluorophores are crucial in organic electronics because of less power
consumption and full-color displays with a wide color gamut.
However, emerging solution-processable NUV emitters for violet
organic light-emitting diodes (VOLEDs) is quiet a formidable task.
On this basis, two efficient NUV/deep blue N,N-diphenyl-3′-(1-(3-
(trifluoromethyl)phenyl)-1H-phenanthro[9,10-d]imidazol-2-yl)-[1,1′-
biphenyl]-4-amine (3-PIMCFTPA) and 3′-(4,5-diphenyl-1-(3-
(trifluoromethyl)phenyl)-1H-imidazol-2-yl)-N,N-diphenyl-[1,1′-bi-
phenyl]-4-amine (3-BICFTPA) emitters were designed and synthe-
sized based on a meta-linking D−π−A design strategy, which
efficiently shortens the π-conjugation length, which results emission
in the higher energy end of the emitters. Experimental and theoretical
investigation reveals materials with efficient NUV emission and good bipolar carrier transporting properties. Hence, the undoped, as
well as doped OLED devices, were fabricated utilizing our synthesized fluorophores. Among them, 3-PIMCFTPA showed the best
electroluminescence performance with maximum external quantum efficiency (EQEmax) of 5.7 and 3.4% with Commission
Internationale d’É nclairage (CIE) coordinates of (0.17, 0.10) and (0.17, 0.02), respectively. Moreover, the 3-PIMCFTPA possesses
a pure violet emission (385 nm) with high performance, allowing the emitter to be used to realize high-performance hybrid white
OLEDs. The 1 wt% yellow emitter-based device displayed pure white light with a PEmax of 22.5 lm W−1, a CEmax of 25.4 cd A−1, and
an EQEmax of 12.0% with a CIE coordinate (0.33, 0.37) at 1000 cd m−2. These results of our emitters make them potential for smart
displays and lighting applications.
KEYWORDS: imidazole, triphenylamine, near-UV emitters, fluorophores, WOLEDs

■ INTRODUCTION
Organic light-emitting diodes (OLEDs) have massive interna-
storage information,15 and so forth. As a result, the
development of UV−blue fluorescent materials is attracting
tional demand both in the academic and industrial circle considerable attention because of their long device lifetimes,
because of their advantages of low-cost fabrication, easy low-efficiency roll-off at high current density, superior color
synthesis, and adjustable performance by a modifiable purity of electroluminescence (EL), and ability to fabricate
structural design since the innovative effort of Tang and cost-effective full-color displays and WOLEDs. In general,
VanSlyke.1 For full-color displays, three primary colors, are NUV−blue emission requires emitters with a controlled
essential with high efficiency, high color purity, and equal conjugation, wide highest occupied molecular orbital
stability.2,3 In full-color OLEDs, efficient violet−blue light- (HOMO), and lowest unoccupied molecular orbital
emitting materials also has a great importance since violet− (LUMO) band gaps, and these properties lead to inferior
blue light not only can generate white light but also efficiently carrier combination in the devices,16 low EL performance, and
minimize the power intake and the color range of full-color
displays, as well as can function as a host for dopants Received: May 15, 2022
emitters.4−7 Additionally, near-ultraviolet (NUV) emissive Accepted: August 30, 2022
pure organic materials also have a promising candidate in Published: September 12, 2022
other areas such as biological sensing,8 antibacterial blue light
treatment (ABL),9 photocopying,10 photodynamic therapy
(PDT),11 sterilizing,12 water purification,13,14 high-density

© 2022 American Chemical Society https://doi.org/10.1021/acsaelm.2c00648

4368 ACS Appl. Electron. Mater. 2022, 4, 4368−4382
ACS Applied Electronic Materials pubs.acs.org/acsaelm Article

low photoluminescence quantum yield. Generally, the charge their easy synthesis method and sufficient thermal stability,
transfer in the simple donor−acceptor structure can realize the they give a very narrow emission band (less FWHM) due to
unwanted redshifted emission, which ultimately does not favor the great twisting conformation of the imidazole unit.
obtaining violet/deep blue emission with color coordinate CIE However, because of its stiff molecular skeleton, morpho-
y value <0.05. To overcome these encountered problems, the logical, thermal, and photochemical stabilities, as well as its
structural molecular design (beyond the conventional way of good hole-transporting properties, triphenylamine (TPA) is
connecting donor−acceptor moieties in a single fluorophore one of the fascinating structural units investigated by material
structure) plays a crucial role that it can separate the charge chemists in the field of OLEDs.30,31 When the imidazole (A)
injection group, selection of electron-donating/withdrawing unit is connected with triphenylamine (D) via a meta-linking
moiety with proper inductive strength, suppression of π- strategy, it may decrease the molecular conjugation and
conjugation length, and intramolecular charge transfer (ICT) effectively suppress the ICT through bond and space
effect to minimize their interactions.17 interactions among the donors and acceptors. Hence, there is
In comparison to prior generations of emitters (phosphor- considerable interest to improve their photophysical and
escent molecular complexes/thermally activated delayed bipolar carrier properties by designing appropriate imidazole−
fluorescence (TADF) based emitters), extensive attempts TPA hybrids, which are expected to exhibit near-UV−blue
have been made to date to investigate the various NUV− emitters.
blue fluorescent emitters. At present, very few reports are Inspired by this approach, twisted 3-PIMCFTPA and 3-
available based on violet−blue emitters with good effi- BICFTPA were prepared by incorporating imidazole as an
ciency.18,19 For instance, more recently, Lee et al. developed electron-carrying moiety, functionalizing the imidazole at the
a novel violet emitter based on meta-oriented bis-fusion of the N1 position with substituted phenyl rings (m-CF3), and TPA
two DMID subunits (m-FLDID). Doped devices based on as a hole-transporting moiety. Here, we use the electron-
these materials display violet emission maxima at 407 nm with withdrawing (EW) group (−CF3) because it will increase the
a CIEy coordinate of ∼0.03.20 Similar observation has also EW ability of the imidazole unit, which ultimately results in
been encountered in pyrene-based (TFPy2, TFPy3, and good electron-transporting properties and device efficacy.
TFPy4) materials.9 In the year of 2013, Gao et al. reported Here, TPA is connected via a meta linkage with both
the derivate based on the phenanthroimidazole (M2) and imidazoles to suppress the conjugation length, which
applied it as a violet−blue OLED displaying a maximum EQE ultimately restricts the unvented redshift and results in near-
of 3.02% with CIE color coordinates of (0.166, 0.056).21 Yang UV−blue emission of the emitters, as displayed in Figure 1.
and co-workers reported benzimidazole and substituted
carbazole (Cz-2pbb). The device based on the Cz-2pbb
shows efficient deep-blue EL with CIE of (0.16, 0.05) having
4.1% EQE. Moreover, based on the Cz-2pbb emitter, a white
OLED was shown to display an EQE above 10% and power
efficiency (PE) of 14.8 lm W−1 at a luminance of 500 cd m−2.22
Another efficient deep-blue/NUV fluorescence material with
balanced charged injection based on twisted 9-phenylcarbazole
and triazole (PCZTZ) was developed. The nondoped-device-
based PCZTZ shows a bright NUV emission with an EQE of
6.57% and CIE coordinates of (0.17, 0.07).23 The new
fluorescent emitter was designed, and the device based on it Figure 1. Design strategy and chemical structure.
demonstrated deep-blue EL with a maximum EQE of 4.34%
and CIExy values of (0.15, 0.05). Additionally, by optimizing Both the fluorophores were well characterized by the different
the emitter composition, cool-white OLEDs have been spectroscopic methods. The theoretical investigation was done
fabricated, and the device displays an EQE of 9% and CIE to have knowledge of the electronic features and optical
coordinates of (0.34 and 0.33).24 Recently, our group properties of the fluorophores. Extremely narrow NUV−blue
developed a new emitter based on imidazole (A) and carbazole emissions in the solution and solid phase were obtained for
(D) by incorporating an alkyl spacer between the donor and both the fluorophores. Electrochemical analysis reveals the
acceptor. The emitter BICFOCz displays a very intense blue HOMO−LUMO energy levels. Furthermore, the blue emissive
EL emission having a CIEy of 0.05 and a maximum EQE of materials were also examined as NUV/deep blue-emitting
3.4%. Additionally, 0.5 wt % of the emitter in the orange−red dopants in solution-processed multilayer OLEDs. The device
dye was found to emit pure white light with an EQE of 11.5% based on 3-PIMCFTPA emitters shows NUV/deep blue
and CIExy values of (0.35, 0.32).25 emission with peaks at ∼395 nm and a CIEy of 0.10 and 0.02
For the last two decades, phenanthroimidazole (PI)-based with an EQEmax of 5.7 and 3.4%, respectively. Additionally,
emitters remain attracting much attention in OLEDs. PI itself inspired by the CIE color coordinates, as well as their EL
is an excellent ultraviolet (UV)-light-emitting unit, showing characteristics of 3-PIMCFTPA, solution-processed hybrid
high fluorescent quantum yield and superior charge-trans- white OLED devices were fabricated. Remarkably, we observed
porting properties. They show structural alteration at N1 and a 1 wt% yellow emitter-based device displaying a PEmax of 22.5
C2 of the imidazole ring and a rigid imidazole structure, great lm W−1, a CEmax of 25.4 cd A−1, and an EQEmax of 12.0% with
thermal stability, and film-forming capability, which lead to a CIE coordinate (0.34, 0.39) at 1000 cd m−2.
enhanced applications as blue emitters in high-performance
OLEDs26,27 and diphenylimidazole,28,29 which is gaining
significant interest in the organic electronics community.
■ RESULTS AND DISCUSSION
Theoretical Calculations. To assimilate the structure and
Since these materials attracted considerable attention due to electronic characteristics of the fluorophores, density func-
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Figure 2. Optimized structures corresponding to FMOs of the fluorophores.

Table 1. Key Photophysical Data of 3-PIMCFTPA and 3-BICFTPA

solution solid absolute quantum yield (Φ)
a b c b c
compounds Td °C abs (nm) PL (nm) abs (nm) PL (nm) solution (%) neat film (%) lifetime (η) ns
3-PIMCFTPA 253 242, 264, 332 408 345 428, 444 69.4 60.3 1.90
3-BICFTPA 220 241, 274, 334 404 352 418 45.1 24.9 1.91
a
Thermal degradation temperature corresponding to 5% weight loss. bAbsorption maximum. cEmission maximum.

tional theory (DFT) and time-dependent DFT (TD-DFT) the 3-PIMCFTPA and 3-BICFTPA fluorophores were
were executed. The optimized geometry at the ground state of localized mainly over imidazole’s N1-functionalized (Ph-CF3)
the targeted fluorophores was done in the gas phase with the part. By carefully inspecting the FMOs (Figure S20), it is seen
help of the basis set of B3LYP/6-31G (d,p) using Gaussian 09 that the complete segregation of the HOMO and LUMO
software package.32,33Figure 2 displays an energy-minimized configurations in both fluorophores, along with the absence of
geometry with the dihedral angle in the gas phase and electron an MO overlap, serves as an indicator of the forbidden nature
density contours of the designed blue fluorophores. The of the transitions. This might be because imidazoles have a
optimized structures of 3-PIMCFTPA and 3-BICFTPA show strong EW group (Ph-CF3) at the N1 position, which draws
a twisted geometry, as the twisted geometries in the molecular electron density to the N1-substituted moiety (shows only the
structure not only result in suppression of π-conjugation, CT character). While the allowed singlet transition is observed
keeping the system in higher energy end, but also help with from HOMO to LUMO + 1 (higher energy level), in this case,
emission in the NUV to the blue area. This diminishes the LUMO + 1 was localized mainly on the acceptor (imidazole)
solid phase aggregation and ICT, which generally influences and the N1-substituted substituted unit, as shown in Figure
the color purity of the fluorophores.34 S20, and the transitions are tabulated in Table S4.36,37
The frontier molecular orbital (FMO) diagram of 3- Theoretical HOMO−LUMO energies, energy band gaps
PIMCFTPA and 3-BICFTPA shows that fully separated (Eg), and first singlet−triplet excited-state energies of
HOMO−LUMO energy levels are advantageous for the fluorophores are summarized in Table S2. The predicted
effective electron and hole carrier properties since it could HOMO/LUMO energies of the targeted fluorophores are
generate a charge hopping route between the charges, which −4.96/−1.58 eV for 3-PIMCFTPA and −4.94/−1.47 for 3-
may be beneficial for the EL performance of the OLEDs.35 BICFTPA, respectively. The estimated theoretical band gap
From Table S2, it was noticed that energy differences of the (Eg) was found to be 3.39 and 3.47 eV for the fluorophores 3-
HOMO and LUMO were very identical for both the PIMCFTPA and 3-BICFTPA, respectively (Table 1).
fluorophores, and the same can be visualized from the Subsequently, simulated UV−vis spectra of the targeted
FMOs(Figure 2). The HOMO of both 3-PIMCFTPA and fluorophores were calculated in the gas and DCM phases, as
3-BICFTPA were mostly distributed on the TPA and π- shown in Figure S19 in the Supporting Information. However,
conjugated aromatic rings (π-spacer). However, the LUMOs of no obvious variations were perceived in the absorption spectra
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Scheme 1. Synthesis Routes for Intermediate I, II, 3-PIMCFTPA, and 3-BICFTPA

of the targeted materials. Table S3 provides an overview of the presence of an inert atmosphere. The reagents and chemicals used
fluorophores’ calculated vertical transition, orbital contribu- were purchased from commercial sources and utilized without
tions, and oscillatory strength (f) in the gas and solvent phases. additional purification. NMR spectra (1H, 13C, and 19F) were
XYZ Cartesian coordinates for optimized geometries of both recorded on an AV 400 Avance-III 400 MHz FT-NMR spectrometer
(Bruker Biospin International, Switzerland) with tetramethylsilane
the fluorophores were specified in SI6 in the Supporting (TMS) as a standard reference, and mass spectra of all the synthesized
Information. fluorophores were recorded on a high-Resolution mass spectrometer

■ EXPERIMENTAL SECTION
General Information and Measurements. The used solvents
(HRMS), Waters, USA, XEVO G2-XS QTOF model. Thermogravi-
metric analysis (TGA) was performed using a TA Instrument
TGAQ50 thermal analysis system. UV−vis absorption was measured
using a UV−vis spectrophotometer (Shimadzu Corporation, Japan/
during the reactions were properly dried and distilled from the
suitable desiccants before use, and all reactions were conducted in the UV-2450 Perkin Elmer, USA/Lamda 25), and photoluminescence
(PL) spectra were recorded using an Edinburgh instrument FLS980
spectrofluorometer. The absolute PL quantum yields (PLQY) were
measured using an Edinburgh instrument spectrofluorometer,
integrating the sphere SC-30 model. Cyclic voltammetry (CV) of
the fluorophores was carried out by using an AUTOLAB 302 modular
potentiostat electrochemical analyzer at 298 ± 1 K. The tests were
conducted using three conventional electrode configurations: an Ag/
AgCl reference electrode, a platinum plate secondary electrode, and a
glassy carbon working electrode. Tetrabutylammonium perchlorate
(Bu 4 NClO 4 ) was used as a supporting electrolyte in the
dimethylformamide (DMF) used for the tests, and the scan rate
was kept at 100 mV s−1. Molecular geometrical properties of the
fluorophores, optimized structure, and HOMO−LUMO energy levels
of the fluorophores were theoretically calculated by using DFT with
B3LYP/6-31G (d,p) basic set using Gaussian09 program package.
Device Fabrication and Measurements. The demonstration of
OLED devices using synthesized materials as a dopant and pure film
was fabricated as ITO/PEDOT:PSS/CBP: emitters of 1, 3, 5, and 100
Figure 3. Thermographs of 3-PIMCFTPA and 3-BICFTPA. wt %/TPBi/LiF/Al (Figure 8). The indium tin oxide (ITO)-

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Figure 4. UV−vis absorption spectra of the fluorophores in (a) solution (b) solid.

Figure 5. PL emission spectra of the fluorophores in (a) solution (b) solid.

Figure 6. Lifetime decay profiles of (a) 3-PIMCFTPA and (b) 3-BICFTPA in solution.

the prepared substrate and baked at 130 °C for 15 min. The emissive
layer (EML) consisted of a (CBP) as a host with dopant 3-
PIMCFTPA and 3-BICFTPA. The host is doped with 1, 3, 5, and
100 wt % of 3-PIMCFTPA and 3-BICFTPA, respectively, in the
tetrahydrofuran solution. The EML (20 nm) was spin-casted onto the
HIL at 2500 rpm for 20 s. Later, the substrate was transferred to a
physical vapor deposition vacuum chamber. TPBi (ETL) (45 nm),
LiF (EIL) (1 nm), and Al (cathode) (150 nm) were thermally
evaporated at a vacuum of <6 × 10−6 torr. To analyze the device, the
EL spectrum, luminance, and the CIE coordinates were measured
using a PR-655 spectrometer. The current density−voltage−
luminance (J−V−L) characteristics were calculated by a voltmeter
Figure 7. Cyclic voltammogram of 3-PIMCFTPA and 3-BICFTPA. (Keithley 2400) and CS-100 Minolta. All the characteristic measure-
ments of the fabricated devices were done at ambient temperature in a
sputtered glass substrate was properly washed with acetone at 50 °C dark room.
and subsequently by isopropyl alcohol at 60 °C. Additionally, the glass Synthesis of Targeted Fluorophores. In the presence of
substrate was exposed to UV�ozone for 15 min and shifted into a ammonium acetate (NH4OAc) and acetic acid (AcOH), intermedi-
N2-filled glovebox for spin-coating. The hole-injection layer (HIL) ates were synthesized via condensation between diketone, aniline
(PEDOT:PSS) (40 nm) was spin-casted at 4000 rpm for 20 s onto derivatives, and aldehyde derivatives, and Suzuki coupling reactions

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Table 2. Electrochemical Properties of 3-PIMCFTPA and 3-BICFTPAa

compounds Eonset
red (V) Eonset
oxd (V) HOMO (eV) LUMO (eV) energy gap Eg (eV) wavelengthb (nm)
3-PIMCFTPA −1.54 1.38 −5.78 −2.86 2.92 424.66
3-BICFTPA −1.21 1.28 −5.68 −3.19 2.49 497.99
a onset b
Ered = onset reduction potential, Eonset
oxd = onset oxidation potential, Eg = electrochemical band gap = ELUMO − EHOMO. The wavelength calculated
from 1240/Eg.

Table 3. Doping Concentration Influences on EL Properties, Such as PE, Current Efficacy (CE), EQE, CIE Coordinates, and
Maximum Luminance (Lmax) of 3-PIMCFTPA and 3-BICFTPA
O. V.
doping con. D.V. (V)@100 cd PE100/ PEmax/ CIExy Lmax
dopant (wt %) (V) m−2 CE100/EQE100 (lm W−1/cd A−1/%) CEmax/EQEmax (lm W−1/cd A−1/%) coordinates (cd m−2)
3-PIMCFTPA 1 4.1 5.2 0.4/0.6/3.0 0.6/0.8/3.4 (0.17, 0.02) 530
3 4.2 5.4 0.4/0.7/2.8 0.6/0.8/3.4 (0.17, 0.07) 614
5 4.2 5.3 0.5/0.8/3.0 0.8/1.2/3.8 (0.17, 0.09) 588
7.5 4.1 5.0 0.9/1.5/5.1 1.1/1.7/5.7 (0.17, 0.10) 1077
100 3.8 5.2 0.2/0.4/0.2 0.3/0.4/0.2 (0.28, 0.38) 213
3-BICFTPA 1 6.3 7.7 0.1/0.1/0.3 0.1/0.1/0.4 (0.16, 0.11) 256
3 6.1 7.7 0.1/0.2/0.3 0.1/0.2/0.4 (0.16, 0.11) 257
5 6.1 7.7 0.1/0.2/0.3 0.1/0.2/0.4 (0.16, 0.11) 418
7.5 6.0 7.3 0.1/0.2/0.5 0.1/0.3/0.5 (0.16, 0.11) 473
100 5.1 7.2 0.1/0.1/0.1 0.1/0.2/0.1 (0.24, 0.35) 112

were used to synthesize final products as shown in Scheme 1. The fluorophore showed better thermal stability than that of 3-BICFTPA
synthetic procedure was adopted from our previous reports.38,39 because of the presence of the rigid aromatic structure of
N,N-Diphenyl-3′-(1-(3-(trifluoromethyl)phenyl)-1H-phenanthro- phenanthroimidazole than that of diphenylimidazole. The TGA
[9,10-d]imidazol-2-yl)-[1,1′-biphenyl]-4-amine (3-PIMCFTPA). results propose that the newly synthesized fluorophores provide
Yield: 70%, mp 178 °C, 1H NMR (400 MHz, CDCl3, TMS, δ desirable thermal properties, and good thermal stabilities are
ppm): 8.91 (d, J = 8.0 Hz, 1H), 8.82 (d, J = 8.4 Hz, 1H), 8.75 (d, J = significant to getting a stable device architecture that endows
8.4 Hz, 1H), 7.93 (d, J = 8.8 Hz, 2H), 7.88−7.68 (m, 5H), 7.58−7.41 operation stability to the fluorophores.
(m, 2H), 7.39 (t, J = 7.6 Hz, 1H).7.34−7.28 (m, 9H) 7.13 (dd, J = Photophysical Properties. The study of optical properties, such
11.6, 7.6 Hz, 5H), 7.07 (t, J = 7.6 Hz, 3H). 13C NMR (100 MHz, as UV−visible absorption and PL behavior of the new fluorophores, is
CDCl3, TMS, δ ppm): 147.59, 147.50, 134.11, 132.70, 129.31, carried out in both the solution [dichloromethane (DCM)] and solid
128.90, 128.37, 127.70, 127.48, 127.33, 126.49, 125.92, 125.19, phase. The absorption spectra are displayed in Figure 4, and the
124.48, 124.38, 123.75, 123.15, 123.04, 122.88, 122.67, 120.48. 19F corresponding data are summarized in Table 1. The absorption
NMR (376 MHz, CDCl3, TMS, δ ppm): −62.41 (s), IR (KBr, ν/ spectra of the blue fluorophore in solution (Figure 4a) show an
cm−1): 1592, 1513, 1495, 1457, 1333, 1279, 1176, 1132, 1091, 1069, absorption band at the higher energy end at ∼242 and ∼264 nm for
752, 696, 510. MS (m/z): calcd for C46H30F3N3, 682.2465 found, 3-PIMCFTPA and ∼241 and ∼274 nm for 3-BICFTPA due to π−π*
682.1555 [M + H]+. transition of the aromatic rings and imidazole rings. Additionally, at
3′-(4,5-Diphenyl-1-(3-(trifluoromethyl)phenyl)-1H-imidazol-2- the higher wavelength side, a weak absorption band at ∼332 and
yl)-N,N-diphenyl-[1,1′-biphenyl]-4-amine (3-BICFTPA). Yield: 76%, ∼334 nm in the case of 3-PIMCFTPA and 3-BICFTPA was observed
mp 150 °C, 1H NMR (400 MHz, CDCl3, TMS, δ ppm) 7.68−7.62 due to the weak ICT between imidazole and TPA units because of
(m, 2H), 7.60−7.50 (m, 2H), 7.43 (t, J = 7.9 Hz, 1H), 7.39−7.25 (m, less communication between triphenylamine (D) and imidazole (A)
14H), 7.23 (dd, J = 7.6, 3.2 Hz, 1H), 7.19−7.02 (m, 9H), 7.08−6.92 due to metaconnectivity between triphenylamine and imidazole.40
(m, 3H). 13C NMR (100 MHz, CDCl3, TMS, δ ppm) 147.60, 147.37, From the solid absorption spectra (Figure 4b), the absorption bands
147.02, 140.69, 138.61, 137.78, 134.25, 133.97, 131.80, 131.50, are found to be redshifted than that of the solution, peaking at 345
131.13, 130.69, 130.25, 130.10, 129.84, 129.03, 128.77, 128.66, and 352 nm for 3-PIMCFTPA and 3-BICFTPA, respectively. This
128.43, 128.28, 127.68, 127.54, 127.42, 127.36, 126.91, 126.87, behavior is seen because of the presence of intermolecular π−π
125.46, 125.43, 124.94, 123.74, 123.00, 122.73, 121.81, 121.68. 19F stacking.41
NMR (376 MHz, CDCl3, TMS, δ ppm): −62.90 (s). IR (KBr, ν/ The PL spectra of the new fluorophores in solution (DCM) and
cm−1): 1592, 1513, 1493, 1452, 1336, 1275, 1174, 1136, 1095, 1069, solid phase are shown in Figure 5 (the key parameters are tabulated in
754, 696, 511. MS (m/z): calcd for C46H32F3N3, 684.2621 found, Table 1). Both the fluorophores show NUV-to-pure blue emission in
684.1241 [M + H]+. dilute solution (Figure 5a, and the PL spectra of 3-PIMCFTPA and
Thermal Properties. The thermal stability of both the blue 3-BICFTPA fluorophores exhibit emission peaking at 408 and 404
fluorophores was studied by using TGA in an inert atmosphere (up to nm, respectively. Similarly, PL spectra of these blue-emissive materials
800 °C), and TGA curves are presented in Figure 3. In general, in the solid phase were observed redshifted than that of the solution
materials with high thermal stabilities are essential since they are phase, and their picking wavelength was found to be 428 nm for 3-
crucial in the device operation and fabrication process. The PIMCFTPA and 418 nm for 3-BICFTPA. The encountered redshift
thermograph reveals that both the fluorophores possess good thermal from solution to solid states suggests an existence of aggregation in
properties, and the thermal degradation temperature (Td) (at 5% the synthesized fluorophores.42 In addition, the PL spectra of 3-
weight loss) of 3-PIMCFTPA and 3-BICFTPA was observed at 253 PIMCFTPA shows two vibronic peaks at around 428 and 444 nm;
and 220 °C, respectively (Table 1). It is observed that due to the these are extra peaks that were observed as a result of excimer
decomposition of the material segments, the final decomposition formation in aggregates states.38 The CIE color coordinates of new
temperature was found to be around ∼570 °C for both the fluorophores in solution and solid are shown in Figure S16, and the
fluorophores, which might be because of the rigid aromatic nature resulting x and y color coordinates are tabulated in Table S1. The
of fluorophores. Among these two fluorophores, the 3-PIMCFTPA PLQY (Φ) of the synthesized fluorophores was calculated in the

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Figure 8. Schematic energy level diagram of doped/undoped emitters. (a) Neat film of 3-PIMCFTPA and 3-BICFTPA and (b) emitters dopped
with host CBP. A proposed energy transmission pathway from host to guest in (c) CBP:3-PIMCFTPA and (d) CBP:3-BICFTPA. (e) Structures
of materials that are used in this research work.

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Figure 9. EL characteristics, such as (a) luminance vs voltage, (b) current density vs voltage, (c) PE vs luminance, and (d) CE vs luminance and
(e) normalized EL spectra and (f) CIE chromatograph of the of 5 wt % doped 3-PIMCFTPA and 3-BICFTPA in CBP host matrix-based solution-
processed deep-blue OLED devices.

solution and solid phase by using an integrating sphere. The absolute ns in the undoped state versus 2.50 ns in the doped state. Similar to
quantum yield (Φ) of the targeted blue-emissive materials was studied this, when doped, 4-BICFTPA exhibits a lifetime of 3.45 ns as
in solution and neat film. The quantum yield (solution/neat film) of opposed to 1.91 ns when undoped.
3-PIMCFTPA is 69.4%/60.3% and 3-PIMCFTPA is 45.1%/24.9%. Electrochemical Properties. An electrochemical study was done
The fluorophores with a good quantum yield are necessary for high- to learn more about the fluorophores’ redox characteristics. Figure 7
performance blue OLEDs. displays the deep-blue-emissive materials’ cyclic voltammograms, and
To know the properties of the excited states of newborn Table 2 contains the relevant electrochemical data. The new blue
fluorophores, the fluorescence lifetime was taken into account using emitters have dissimilar redox behavior, which indicates bipolar
the time-correlated single-photon counting technique under the charge transport characteristics. The onset oxidation potential (Eonset
oxd )
excitation by an appropriate laser source, and the decay curve of the was found to be 1.38 and 1.28 V versus Ag/AgCl, and onset reduction
fluorophores is shown in Figure 6. The data obtained for the potential (Eonset
red ) occurs at −1.54 and −1.21 V versus Ag/AgCl for 3-
fluorescence lifetime are summarized in Table 1. Owing to the PIMCFTPA and 3-BICFTPA, respectively. Redox behavior of the
presence of a single emissive site, the decays were fitted into a fluorophores is very important to evaluate the HOMO and LUMO
monoexponential, and the lifetime of blue emissive materials was energy for the application in OLEDs. Equations 2 and 3 reported by
calculated by using eq 1 de Leeuw et al. can be used to determine the HOMO−LUMO energy
levels.44
i ty
( ) = I0 + A1expjjj zzz onset
k { (1) E HOMO = (Eox + 4.4) eV (2)

where t is the time in ns, I0 is the offset value (I0 = 0), A1 is the scalar
onset
quantity determined from curve fitting, and τ is the exponential decay E LUMO = (Ered + 4.4) eV (3)
time.43 The blue-emissive materials doped in the CBP host were also
subjected to an examination of excited-state lifetimes, and the decay The HOMO/LUMO energy of deep-blue-emissive materials is
curves are displayed in Figure S17. It is observed that in comparison found to be −5.78/−2.86 eV (3-PIMCFTPA) and −5.68/−3.19 eV
to their undoped state, the emitters had a longer lifetime after being (3-BICFTPA), with an energy band gap of 2.92 eV (3-PIMCFTPA)
doped with 1 wt % of CBP. 3-PIMCFTPA exhibits a lifetime of 1.90 and 2.49 eV (3-BICFTPA).37

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Figure 10. Schematic energy level diagram of (a) hole-only and (b) electron-only devices having different materials, 3BICFTPA and 3PIMCFTPA,
while (c,d) displays their corresponding current−density−voltage characteristics.

Figure 11. Atomic force microscopic images of (a−c) ITO/PEDOT:PSS/CBP:5 wt % 3-BICFTPA and (d−f) ITO/PEDOT:PSS/CBP:5 wt % 3-
PIMCFTPA. Where left to right images in each display correspond to the height, amplitude, and phase image. 3-BICFTPA-based EML exhibits Ra
= 0.5 nm and Rq = 0.7 nm, while 3-PIMCFTPA-based EML displays Ra = 0.4 nm and Rq = 0.5 nm.

Electroluminescence Properties. We are inspired to explore the architecture and unique fluorescent emitters were fabricated. The
electroluminescent properties of newly synthesized fluorophore-based investigated undoped and doped stacked devices are displayed in
OLED devices with novel fluorophores’ superior characteristics, such Figure 8a,b. The undoped device configuration exhibits the respective
as high thermal stability, superb redox activity, and suitable device structure: ITO (150 nm)/PEDOT:PSS (35 nm)/3-PIMCFT-
photophysical properties. To examine the EL performance of these PA or 3-BIPTPA (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (200 nm).
dyes, a number of nondoped/doped OLEDs having optimal device Moreover, according to the report, the EL performance of the device

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Figure 12. (a) Energy level diagram of the studied hybrid white OLED. (b) CIE chromatograph, which shows CIE coordinates (0.35, 0.39), (0.34,
0.39), and (0.33, 0.37) at the brightness of 100, 1000, and 10000 cd m−2, respectively. (c) Energy transmission paths from host to dopants.

can be subsequently enhanced by utilizing an appropriate host for the Figures S21,S22. This resulting lower EL is attributed to the
emitters and effective device-making ideas. Therefore, for examining respective key factors: (i) leakage of electrons and holes from the
the primary required tools such as HOMO/LUMO, singlet and triplet recombination layer at the interface/electrodes, (ii) mismatched hole
energy levels, and band gap of newly synthesized fluorescent emitters, and electron injection barriers, which provided imbalance between
a carbazole-derivative-based suitable bipolar host named CBP was these charge carriers in the emissive zone, (iii) exciton quenching
incorporated, and numerous doped devices were made. The doped induced by self-aggregation of emitters, and (iv) generation of
device configuration contains the respective device structure: ITO nonradiative excitons at the junction between the charge-transporting
(150 nm)/PEDOT:PSS (35 nm)/CBP: X wt % 3-PIMCFTPA or 3- layers and the EML.45,46 We also detected that the doped devices
BIPTPA (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (200 nm), where X exhibited better performance as compared with undoped devices.47,48
is 1, 3, 5, 7.5, and 100 wt % of dopants in the host material. Herein, We observed that the doped devices fabricated with 5 wt% 3-
ITO and LiF/Al bilayers were incorporated as the anode and cathode, PIMCFTPA and 3-BICFTPA emitters doped in CBP displayed
which help to improve the hole and electron injection into studied brightness of 588 and 418 cdm−2, respectively, as shown in Table 3.
devices, and Al also works as a light reflector, which improves the The proposed energy transfer route from host to dopants has been
emission of light toward the glass substrate side. The conducting shown in Figure 8c,d. The energy transfer route from CBP to 3-
organic materials, such as polyethylenedioxythiophene/polystyrene PIMCFTPA demonstrates that the higher singlet (3.3 eV) energy
sulfonate (PEDOT:PSS) and 2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phe- level of CBP as compared with that of the 3-PIMCFTPA singlet (3.2
nyl-1-H-benzimidazole) (TPBi), are utilized as the HIL and electron- eV) energy level helps to transfer sufficient energy from the host
transport layer (ETL)/hole blocking layer (HBL), respectively, while material to the guest and prevent back energy transmission from guest
lithium fluoride (LiF) has been incorporated as an electron injection to host. While the energy transfer route from CBP to 3-BICFTPA
layer. The PEDOT:PSS and EML are spin coated on ITO-sputtered displays that the singlet energy level (3.3 eV) of CBP is equivalent to
substrates by the low-cost wet-process method, while the remaining the singlet energy level (3.3 eV) of 3-BICFTPA, which might have
layers of organic and inorganic materials, that is, TPBi, LiF, and Al, some back energy transmission from guest to host, encouraging low
have been deposited via the thermal evaporation method, which performance in the OLED device. In this energy transfer route, the
supports production of the best performance-based devices. The Förster energy transfer process dominates more, and the triplet energy
structures of organic materials utilized in this research have been transfer process causes nonradiative exciton recombination in
revealed in Figure 8c. Initially, the undoped devices experienced fluorescent OLEDs. This demonstrates that the singlet excitons that
significant hole carrier confinement into the undoped EML and participate in PL generation provide 25% internal quantum efficiency
effective exciton generation because of the employed TPBi layer, and 5% external quantum efficiency.
which has a deep HOMO and high triplet energy. However, all the Initially, the concentration of dopants is optimized by incorporat-
undoped devices exhibited poor performance. The summarized EL ing 1, 3, 5, and 7.5 wt% in CBP. The investigated EL performances for
properties of fabricated OLED devices are shown in Table 3. We doped devices with the different concentration devices are presented
observed that the undoped devices fabricated with 3-PIMCFTPA and in Figures S21,S22 and summarized in Table 3. It is displayed in these
3-BICFTPA emitters displayed brightness of 213 and 112 cdm−2, figures that the maximum PE and CE increase as the concentration
respectively. Furthermore, we also observed that the undoped devices varies between 1 and 5 wt%. We also found that the current density
exhibited low luminance and also high current density, as displayed in rises rapidly with respect to the increase in voltage, indicating that the

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Figure 13. Effects of the concentration on EL properties (a) luminance vs voltage, (b) current density vs voltage, (c) PE vs luminance, (d) CE vs
luminance, and (e) EL spectra of the OLED embedded with CBP as a host and emitters, 5 wt% 3-PIMCFTPA and x wt% PO-01. Where x is 0.5,
1.0, 1.5, and 3.0% dopant concentration.

devices had diode characteristics. The EL spectra return to the blue- transfer from host to guest has a significant impact on EL emission.
emissive area once the emitters are doped into the CBP host, and the Moreover, a higher LUMO (2.86 eV) of 3-PIMCFTPA exhibits
color emission also stays steady as the dopant concentrations are effective electron confinement in the EML and causes higher EL
increased. It advocates the suppression of aggregation as the different performance as compared with the 3-BICFTPA-based deep blue
concentrations of dopants doped into the CBP host. It is seen that the OLED. When we compared the power and PE of 3-PIMCFTPA with
dopant concentration is increased, and the luminance is also increased 3-BICFTPA, 3-PIMCFTPA exhibited superior performance, as
up to 3 wt% of dopants as the density of radiative exciton increases. displayed in Figure 9c,d. The 5 wt% 3-PIMCFTPA-based deep
However, the luminance instigated to reduce at 5 wt% dopant blue OLED exhibited a maximum PEmax of 0.8 lm/W, a CEmax of 1.2
concentration of 3-PIMCFTPA, which may be a result of self- cdA−1, and an EQEmax of 3.8% along with a brightness of 588 cdm−2,
aggregation. The OLED device consisting of 1, 3, 5, and 7.5 wt % 3- while 5 wt% 3-BICFTPA doped in the CBP host-based device
PIMCFTPA dopant concentration exhibited an EQEmax of 3.4, 3.4, displayed a PEmax of 0.1 lmW−1, a CEmax of 0.2 cdA−1, and an EQEmax
3.8, and 5.7%, with CIE coordinates (0.17, 0.02), (0.17, 0.07), (0.17, of 0.4%, along with a maximum brightness of 418 cdm−2. The attained
0.09), and (0.17, 0.10). While the OLED device consisting of 1, 3, 5, EQE of 3.8% and CIE showed around (0.17, 0.02) of the solution-
and 7.5 wt% 3-BICFTPA dopant concentration exhibited an EQEmax processed OLED device, which is comparable to the previous report,
of 0.4, 0.4, 0.4, and 0.5%, with CIE coordinates (0.16, 0.11), (0.16, as summarized in Table S4.49,50 The superior performance of the 3-
0.11), (0.16, 0.11), and (0.16, 0.11). The device performance is PIMCFTPA-based deep blue OLED device may be attributed to
optimized at 7.5 wt% for the deep blue fluorophore dopants 3- efficient radiative exciton generation, effective energy transfers from
PIMCFTPA and 3-BICFTPA. The summarized EL properties of host to guest, and high quantum yield of the deep blue emitter.
deep blue OLED devices fabricated with 3-PIMCFTPA and 3- Moreover, the 3-PIMCFTPA-based deep blue OLED possesses a
BICFTPA emitters have been displayed in Figure 9 and Table 3. The 60.3% internal quantum yield, while 3-BICFTPA displays a 24.9%
high current density and high luminance are displayed for 5 wt% 3- internal quantum yield. Exciton utilization efficiency (EUE) values of
PIMCFTPA doped into CBP, which is higher than the 5 wt% doped 3-PIMCFTPA and 3-BICFTPA are calculated to be ≈ 47.5 and
3-BICFTPA-based deep blue devices, as shown in Figure 9a,b. The 10.0%. We observed that 3-PIMCFTPA’s EUE is substantially higher
higher current density and high luminance of the 3-PIMCFTPA- than the theoretical 25% limit of conventional fluorescent emitters,
based device as compared with those of the 3-BICFTPA-based device showing that many triplet excitons are being converted to singlet
indicate that despite charge trapping effects in the host, energy excitons throughout the EL process. While EUE of 3-BICFTPA is

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lower than 25%, this may be due to back energy transfer from guest to
Lmax (cd
Table 4. Summary of EL Properties of the Studied OLED Embedded with CBP as a Host and Emitters 3-PIMCFTPA at 3 wt% and PO-01 at Different Concentrations

13,690
17,680
20,590
23,070
host. Both dopant materials 3-PIMCFTPA and 3-BICFTPA
m−2)
displayed ultraviolet deep blue emission having CIE of (0.17, 0.09)
and (0.16, 0.11), respectively, and exhibited emission maximum
0.37) centered at 385 and 390 nm wavelength. In addition, the EL spectra at
0.37)
0.41)
0.47)
different voltages for different doping concentrations of 3-
PIMCFTPA and 3-BICFTPA were also carried out and presented
0.38)/(0.29,
0.39)/(0.33,
0.42)/(0.37,
0.49)/(0.41, in Figure S23. From the respective Figure S23, it is observed that EL
CIExy coordinates

spectra are stable at different applied voltages. At a lower voltage, the

5 wt% doped 3-BICFTPA-based device showed slight redshifting in
the spectra, which may be accredited to insufficient energy
0.38)/(0.30,
0.39)/(0.34,
0.42)/(0.39,
0.49)/(0.43,

transmission.
The fabrication of single charge carrier devices with 3-BICFTPA
and 3-PIMCFTPA compounds was done to realize if these materials
exhibit better charge transport ability and to investigate charge
(0.31,
(0.35,
(0.40,
(0.44,

injection from electrodes. Hole-only devices are fabricated with the

layers of 3-BICFTPA and 3-PIMCFTPA sandwiched between TAPC
hole-transport contacts having device configuration ITO/PE-
CEmax/EQEmax (lm W−1/cd A−1/%)

DOT:PSS/TAPC/3-BICFTPA or 3-PIMCFTPA/TAPC/Al, while

electron-only devices consisted of the ITO/TPBi/3-BICFTPA or 3-
PIMCFTPA/TPBi/LiF/Al device layout, as displayed in Figure
17.5/20.2/10.2
22.5/25.4/12.0
20.8/30.8/14.2
19.1/29.0/14.8

10a,b, respectively. Their corresponding current−density−voltage

characteristics are displayed in Figure 10c,d, respectively.
PEmax/

For the hole-only devices, it is observed that the 3-PIMCFTPA-

based device exhibits higher hole transport as compared with 3-
BICFTPA-based devices, while for electron-only devices, the 3-
BICFTPA- and 3-PIMCFTPA-based devices display a similar trend
in current density. It is also observed that the device fabricated with 3-
PIMCFTPA exhibits good current density at a lower voltage as
compared with that of 3-PIMCFTPA-based devices. The electron and
CE1000/EQE1000 (lm W−1/cd A−1/%)

hole currents are very similar for the 3-PIMCFTPA material,

representing balanced bipolar charge transport in 3-PIMCFTPA as
compared with that in 3-BICFTPA. Moreover, it is also observed that
the current slightly depends on the voltage at lower voltages, which
21.4/24.9/11.6
20.8/24.6/11.3
19.1/27.5/14.3
17.5/20.8/9.6

may be attributed to the behavior of trap filling, while the devices

PE1000/

exhibit trap-free transport of current. Additionally, the hole- and

electron-current−density curves of these materials are equivalent to
each other, confirming their bipolar charge transport nature.
Furthermore, the morphological properties of EML affect the
performance of overall devices. To investigate the roughness,
morphologies, and its influence on the device performance, we have
captured the AFM images of EMLs containing an optimized
concentration of 3-BICFTPA and 3-PIMCFTPA compounds. We
CE100/EQE100 (lm W−1/cd A−1/%)

have spin-coated 5 wt% 3-BICFTPA doped in CBP and 5 wt % 3-

PIMCFTPA doped in CBP on glass/ITO/PEDOT:PSS surfaces. The
AFM images were captured with tapping mode having a 5 × 5 μm2
13.4/14.9/10.2

11.8/13.2/14.2
15.8/17.6/14.8
10.0/11.1/8.6

scanning area, which are displayed in Figure 11. We observed that 3-

PE100/

BICFTPA-based EML exhibits Ra = 0.5 nm and Rq = 0.7 nm, while 3-

PIMCFTPA-based EML displays Ra = 0.4 nm and Rq = 0.5 nm, which
indicates that 3-BICFTPA-based EML has a rougher surface as
compared with 3-PIMCFTPA-based EML. This higher roughness
confirms the poor brightness in 3-BICFTPA-based devices as
compared with that of 3-PIMCFTPA-based OLEDs. Furthermore,
higher roughness of the 3-BICFTPA-based EML also hinders the
transport of charge carriers in the EML, influencing sufficient exciton
voltagesa (V)

formation in this region resulting in poor performance as compared

3.4/3.8/5.5
3.2/3.7/5.1
3.3/3.7/4.9
3.4/4.5/5.7
operating

with that of 3-PIMCFTPA-based deep blue OLEDs.

Finally, we are inspired by superior EL characteristics of the 3-
PIMCFTPA-based deep blue OLED and fabricated a solution-
processed hybrid white OLED having single EML by incorporating a
deep blue fluorescent emitter (5 wt% 3-PIMCFTPA) along with
PO-01 (wt %)

different concentrations (0.5, 1.0, 1.5, and 3 wt%) of yellow

phosphorescent emitter PO-01,51,52 which involves the resulting
0.5
1.0
1.5
3.0

device configuration: ITO (150 nm)/PEDOT:PSS (35 nm)/CBP: 5

wt % 3-PIMCFTPA and x wt% PO-01 (20 nm)/TPBi (40 nm)/LiF
(1 nm)/Al (200 nm). The energy level diagram of the hybrid white
OLED is presented in Figure 12a, and the corresponding CIE at
(wt %)
dopant

different brightness is shown in Figure 12b. The summarized key

5.0

parameters are presented in Figure 13a−d and Table 4. We have

achieved a hybrid white OLED by incorporating 5 wt% 3-

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PIMCFTPA and 1.0 wt% PO-01, which is operated at a low voltage

(3.2 V) and superior performance, as indicated by a PEmax of 22.5
lmW−1, a CEmax of 25.4 cdA−1, and an EQEmax of 12.0%, along with a
■ AUTHOR INFORMATION
Corresponding Author
maximum brightness of 17680 cdm−2. Furthermore, we also observed Sivakumar Vaidyanathan − Department of Chemistry,
that the resultant device demonstrated CIE of (0.35, 0.39), (0.34, National Institute of Technology Rourkela, Rourkela 769008,
0.39), and (0.33, 0.37) at 100, 1000, and 10000 cdm−2, which are very India; orcid.org/0000-0002-2104-2627; Phone: +91-
much close to pure white emission of (0.33, 0.33), as defined by 661-2462654; Email: [email protected]
NTSC. The obtained hybrid white emission is sufficient for use
indoors, outdoors, and in general-purpose lighting applications. Authors
Figure 13e displays that the EL spectra of the studied device are Jaipal Devesing Girase − Department of Chemistry, National
more triggered by the dopant concentrations of yellow dye PO-01. Institute of Technology Rourkela, Rourkela 769008, India
The device has a 1 wt% doping concentration of yellow, and the 5 wt Mangey Ram Nagar − Department of Materials Science and
% deep blue dye exhibited a broad emission peak of blue light as Engineering, National Tsing Hua University, Hsinchu 30013,
compared with the yellow emission peak, which causes white emission Taiwan
from the device. Furthermore, it is identified that the increment in the Shahnawaz − Department of Materials Science and
concentration of yellow dye from 0.5 to 3.0 wt% displayed a reduced Engineering, National Tsing Hua University, Hsinchu 30013,
intensity of blue emission, and yellow emission became broader as Taiwan
compared with blue emission. This EL spectra exhibited two emission
Abhijeet Choudhury − Department of Materials Science and
peaks corresponding to 3-PIMCFTPA and PO-01 dye. On the other
hand, the changes in emission peaks as the concentration of PO-01
Engineering, National Tsing Hua University, Hsinchu 30013,
changes may be attributed to efficient radiative exciton generation at Taiwan
the yellow dye and partial energy transfer to PO-01 from 3- Jwo-Huei Jou − Department of Materials Science and
PIMCFTPA to PO-01. The energy transmission route from host to Engineering, National Tsing Hua University, Hsinchu 30013,
guest is shown in Figure 12c, which exhibited Dexter energy transfer Taiwan; orcid.org/0000-0002-9413-0206
from CBP to PO-01 and 3-PIMCFTPA to PO-01 and Förster energy Complete contact information is available at:
transfer from host CBP to 3-PIMCFTPA and PO-01 emitters. This https://pubs.acs.org/10.1021/acsaelm.2c00648
work offers a new material design approach and device engineering
methodology to fabricate highly efficient, cost-effective, and energy-
Author Contributions
saving hybrid white and deep blue OLEDs for general-purpose §
lighting applications. These two authors are equally contributed (J.D.G. and
M.R.N.).

■ CONCLUSIONS
In summary, we exploited two new NUV/deep blue emitters,
Notes
The authors declare no competing financial interest.
3-PIMCFTPA and 3-BICFTPA, by integrating TPA as a hole-
transporting moiety (D) and imidazole as an electron
transporting moiety (A) with metaconnectivity using a
■ ACKNOWLEDGMENTS
S.V. acknowledges SERB, Department of Science and
Technology (DST), India (EMR/2016/002462), for financial
solution-processed technique. These emitters offered intense
support.
blue emissions in solution and solid. Using 3-PIMCFTPA
fluorophores as the dopant material, the doped OLED was
fabricated, and the devices exhibited NUV/deep-blue EL with
greater efficiencies, a PEmax of 0.6 lm W−1, a CEmax of 0.8 cd
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4382 https://doi.org/10.1021/acsaelm.2c00648
ACS Appl. Electron. Mater. 2022, 4, 4368−4382