Aromatic Extension at 2,6-Positions of Anthracene toward an Elegant Strategy for Organic Semiconductors with Efficient Charge Transport and Strong Solid State Emission

Article abstract of DOI:10.1021/jacs.7b09381

Organic semiconductors integrating excellent charge transport with efficient solid emission are very challenging to be attained in the construction of light-emitting transistors and even for realization of electrically pumped organic lasers. Herein, we introduce naphthyl units at 2,6-positions of anthracene to achieve 2,6-di(2-naphthyl)anthracene (dNaAnt), which adopts J-aggregated mode in the solid state as a balanced strategy for excellent charge transporting and efficient solid state emission. Single crystal field-effect transistors show mobility up to 12.3 cm²·V^-1·s^-1 and a photoluminescence quantum yield of 29.2% was obtained for dNaAnt crystals. Furthermore, organic light-emitting transistors (OLETs) based on dNaAnt single crystals distribute outstanding balanced ambipolar charge transporting property (μ_h = 1.10 cm²·V^-1·s^-1, μ_e = 0.87 cm²·V^-1·s^-1) and spatially controllable emission, which is one of the best performances for OLETs.

Full text of DOI:10.1021/jacs.7b09381

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Communication
Aromatic extension at 2,6- positions of anthracene towards
an elegant strategy for organic semiconductors with
efficient charge transport and strong solid state emission
Jie Li, Ke Zhou, Jie Liu, Yonggang Zhen, Li Liu, Jidong Zhang,
Huanli Dong, Xiaotao Zhang, Lang Jiang, and Wenping Hu
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b09381 • Publication Date (Web): 07 Nov 2017
Downloaded from http://pubs.acs.org on November 7, 2017
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Aromatic extension at 2,6- positions of anthracene towards an
elegant strategy for organic semiconductors with efficient
charge transport and strong solid state emission
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Jie Li,†,‡,# Ke Zhou,†,‡,# Jie Liu,† Yonggang Zhen,*,† Li Liu,§ Jidong Zhang,§ Huanli Dong, *,† Xiaotao
Zhang,ǁ Lang Jiang,† Wenping Hu*,†,ǁ
†Beijing National Laboratory for Molecular Science, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese
Academy of Sciences, Beijing 100190, China.
ǁTianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin Uniꢀ
versity and Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China
‡University of Chinese Academy of Sciences, Beijing 100190, China.
§State Key Laboratory of Polymer, Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of
Sciences, Changchun, 130022, China
Supporting Information
inefficient solid state emission;13,14 (ii) low charge carrier mobiliꢀ
ABSTRACT: Organic semiconductors integrating excellent
charge transport with efficient solid emission are very challenging
ty;14ꢀ16 (iii) unmatched energy levels with the metal electrodes.17
to be attained in the construction of lightꢀemitting transistors and
Among the diverse molecular systems, anthracene, known as
a highly luminescent molecule, has recently emerged as novel
promising high performance organic emissive semiconductor. In
2012, Perepichka and coworkers reported the first anthracene
based organic semiconductor with integrated high mobility and
solid state emission, 2ꢀ(4ꢀhexylphenylvinyl) anthracene
(HPVAnt).8 Although reasonable hole mobility (µSC = 2.62
cm2·Vꢀ1·sꢀ1) and high emission (PLQY = 70%) was achieved, the
emission area mainly located in the vicinity of the electrode due to
the unbalanced electron mobility in the channel, resulting from
the mismatch of the energy levels of HPVAnt and the electrodes.
In 2015, our group developed a highly emissive organic semiconꢀ
ductor, 2,6ꢀdiphenylanthracene (DPA), exhibiting a mobility up to
34 cm2·Vꢀ1·sꢀ1 and a PLQY of 41.2% for crystals.11 Unfortunately,
DPA suffers from high threshold voltage due to the large offset
between the energy levels of DPA and the electrodes. Here, we
introduce naphthyl units into the 2,6ꢀ positions of anthracene to
design a new anthracene derivative, 2,6ꢀdi(2ꢀnaphthyl)anthracene
(dNaAnt) with the following considerations: (i) the substitution at
the same sites as DPA and HPVAnt might maintain the Jꢀ
aggregated mode and thus retain efficient emission; (ii) the introꢀ
duction of naphthyl units into the anthracene core can prolong the
conjugation length, which is expected to tune the energy levels
and packing arrangements for the efficient charge injection and
charge transport. Encouragingly, dNaAnt crystals adopt the Jꢀ
aggregated mode, leading to a PLQY of 29.2%. Thanks to the
prolonged conjugated length and compact packing motif, dNaAntꢀ
based fieldꢀeffect transistors show a single crystal mobility as
high as 12.3 cm2·Vꢀ1·sꢀ1. Furthermore, lightꢀemitting transistors of
dNaAnt single crystals demonstrate outstanding balanced ambipoꢀ
larity: µh = 1.10 cm2·Vꢀ1·sꢀ1, µe = 0.87 cm2·Vꢀ1·sꢀ1, which is
among the highest performances for OLETs. Conspicuous emisꢀ
sion and obvious shift of the emission zone can be observed in
OLETs, which can be attributed to efficient injection and transꢀ
porting of charge carriers because of the suitable energy level
alignment. These results make dNaAnt a promising candidate for
even for realization of electrically pumped organic lasers. Herein,
we introduce naphthyl units at 2,6ꢀpositions of anthracene to
achieve 2,6ꢀdi(2ꢀnaphthyl)anthracene (dNaAnt), which adopts Jꢀ
aggregated mode in the solid state as a balanced strategy for exꢀ
cellent charge transporting and efficient solid state emission. Sinꢀ
gle crystal fieldꢀeffect transistors (SCꢀFETs) show mobility up to
12.3 cm2·Vꢀ1·sꢀ1 and a photoluminescence quantum yield (PLQY)
of 29.2% was obtained for dNaAnt crystals. Furthermore, organic
lightꢀemitting transistors (OLETs) based on dNaAnt single crysꢀ
tals distribute outstanding balanced ambipolar charge transporting
property (µh = 1.10 cm2·Vꢀ1·sꢀ1, µe = 0.87 cm2·Vꢀ1·sꢀ1) and spatialꢀ
ly controllable emission, which is one of the best performances
for OLETs.
Multifunctional organic semiconductors are highly pursued
for the development of integrated optoelectronic devices, which is
regarded as a gateway for a variety of applications.1,2 Particularly,
OLETs, embodying the smallest possible integration of organic
light emitting diodes (OLEDs) and fieldꢀeffect transistors
(OFETs), remarkably simplify the structure of active matrix disꢀ
plays.3,4 However, it remains a formidable task to design moleꢀ
cules combining high carrier mobility with efficient solid state
emission since compact packing with strong and plentiful interꢀ
molecular interactions usually not only give rise to excellent
charge transporting property but also quench terribly the solid
state luminescence. This contradiction severely hinders the adꢀ
vancement of OLETs and the realization of electrically pumped
organic lasers.3ꢀ6 For example, rubrene, with a single crystal moꢀ
bility (µSC) about 15 cm2·Vꢀ1·sꢀ1,7 has a photoluminescence quanꢀ
tum yield (PLQY) less than 1% in crystalline state. Though conꢀ
siderable efforts have been devoted to the design and synthesis of
such kind materials, till now, very few molecular systems can
compromise charge transporting and solid state emission.8ꢀ12 Most
of them suffer from either one or all of the following problems: (i)
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integrated optoelectronic applications and offer a facile strategy to
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the design and synthesis of such kind materials.
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As described in scheme 1, dNaAnt was synthesized through
three simple steps in a total yield of 40.5%. First, 2,6ꢀ
dihydroxyanthraquinone (1) was reduced by sodium borohydride
to give 2,6ꢀdihydroxy anthracene (2), which further proceed the
esterification reaction to afford 2,6ꢀbis(trifluoromethanesulfonate)
anthracene (3). Finally, dNaAnt was achieved by a Suzuki couꢀ
pling and was further purified by sublimation for device fabricaꢀ
tion.
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Scheme 1. Synthetic route to dNaAnt
Figure 1. (a, b) UVꢀvis absorption and photoluminescence spectra
of dNaAnt solution (10ꢀ5 M in THF, black), thin film (red) and
single crystals (blue); (c) Fluorescence microscopy of dNaAnt
single crystals under UV light; (d) The frontier molecular orbitals
of dNaAnt from DFT calculations at the B3LYP/6ꢀ31G(d) level.
The absorption spectra of dNaAnt in THF solution show a
wellꢀstructured vibrational band of typical anthracene derivatives
peaking at λ = 404, 384, and 365 nm (Figure 1a.), which correꢀ
sponds to 0ꢀ0, 0ꢀ1 and 0ꢀ2 vibronic peak respectively. Compared
with that of solution, the absorption of thin film and single crysꢀ
tals demonstrate an obvious bathochromic shift (33 nm) with
peaks at 437 nm, 411 nm and 388 nm, indicating strong interacꢀ
tions between molecules in the solid state. The 0ꢀ0 peak of
dNaAnt single crystals in the photoluminescence spectra (Figure
1b) appears at 452 nm, generating a Stokes shift of ~707.2 cmꢀ1,
much smaller than that of solution (1055.8 cmꢀ1). This is probably
because of the smaller configuration difference between the excitꢀ
ing state and the ground state for solid state than that for solution
and less energy loss was obtained for the solid state. Bright blueꢀ
green emission can be observed from the dNaAnt crystals, as
displayed in Figure 1c. The photoluminescence quantum yield of
dNaAnt was 61.2% in solution and 29.2% for single crystals reꢀ
spectively. The red shift of the 0ꢀ0 absorption, the enhanced 0ꢀ0
vibronic peak intensity and the increased radiative decay rate (Kf
= Фf/τ, Фf: the fluorescence quantum yield; τ: the fluorescence
lifetime; Figure S1) suggest a Jꢀaggregated mode of dNaAnt in
solid state,18,19 which is thought to be the balanced strategy to
achieve high mobility and efficient solid state emission coordiꢀ
nately. From the UVꢀVis absorption spectra in crystal state, the
energy gap was calculated to be 2.73 eV. The highest unoccupied
molecular orbital level (HOMO) and lowest unoccupied molecuꢀ
lar orbital (LUMO) level estimated from ultraviolet photoelectron
spectroscopy (UPS, Figure S2) and energy gap was ꢀ5.33 eV, ꢀ
2.60 eV respectively, corresponding well with cyclic voltammetry
(CV) results (Figure S3). The HOMO energy level of dNaAnt is
about 0.3 or 0.17 eV higher than that of DPA or HPVAnt respecꢀ
tively (Figure S4), ensuring better match with Femi energy level
of the gold electrode. DFT calculations were further performed to
shed insights into the frontier molecular orbitals distribution (Figꢀ
ure 1d). πꢀelectron densities of HOMO and LUMO distribute over
the whole molecule. As shown in Figure S5 by thermal gravimetꢀ
ric analysis and differential scanning calorimetry, dNaAnt subliꢀ
mates at 368 °C, and the melting point is as high as 355 °C. The
good thermal stability paves the way for its application in severe
environment.
Using the physical vapor transfer method, the plateꢀlike miꢀ
crocrystals (size: 30 ± 10 ꢁm) were directly grown on the octadeꢀ
cyltrichlorosilane (OTS) modified SiO2 (300 nm)/Si substrate
(Figure 2a, S6). As the deposition time and temperature change,
the thickness of the crystals varies from tens of nanometers to
hundreds of nanometers, showing obvious stepꢀlike layers on the
crystal surface (Figure S7). The outꢀofꢀplane Xꢀray diffraction
(XRD) patterns of the crystals are shown in Figure 2b, where a
series of peaks can be defined as (h00). The strong and sharp difꢀ
fraction peaks indicate the high quality of the crystals. Transmisꢀ
sion electron microscopy (TEM) image of an individual crystal
and its corresponding selectedꢀarea electron diffraction (SAED)
pattern are displayed in Figure 2c. The directions [0k0] and [00l]
can be assigned with the included angle of 90°. The monoclinic
crystal system with lattice constants a = 23.345 Å, b = 7.604 Å, c
= 5.941 Å, β = 92.83° can be determined using SAED pattern
combined with powder XRD pattern and the inꢀplane XRD, which
was indexed in Figure S8. The dꢀspacing (23.28 Å) calculated
from the first order diffraction (3.79°) of outꢀofꢀplane XRD is
nearly the same as the molecular length (22.61 Å) of dNaAnt via
DFT calculation (Figure S9). Same as DPA, the dNaAnt molecule
stands almost perpendicularly to the substrate, which is most faꢀ
vorable for charge transport.20,21 The regular shape, sharp and
strong diffraction peaks, clear and steady diffraction spots imply
the superior quality of the dNaAnt crystals.
The “organic ribbon mask” method was applied to build the
in situ bottom gate top contact single crystal fieldꢀeffect transisꢀ
tors (SCꢀFETs) to evaluate the intrinsic charge transporting propꢀ
erty of dNaAnt.22 Typical optical image of an individual device is
shown in Figure 2d. Representative transfer and output curves are
presented in Figure 2e, 2f. An average mobility of 7.0 cm2·Vꢀ1·sꢀ1
is achieved based on 10 devices (Figure S10a). The mobility for
the best device is 12.3 cm2·Vꢀ1·sꢀ1, with a threshold voltage (VT)
around ꢀ10 V and an on/off ratio about 3.9×107. It is noteworthy
that the device displays not only relatively low threshold voltage
but also almost perfect linearity for the (ꢀIDS)
1/2ꢀVG curve, which
is rare for ultrahigh mobility (>10 cm2·Vꢀ1·sꢀ1) organic semiconꢀ
ductors. The negligible gate voltage dependence of charge
transport for the traditional transistor equations indicates a narrow
density of state with few shallow traps in crystal state (Figure
S10).20,23 The threshold voltage is strongly related to the trap denꢀ
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sity at the interface between the dielectric and the semiconductor
as revealed by the following equation: VT ≈ Vfb ꢀ qNtr / Ci , where
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Vfb is the flat band voltage, Ntr is the trap density, Ci is the dielecꢀ
tric capacitance.24 Since Vfb is normally too low to be counted
compared with VT, we can estimate the trap density to be
6.88×1011 cmꢀ2 by neglecting the contribution of Vfb. In addition,
the maximum current of the transfer curve matches well with that
of output curve, which is important for practical applications.
These characteristics of dNaAnt devices result from the suitable
HOMO level, excellent crystal quality and efficient packing strucꢀ
ture, which eliminate the traps in the device and facilitate charge
transport.
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Figure 3. (a, b) Schematic device configuration of the lightꢀ
emitting transistors; (b) Optical microscopy of the organic lightꢀ
emitting transistors; (c) Energy level alignment for efficient
charge injection; (d) Typical ambipolar transfer curves of the
organic lightꢀemitting transistors.
Though the electroluminescence (EL) spectrum is much
more resolved with increased intensity in the low energy bands
(Figure 4a), the main peaks (452 nm, 474 nm, 516 nm) are almost
the same as that of the PL (452 nm, 476 nm, 512 nm). Figure 4b
shows the images of the EL with drainꢀsource bias kept constant
and the gate voltage being swept. When the drainꢀsource bias is
fixed at ꢀ60 V, much more negative than the initiated gate voltage
(20 V), electrons dominate in the channel. As the gate voltage
become more negative, the hole injection starts and the emission
was observed at the hole injecting electrode (Au). When the gate
voltage is further decreased, the emission zone moves across the
channel towards the electron injecting electrode (Ca/CsF). While
positive drainꢀsource voltage (60 V) is applied, similar movement
of the emission towards the hole injection electrode can be clearly
observed (Figure 4c). These characteristics evidenced the ambipoꢀ
lar working mode of the device, which may lead to higher exterꢀ
nal quantum efficiency than unipolar lightꢀemitting transistors and
is believed to be more useful in practical applications.
Figure 2. (a) Optical microscopy of dNaAnt micro single crystals;
(b) XRD pattern of the single crystals; (c) TEM image of an indiꢀ
vidual crystal and its corresponding SAED pattern; (d) Optical
microscopy of the dNaAntꢀbased SCꢀFET device; (e, f) Typical
transfer curve and corresponding output curve of a dNaAntꢀbased
SCꢀFET device.
In conclusion, the introduction of a naphthyl group into the
2,6ꢀsites of the anthracene core indeed allows the following feaꢀ
tures: (i) prolonged conjugation lengthand compact packing; (ii)
Jꢀaggregated mode; (iii) well alignment of the energy levels with
the electrodes. Thus, dNaAnt crystals integrate high mobility (µSC
= 12.3 cm2·Vꢀ1·sꢀ1) with efficient solid state luminescence (PLQY
= 29.2%). Furthermore, lightꢀemitting transistors of dNaAnt show
almost balanced ambipolarity (µh = 1.10 cm2·Vꢀ1·sꢀ1, µe = 0.87
cm2·Vꢀ1·sꢀ1) and conspicuous emission can be observed, proving
to be one of the best behaviors for ambipolar OLETs. These reꢀ
sults make dNaAnt an excellent candidate for integrated optoelecꢀ
tronic applications and offer a facile strategy to the effective comꢀ
bination of excellent charge transporting and efficient solid state
emission.
In view of the excellent electrical and optical property of
dNaAnt, lightꢀemitting transistors of dNaAnt single crystals were
fabricated with asymmetrical electrodes (Au/MoO3: Ca/CsF), as
shown in Figure 3a, 3b. Owing to the well alignment of the enerꢀ
gy levels with the electrodes (Figure 3c), balanced ambipolar
charge carrier mobility (µh = 1.10 cm2·Vꢀ1·sꢀ1, µe = 0.87 cm2·Vꢀ
1·sꢀ1) can be derived from the transfer curve at a relatively low
voltage of ꢀ60 V or 60 V (Figure 3d), which is one of the best
performances for ambipolar OLETs.12,25,26 The anisotropy characꢀ
teristics are displayed in Figure S11, indicating there was no sigꢀ
nificant difference of the charge transporting property along difꢀ
ferent packing directions.
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Figure 4 (a) Electroluminescence spectrum (EL) of dNaAnt single
crystal; (b, c) Shift of the emission zone within the device channel
by tuning the gate voltage.
ASSOCIATED CONTENT
Supporting Information
Experimental details, synthesis, characterization, device fabricaꢀ
tion, and theoretical studies. This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*zhenyg@iccas.ac.cn
*dhl522@iccas.ac.cn
*huwp@tju.edu.cn
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B. H.; McNeill, C. R.; Friend, R. H.; Sirringhaus, H. Adv. Mater. 2012, 24,
2728.
Author Contributions
#J.L., K.Z.: These authors contributed equally to this work.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
We thank Dr. Yang Li and Mr Jinyu Liu for the calculations and
Mr Qiang Zhao for drawing figures. The authors acknowledge the
Shanghai Synchrotron Radiation Facility (BL17U1) for the XRD
measurements. We are grateful for the financial support from the
Ministry of Science and Technology of China (Grants
2016YFB0401100, 2017YFA0204503 and 2015CB856502), the
National Natural Science Foundation of China (51733004,
91433115, 51633006, 21661132006, 21473222), the Strategic
Priority Research Program (Grant No. XDB12000000) and the
Youth Innovation Promotion Association of the Chinese Academy
of Sciences.
REFERENCES
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ACS Paragon Plus Environment