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Article
High-Performance Organic Light Emitting Diode
with Substitutionally Boron-doped Graphene Anode
Tien-Lin Wu, Chao-Hui Yeh, Wen-Ting Hsiao, Pei-Yun Huang, Min-Jie Huang,
Yen-Hsin Chiang, Chien-Hong Cheng, Rai-Shung Liu, and Po-Wen Chiu
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b03597 • Publication Date (Web): 07 Apr 2017
Downloaded from http://pubs.acs.org on April 9, 2017
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Page 1 of 29 ACS Applied Materials & Interfaces
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High-Performance Organic Light Emitting Diode with Substitutionally
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8 Boron-doped Graphene Anode
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14 Tien-Lin Wu,1,2 Chao-Hui Yeh,1 Wen-Ting Hsiao,1 Pei-Yun Huang,2 Min-Jie Huang,2 Yen-Hsin Chiang,2
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17 Chien-Hong Cheng,2* Rai-Shung Liu,2* Po-Wen Chiu1*
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23 Department of Electrical Engineering, National Tsing Hua University, Hsinchu 30013, Taiwan
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26 Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan
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35 ABSTRACT
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38 Hole injection barrier between anode and hole injection layer is of critical importance to
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determine the device performance of organic light-emitting diodes (OLEDs). Here, we
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report on a record-high external quantum efficiency (24.6 % in green phosphorescence)
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48 of OLEDs fabricated on both rigid and flexible substrates, with the performance
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51 enhanced by the use of nearly defect-free and high-mobility boron-doped graphene as an
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54 effective anode and hexaazatriphenylene hexacarbonitrile as a new type of hole injection
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57 layer. This new structure outperforms the existing graphene-based OLEDs, in which
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ACS Applied Materials & Interfaces Page 2 of 29
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MoO3, AuCl3, or bis(trifluoromethanesulfonyl)amide (TFSA) are typically used as a
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doping source for p-type graphene. The improvement of the OLED performance is
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11 attributed mainly to the appreciable increase of hole conductivity in nearly defect-free
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14 boron-doped monolayer graphene, along with the high work function achieved by the use
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17 of newly developed hydrocarbon precursor containing boron in the graphene growth by
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20 chemical vapor deposition.
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48 KEYWORDS: organic light-emitting diodes, graphene, boron doping, polycyclic
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51 aromatic hydrocarbons, chemical vapor deposition, flexibility
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57 *E-mail: chcheng@mx.nthu.edu.tw, rsliu@mx.nthu.edu.tw, pwchiu@ee.nthu.edu.tw
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INTRODUCTION
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Graphene has been considered as an ideal candidate for transparent and flexible
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11 electrode in electronic devices such as organic light-emitting diodes (OLEDs)1-7 and
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14 organic photovoltaic (OPV).8-10 To act as an effective anode in OLEDs, highly p-doped
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17 graphene is essential because it reduces the hole transport barrier while in contact with a
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20 hole injection layer (HIL).2-3,11-12 Generally, two different approaches have been used to
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23 create p-doped graphene films: (1) charge transfer by means of molecular adsorption or
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26 oxide deposition; (2) introduction of substitutional dopant atoms in carbon lattice. For
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29 molecular adsorption or oxide deposition, the doping can be readily achieved through a
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32 dip- or spin-coating of the dopant chemical such as acids,2,11,13 metal chlorides,12,14 metal
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35 oxides,15-17 or molecules with strong electronegativity functional groups.4,18-21 Despite of
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38 its facile implementation, several disadvantages might have long been overlooked. For
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example, a non-negligible doping degradation occurs as exposed to the ambient
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atmosphere over time.9 Increase of surface roughness and decrease of light transmittance
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48 are also unavoidable side effects in this approach that negatively impact device
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51 performance. Likewise, AuCl3 was reported as a potent p-type doping on graphene, with
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54 a remarkable increase of work function of up to 5.1 eV.2,22 However, segregation of gold
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57 clusters causes opaque spots or even short circuits. As such, a highly stable means of
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doping in the anode made of graphene becomes an imminent need in the development of
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high-efficiency OLEDs.
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11 Recently, a few OLED devices using p-doped graphene as the anode have been
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14 demonstrated. The graphene doping was mostly carried out by molecular adsorption or
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17 deposition of transition metal oxides, as discussed above. In this work, we show the
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20 growth of boron-doped graphene using a lab-synthesized precursor which allows
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23 incorporation of boron atoms into hexagonal carbon lattice without introducing much
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26 defects, effectively increasing carrier mobility and work function for its use as a
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29 high-quality anode material in OLEDs. HIL, an adjacent layer in direct contact with the
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32 graphene anode, is another critical issue in the context of OLED performance.
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35 Hexaazatriphenylene hexacarbonitrile (HAT-CN) has been known as an effective anode
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38 modifier due to its large electron affinity and shown to reduce hole injection barrier as
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deposited on graphene.23 Here, we report the fabrication of OLEDs on rigid and flexible
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substrates, on which high-mobility boron-doped graphene is used as an effective anode
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48 and HAT-CN works as a new type of HIL. The resultant OLEDs exhibit the highest
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51 external quantum efficiency in green phosphorescence, outperforming the reported
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54 graphene-based OLEDs with MoO3,3,15,24 AuCl3,2 or (bis(trifluoromethanesulfonyl)amide,
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57 (TFSA)4 as the graphene doping source.
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8 RESULTS AND DISCUSSION
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11 Boron is an element that is adjacent to carbon in the periodic table and known to
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14 induce a p-type conduction as substitutionally doped in graphene. To date, numerous
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17 boron-containing precursors, including diborane (B2H6),25-27 triethlyborane (BEt3),28-29
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20 phenyboronic acid (C6H7BO2)30 and polycyclic aromactic hydrocarbons (PAHs),31-32 have
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23 been used to dope graphene in the growth using chemical vapor deposition (CVD).
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26 Theoretical understanding33-35 of the electronic structure and proof-of-concept
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29 demonstrations of various applications such as field-effect transistors30 and gas sensors28
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32 have also extensively studied on these boron-doped graphene films. However, doping
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35 graphene using the above-mentioned boron-containing precursors have shown to cause
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38 high-density defects. To cope with this problem, we use molecules with
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9,10-dihydro-9,10-diboraanthracene (DBA) core structures, which have been reported to
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act as a building block to assemble graphene nanoribbons with boron heteroatoms.36-37
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48 We synthesized 9,10-dimesityl-9,10-diboraanthracene (DBA(Mes)2) using a convenient
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51 one-pot reaction, and the fresh DBA(Mes)2 was dissolved in toluene and used as a
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54 boron-containing carbon precursor for graphene growth on copper foils in a hot-walled
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57 ambient-pressure CVD system. Pristine graphene sheets grown using only pure toluene as
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a carbon precursor in the same CVD growth conditions were used as the control. Details
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of DBA(Mes)2 synthesis and graphene growth are described in Supporting Information
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11 and Experiment Section.
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14 Raman spectroscopy is a powerful tool to inspect structural properties of CVD
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17 graphene, including the number of layers, stacking order, structural disorders, and
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20 doping.4,22,27-28 Figure 1a shows the Raman spectra of pristine graphene and boron-doped
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23 graphene transferred onto a SiO2/Si substrate. Two prominent peaks, located at ~1590
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26 cm-1 (G peak) and ~2700 cm-1 (2D peak), appear in the spectra. Of particular unique
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29 feature here is a negligible D peak induced by defects in the boron-doped graphene,
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32 indicating that DBA(Mes)2 functions as an excellent boron source for incorporating
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35 boron atoms into the sp2-hybridized carbon network without introducing much structural
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38 disorders. This result is in sharp contrast to the previous works in which commercial
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available B2H625-27 and BEt328-29 were used as the boron sources and caused appreciable
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amount of lattice defects. The hole doping in our graphene sheets is evident in the upshift
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48 of both the G and 2D peaks, consistent with previous experimental and theoretical works
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51 where the p-doping is achieved by different approaches.38-40 The doping level can be
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54 calculated from the shift of the G peak or the 2D peak.41 A p-doping level as high as
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57 3.6×1012 cm-1 can be achieved in our boron-doped graphene using an empirical formula
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derived in Ref. 32. Figure 1b-c display the X-ray photoelectron spectroscopy (XPS) of
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the boron-doped graphene. The peak near 190 eV is correlated with the B 1s core levels,
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11 corroborating the existence of graphitic borons.28,42 This peak can be decomposed into
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14 two subpeaks, assigned to the ideal BC3 at 190.6 eV and the BC4 at 187.5 eV. Figure 1c
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17 shows the C 1s spectrum which is also deconvoluted into two subpeaks. The main peak at
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20 ~284.1 eV is assigned to sp2 carbon bonding and the shoulder peak at ~285.6 eV could be
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23 assigned to C-B or C-O species.28 The boron-doping level in the graphene by using the
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26 area ratio of the two peaks after considering the relative sensitivity factor (RSF), was
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29 estimated to be 4.6 atom %.
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32 The work function, light transmittance, chemical stability, and sheet resistance are
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35 the three most relevant parameters in the context of using graphene as a transparent anode
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38 in OLEDs. Figure 1d shows the sheet resistance ( ) as a function of aging time for four
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different graphene sheets prepared on glass. Pristine graphene, TFSA-coated graphene,
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AuCl3-coated graphene, and boron-doped graphene are compared. For pristine graphene,
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48 the ~350 Ω/ is the highest and stays constant over time. Similarly, the of
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51 TFSA-coated graphene is stable throughout the measurements. In contrast, the
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54 AuCl3-coated graphene exhibits a lowest right after the coating, but rising up
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57 progressively from 100 Ω/ to 270 Ω/ after 300 h. For the boron-doped graphene, the
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doping state is rather stable over time and shows the lowest value (240 Ω/ ) after 300 h
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of aging in ambient conditions. Figure 1e shows the transmittance as a function of light
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11 wavelength for the four different samples. Pristine and boron-doped graphene adsorb 2.3
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14 % and 2.5 % of the incident light at 550 nm with respect to the glass substrate,
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17 respectively, while the TFSA- and AuCl3-coated graphene take up 5.6 % and 5.9 % of the
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20 light at the same conditions, respectively. The light transmittance of boron-doped
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23 graphene is superior than that of graphene doped by molecular or AuCl3 adsorption.
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26 Reduction of the hole-injection barrier from the p-type graphene anode to HIL is
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29 crucial in OLED performance. To evaluate this energy barrier, ultraviolet photoelectron
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32 spectroscopy was used to measure the work function of graphene sheets doped with
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35 different approaches (Figure 1f). It is found that the work function of pristine, boron-,
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38 TFSA-, and AuCl3-doped graphene sheets are 4.7, 5.0, 5.1, and 5.2 eV, respectively. The
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hole density in the boron-doped graphene is compatible with both the TFSA- and
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AuCl3-coated graphene, consistent with the sheet resistance measurements where we see
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48 very close for the boron-, TFSA-, and AuCl3-doped graphene sheets.
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51 Electrical transport provides a measure of fundamental physical properties of the
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54 boron-doped graphene, in particular the doping level and hole mobility. Back-gated
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57 field-effect transistors of pristine and boron-doped graphene were made to extract the
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doping level and hole mobility. Figure 2a shows the optical image of a back-gated
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graphene field-effect transistor. The detail of the fabrication process is provided in the
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11 method section. Transport measurements of the pristine and boron-doped graphene
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14 field-effect transistors were carried out at 300 K under ambient conditions. Figure 2b
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17 shows the transfer characteristics for both transistors. A p-type conduction, as is usually
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20 the case for pristine graphene, can be seen in a slight upshift of the charge neutrality point
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23 to a positive gate voltage. For the boron-doped graphene, the charge neutrality point is
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26 highly upshift to a gate voltage of 41 V, indicating a stronger hole doping in boron-doped
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29 graphene than in pristine graphene caused by moisture adsorption. The carrier
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32 concentration can be calculated from the product of the gate capacitance and the
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35 voltage shift of the charge neutrality point ∆ through the formula ∆ /, yielding
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38 a doping level of ~1.6×1012 cm-1. This doping value is in good agreement with that
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calculated from the Raman shift. In addition, we also extract the hole mobility of
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boron-doped graphene from the transfer characteristics using a constant-mobility model.
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48 The hole mobility of boron-doped graphene at room temperature is around 1600 cm2/V⋅s.
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51 To further examine the mobility, Hall measurements for boron-doped graphene on
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54 SiO2/Si substrate was carried out. The Hall mobility is 1440 cm2/V⋅s at room temperature,
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57 which is rather close to that measured in a FET configuration. In comparison with other
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reported boron-doped graphene on SiO2/Si substrate,30,42 our results presented here show
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a relatively higher hole mobility. The higher hole mobility is attributed to the very low
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11 defect density generated in the current CVD doping methodology.
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14 Graphene-based OLEDs usually use multilayer graphene as an anode due to its
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17 lower sheet resistance.1-2,4,11 However, it requires multiple transfers of graphene to the
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20 substrate in a wet etching process and has to pay the price of more polymer
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23 contaminations and of lower light transmittance. In our OLED devices, we use
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26 boron-doped monolayer graphene as an anode to achieve the same performance as
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29 multilayer graphene does. Pristine graphene and conventional indium-doped tin oxide
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32 (ITO) were used as the control anodes in the same OLED structure and fabrication
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35 process. Figure 3 shows the schematics of fabrication procedure for an OLED device
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38 with a graphene anode. The graphene film was first grown on a copper foil and then
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transferred onto a polyethylene terephthalate (PET) substrate. Optical lithography and O2
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plasma were employed for graphene pattering. In the last step, thermal evaporation is
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48 applied to deposit metal electrodes and the subsequent organic layers. In the current
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51 OLED structure, we replace MoO3 with HAT-CN as a HIL to improve the hole injection
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54 efficiency. The conventional metal oxide tends to form a non-stoichiometric phase at the
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57 high-temperature thermal evaporation process and results in an ineffective hole injection
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in OLEDs.43
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Figure 4a-b shows the device structure and energy diagram of graphene-based OLED
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11 comprising of HAT-CN (10 nm)/TAPC:HAT-CN (10%) (170 nm)/TCTA (45%):TPBi
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14 (45%):Ir(ppy)3 (10%) (30 nm)/TPBi (60 nm)/LiF (1 nm)/Al (100 nm). The combination
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17 of graphene and HAT-CN is first used in the graphene-based OLEDs. All devices showed
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20 a low activation voltage of 2.5 V and OLED performance is summarized in Table 1. The
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23 external quantum efficiency vs. luminance, current efficiency vs. current density, and
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26 power efficiency vs. current density are shown in Figure 4c-d, while the current density
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29 vs. voltage vs. luminance is revealed in Figure S6. Compared to the devices in which
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32 pristine graphene and UV/ozone ITO were used as an anode, the OLED device with
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35 boron-doped graphene exhxibits the highest external quantum efficiency (EQE, 24.6 %),
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38 current efficiency (CE, 95.4 cd/A), and power efficiency (PE, 99.7 lm/W) with 520 nm
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green emission and CIE (x, y) coordinates of (0.31, 0.63). The excellent performance is
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likely due to the higher work function (5.0 eV) and lower sheet resistance. Although the
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48 UV/ozone ITO anode also exhibits the properties of low sheet resistance and high work
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51 function (~4.9 eV), its hole injection efficiency is obviously poorer than that made with
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54 boron-doped graphene. In contrast, the device with pristine graphene anode shows the
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57 lowest efficiency (19.5 %) among the tested OLEDs due to the highest sheet resistance
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and lower work function (4.7 eV). To compare the hole injection efficiency between
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HAT-CN and MoO3, boron-doped graphene OLEDs with 5 nm MoO3 as a HIL were also
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11 made. It is found that HAT-CN provides higher current density and luminance as well as
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14 external quantum efficiency. The comparison of the two device properties are
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17 summarized in the Supporting Information. These results show that the use of
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20 boron-doped monolayer graphene in combination with HAT-CN effectively boosts the
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23 OLED performance by an appreciable higher external quantum efficiency, current
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26 efficiency, and power efficiency, outperforming the previous works that use pristine
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29 graphene as an anode. Besides, we also demonstrate the flexibility of boron-doped
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32 graphene on a 125-µm thick PET substrate. Figure 5 displays the change of
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35 boron-doped graphene in the bending test with a curvature radius of 0.75 mm and the
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38 performance of graphene-based OLED on PET. The slight increase of after 3000
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bending cycles, along with the highest EQE value of 19.4 % in the resulting OLED,
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suggest that boron-doped graphene is highly suited for flexible OLEDs with stable and
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48 remarkable performance.
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54 CONCLUSION
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57 In summary, we have successfully demonstrated the use of boron-containing PAH
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for boron-doped-graphene growth. The doped graphene shows high transmittance
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(97.5 %), low sheet resistance (240 Ω/ ) and p-type behavior with hole mobility of 1600
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11 cm2/V⋅s which appear suitable as anode for OLEDs. The boron-doped graphene was
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14 synthesized and characterized by Raman spectroscopy and FET devices. Compared to the
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17 general doping method, this substitutionally boron-doped graphene is more stable and
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20 higher transparent than charge-transfer doped graphene. The boron doping not only
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23 decreases the sheet resistance, but also raises the work function of the graphene resulting
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26 in appreciable increase of hole transport ability. Furthermore, we have demonstrated the
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29 combination of graphene anode and HAT-CN as HIL to achieve a record-high
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32 performance (EQE, 24.6 %) among graphene OLEDs without any out-coupling
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35 treatment.
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EXPERIMENTAL SECTION
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Pristine and boron-doped graphene growth and transfer:
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48 Clean Copper foils (99.8% purity, 25 µm thick) placed on a quartz boat were
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51 inserted into a quartz tube of an atmospheric pressure chemical vapor deposition
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54 (APCVD) system. The sample area, located at the center of the furnace, was heated up to
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57 1000 °C within 60 min, followed by an annealing at this temperature for 30 min. Ar and
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H2 were introduced into the reaction chamber at a flow rate of 230 sccm and 10 sccm,
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respectively. During the growth, toluene or toluene solution (DBA(Mfes)2, 5×10-2 M) is
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11 used as a carbon source, and carried out by H2 (2 sccm) bubbling. The growth duration
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14 took only 6 min. After the growth, cool down the copper foils from 1000 °C to room
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17 temperature rapidly by moving the furnace. Pristine and boron-doped graphene grown on
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20 copper foils were then spin-coated with poly(bisphenol A carbonate) (PC) as a supporting
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23 layer for a wet-transfer process in an HCl/H2O2 etching solution. The remaining
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26 PC/graphene membranes were washed with deionized water and finally transferred onto a
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29 transparent substrate such as a plastic or glass.
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35 Fabrication of back-gate field-effect transistor:
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38 To fabricate graphene FETs, pristine graphene or boron-doped graphene films were
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transferred onto silicon substrates with 300 nm SiO2 atop. Electron beam lithography and
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reactive-ion etching were employed for graphene patterning. Metal contact (Cr 1 nm and
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48 Au 60 nm) were thermally evaporated onto the restricted patterns by electron beam
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51 evaporator. Electrical transport measurements were carried out using a Keithley 4200
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54 semiconductor system.
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Fabrication of an OLED device:
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The OLED devices with the configuration of HAT-CN (10 nm)/TAPC : HAT-CN (10%)
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11 (170 nm)/TCTA (45%) : TPBi (45%) : Ir(ppy)3 (10%) (30 nm)/TPBi (60 nm)/LiF (1
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14 nm)/Al (100 nm) were fabricated by sequential thermal evaporations onto clean glass or
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17 plastic substrates with different experimental anodes. The effective area of the light
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20 emitting diode is 9.00 mm2. Current, voltage, and light-intensity measurements were
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23 recorded simultaneously using a source meter (Keithley 2400) and an optical meter
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26 (Newport 1835-C) equipped with a silicon photodiode (Newport 818-ST). EL spectra
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29 were measured on a fluorescence spectrophotometer (Hitachi F-4500). All the
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32 measurements were performed at 23 °C in air.
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38 Characterization:
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Raman spectra were taken using a Raman spectrometer (Thermo Scientific DXR
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microscope) equipped with a 532 nm wavelength laser. The sheet resistance of the
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48 graphene samples were measured by using van der Pauw method. The optical
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51 transmittance of the graphene samples was measured by UV-Vis spectrometer (HITACHI
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54 U-4100 spectrophotometer). The work function of each doped graphene was obtained
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57 from ultraviolet photoelectron spectroscopy (ULVAC-PHI 5000 Versaprobe II), using a
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bias of 5 V and light source of HeI (21.22 eV) within beam spot size of ~1 mm diameter
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on graphene sample at an angle of 45° to the horizontal surface. The photoelectron
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11 spectrometer records the data within the resolution of 0.01 eV. XPS analysis was
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14 conducted on a spectrophotometer (ULVAC-PHI Quantera SXM/AES 650) with the Al
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17 X-ray. UPS/XPS measurement was performed under 5 ×10-8 Torr at room temperature.
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23 ASSOCIATED CONTENT
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26 Supporting Information
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29 The Supporting Information is available free of charge on the ACS Publications website.
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32 Synthetic route of DBA(Mes)2, NMR spectrum, Mass spectra, CVD growth scheme, UPS
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35 spectra and OLED performance.
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38 AUTHOR INFORMATION
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Corresponding Author
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*E-mail: chcheng@mx.nthu.edu.tw, rsliu@mx.nthu.edu.tw, pwchiu@ee.nthu.edu.tw
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48 Notes
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51 The authors declare no competing financial interest.
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54
55
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57 ACKNOWLEDGMENT
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The authors appreciate the project support of Taiwan Ministry of Science and
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Technology: (MOST 105-2633-M-007-003; MOST 103-2628-M-007-004-MY3; MOST
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11 103-2119-M-007-008-MY3) and Instrumentation Center of NTHU for the use of
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14 photoelectron spectrometer. T.-L.W. would like to acknowledge Mr. Chien-Min Lu for
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17 the support of 3D-drawing object, Mr. Zheng-Yong Liang for the transistor fabrication
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20 and Mr. Chiu-Chuan Liao for the construction of CVD system.
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23 Reference:
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35 Molybdenum Oxide in Organic Light Emitting Devices. J. Appl. Phys. 2010, 107,
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38 053703.
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45 Figure, Caption and Table
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26 Figure 1. (a) Raman spectra of boron-doped (red) and pristine (black) monolayer
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29 graphene. (b) XPS B 1s core-level spectra of heavily boron-doped graphene, with peak
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32 deconvolution. (c) XPS C 1s core-level spectra of heavily boron-doped graphene, with
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35 peak deconvolution. (d) Variation of sheet resistance over time for pristine, boron-doped,
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38 AuCl3-coated, and TFSA-coated graphene under ambient conditions. (e) Light
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transmittance of pristine, boron-doped, AuCl3-coated, and TFSA-coated graphene. (f)
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Ultraviolet photoelectron spectroscopy spectra (UPS) of pristine, boron-doped,
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48 AuCl3-coated, and TFSA-coated graphene.
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20 Figure 2. (a) Optical microscopy image of a boron-doped graphene device; scale-bar: 20
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23 µm. The rectangle framed by the dashed lines indicates the patterned graphene channel.
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26 (b) Resistivity as a function of back gate voltage.
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51 Figure 3. Schematic illustrations of fabrication processes for graphene-based OLED.
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34 Figure 4. (a) Device architecture of OLED with boron-doped graphene as an anode. (b)
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37 Energy levels of the constituent materials in an OLED. (c) External quantum efficiency
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40 vs. luminance of the graphene-based OLED. The inset shows the optical image of the
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43 lighting OLED device. (d) Current and power efficiency as a function of current density.
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18 Figure 5. (a) Sheet resistance ratio v.s. bend cycle of boron-doped graphene on PET; the
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21 inset shows the optical image of the test samples. (b) External quantum efficiency vs.
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voltage characteristic for a boron-doped graphene OLED made on a PET substrate; the
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28 inset shows the optical image of a lighting boron-doped graphene OLED device on a
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31 bended PET substrate.
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36 Table 1. Comparison of OLED performance and photophysical properties for devices
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38 comprising of different anode materials.
b c d
39 Doping Graphene Graphene HIL ηEQE ηCE ηPE
40 Reference
41 Anode layer [%] [cd/A] [lm/W]
42 G-HNO3 4 GraHIL - 98.1 102.7 Nat. Photon.2
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44 G-(C2H5)3OSbCl6 1 MoO3 20 80 - Nat. Commun.3
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G-CF3SO3H 4 DNTPD - 104.1 80.7 Angew. Chem.11
47 G-GO 3 MoO3 - 82.0 98.2 Nanoscale24
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49 Pristine 1 HAT-CN 19.5 75.3 78.5 This Work
50 a
1 HAT-CN 24.6 95.4 99.7 This Work
Boron-doped
51 a
52 ITO - HAT-CN 22.8 85.5 89.1 This Work
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Structure of device: anode/HAT-CN (10 nm)/TAPC:HAT-CN (10%) (170 nm)/TCTA (45%) : TPBi
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55 (45%) : Ir(ppy)3 (10%) (30 nm)/TPBi (60 nm)/LiF (1 nm)/Al (100 nm). bThe maximum external
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57 quantum efficiency. c The maximum current efficiency. d The maximum power efficiency.
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