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1 s2.0 S0030399217311854 Main PDF
1 s2.0 S0030399217311854 Main PDF
a r t i c l e i n f o a b s t r a c t
Article history: Solution-processed techniques attract increasing attentions in organic electronics for their low-cost and
Received 14 August 2017 scalable manufacturing. We demonstrate the favorite hole injection material of solution-processed aque-
Received in revised form 24 October 2017 ous MoOx (s-MoOx) with facile fabrication process and cast successful application to constructing efficient
Accepted 8 November 2017
organic light-emitting diodes (OLEDs). Atomic force microscopy and X-ray photoelectron spectroscopy
analysis show that s-MoOx behaves superior film morphology and non-stoichiometry with slight oxygen
deficiency. With tris(8-hydroxy-quinolinato)aluminium as emitting layer, s-MoOx based OLED shows
Keywords:
maximum luminous efficiency of 7.9 cd/A and power efficiency of 5.9 lm/W, which have been enhanced
OLED
Solution process
by 43.6% and 73.5%, respectively, in comparison with the counterpart using conventional vacuum ther-
MoOx mal evaporation MoOx. Current-voltage, impedance-voltage, phase-voltage and capacitance-voltage char-
Hole injection acteristics of hole-only devices indicate that s-MoOx with two processes of ‘‘spin-coating/annealing”
Interface engineering shows mostly enhanced hole injection capacity and thus promoting device performance. Our experi-
ments provide an alternative approach for constructing efficient OLED with solution process.
Ó 2017 Elsevier Ltd. All rights reserved.
https://doi.org/10.1016/j.optlastec.2017.11.010
0030-3992/Ó 2017 Elsevier Ltd. All rights reserved.
86 Q. Zheng et al. / Optics and Laser Technology 101 (2018) 85–90
aqueous solution and subsequent annealing don’t involve ammo- cess of ‘‘spin-coating/annealing” refers as s-MoOx1 (Device A1).
nium molybdate ((NH4)6Mo7O244H2O) precursor [33,34] and While the MoOx HIL with two or three processes of ‘‘spin-coat
plasma treatment [9], which considerably simplifies device fabrica- ing/annealing” refers as s-MoOx2 (Device A2) or s-MoOx3 (Device
tion. In addition, in comparison with conventional one process of ‘ A3). The OLED without HIL (Device B) or using vacuum thermal
‘spin-coating/annealing” [30], the hole injection capacity of s- evaporation MoOx (e-MoOx, 2 nm) as HIL (Device C) was also con-
MoOx can be further enhanced by employing two processes of ‘‘spi structed for comparison. The active area of these devices was 5 5
n-coating/annealing”, which contributes to extremely enhance- mm2. The layer thickness and deposition rate were monitored and
ment in device efficiency and decrease in driving voltage. Our controlled in situ with an oscillating quartz thickness monitor.
results pave an alternative way for advancing OLEDs with solution Typical deposition rate for organics was 2 Å/s. Fig. 1 shows the
process. schematic structure of s-MoOx based OLEDs. The molecular struc-
tures of organic materials used are shown in Fig. S1 in Supporting
2. Experiment details Information.
The current-voltage-luminance (I-V-L) characteristics were
MoOx solution (0.25% in weight ratio) was obtained by simultaneously measured with a computer controlled pro-
dissolving MoO3 powders (>99.5%) into de-ionized water with grammable Keithley 2636B Source Meter and Konica Minolta LS-
continuously-prolonged stirring and heating at about 75 °C. The 150 Luminance Meter. The electroluminescent (EL) spectrum and
hydrolysis reaction of MoO3 was occurred as Eq. (1). 1931 Commission Internationale d’Eclairage (CIE) color coordi-
nates were measured with an Ocean Optics Maya-2000-Pro Spec-
þ
MoO3 þ H2 O ¼ MoO2
4 þ 2H ð1Þ trum Scan. All measurements were carried out at room
It is obvious that accumulation of H+ ions significantly retards temperature under ambient conditions. An atomic force micro-
hydrolysis and weakens solubility of MoO3 powders in de- scopy (AFM, Bruker Dimension Edge) was used for characterizing
ionized water. The maximum concentration of MoOx aqueous surface morphology. The X-ray photoelectron spectroscopy (XPS)
solution was 0.25% in our experiments. ITO coated glass was chem- was characterized with Thermo Scientific Escalab 250Xi System.
ically cleaned and served as substrate/anode for studied OLEDs. A monochromatic Al Ka (1486.6 eV) was used in the XPS measure-
The HIL was formed by spin-coating MoOx solution (filtered ment. An Agilent 4294A Precision Impedance Analyzer was used
through a 0.22 lm filter) at 4000 rpm for 60 s and subsequently for impedance spectroscopy analysis.
heat treated at 120 °C for 20 min in air conditions. The hole trans-
port layer (55 nm) of N,N0 -bis(naphthalen-1-yl)-N,N0 -bis(phenyl)- 3. Results and discussions
benzidine (NPB), emitting layer (25 nm) of tris(8-hydroxy-quinoli
nato)aluminium (Alq3), electron transport layer (15 nm) of 4,7- Fig. 2 shows the AFM images of bare ITO and s-MoOx2 film coat-
diphenyl-1,10-phenanthroline (BPhen) and bilayer cathode of LiF ing onto ITO substrate. One sees that bare ITO shows distinct grains
(0.8 nm)/Al (100 nm) were sequentially piled by thermal deposi- and grain boundaries embedded with a small amount of pin-holes
tion under a vacuum of 4 104 Pa. The MoOx HIL with one pro- on film surface. With MoOx coating onto ITO, smooth surface with
Fig. 1. Schematic structure of OLEDs with HIL of s-MoOx formed by spin-coating MoOx aqueous solution. The image of 0.25% MoOx aqueous solution (faint yellow) is also
incorporated in the figure. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 2. The AFM images of (a) ITO and (b) ITO/s-MoOx2 with scanning area of 2 lm 2 lm.
Q. Zheng et al. / Optics and Laser Technology 101 (2018) 85–90 87
improved flatness is observed. The average roughness (Ra) of ITO/ amounts of Mo5+, observed at 1.1 eV lower binding energies,
MoOx is reduced to 1.11 nm in comparison with that (1.35 nm) of accounts for the existence of oxide vacancy [1,7,21,35]. Moreover,
bare ITO. It indicates that the incorporation of MoOx fills some detailed calculation shows that x = 2.95 for s-MoOx film in this
existing pin-holes and/or removes some spikes of ITO, suggesting study. It is quite similar to e-MoOx film (x = 2.98) [1], behaving
homogeneous MoOx film formation on ITO substrate. non-stoichiometric and thus semi-conducting properties. Such
Atomic composition analysis of s-MoOx film is conducted by special characteristics of MoOx play a key role in tailoring hole
XPS measurements, as shown in Fig. 3(a) and (b). The Mo 3d core injection characteristics in OLEDs [1,7–9].
level spectrum exhibits two bands of Mo 3d3/2 and Mo 3d5/2, The electro-optic properties of Devices A1, A2, A3 and compar-
resulting predominantly from the existence of Mo6+. Small ing with Devices B and C are shown in Fig. 4. Some of critical
Fig. 3. The XPS spectra of s-MoOx film: (a) full spectrum and (b) corresponding Mo 3d core level spectrum.
Fig. 4. (a) Luminous and (b) power efficiencies as a function of current density, and (c) current density and (d) luminance as a function of voltage characteristics of OLEDs
with different HILs.
88 Q. Zheng et al. / Optics and Laser Technology 101 (2018) 85–90
parameters are displayed in Table 1. It is observed that Device A2 gives Alq3 emission with EL peak of 535 nm and CIE color coordi-
(s-MoOx2 as HIL) shows maximum luminous efficiency of 7.9 cd/A nates of (0.338, 0.556), as shown in Fig. S2 in Supporting
and power efficiency of 5.9 lm/W, which have been enhanced by Information.
83.7% and 1.8 times, respectively, as compared with those (4.3 It should be noted that Device A2 shows the best performance
cd/A and 2.1 lm/W) of Device B (without HIL). This is explicitly in comparison with Devices A1 and A3. As is known that MoO3
resulted from the fact that s-MoOx promotes hole injection. More- powders behave lower concentration in water, the two processes
over, the performances of Device A2 are superior to Device C of ‘‘spin-coating/annealing” (s-MoOx2) may better favors filling sur-
(e-MoOx as HIL). For instance, in comparison with Device C, the face pinholes and/or removing corrugations than one process of ‘‘
maximum luminous efficiency and power efficiency of Device A2 spin-coating/annealing” (s-MoOx1), which improves film morphol-
have been enhanced by 43.6% and 73.5%, respectively. The driving ogy. Consequently, we propose that s-MoOx2 forms continuous film
voltage at luminance of 1000 cd/m2 has been decreased from 4.9 V during fabrication process, as schematically depicted in Fig. S3(a)
(Device C) to 4.0 V (Device A2). It suggests that s-MoOx to an in Supporting Information. While 2-nm-thick e-MoOx tends to pro-
extremely extent enhances hole injection in comparison with duce film discontinuity, as schematically depicted in Fig. S3(b) in
e-MoOx. This can also be verified by the current density versus Supporting Information. In such a case, some holes still injecting
voltage curves as shown in Fig. 4(c), i.e., Devices A1, A2 and A3 from ITO directly to NPB without the MoOx HIL, which deteriorates
(s-MoOx as HIL) show higher current density than Device C hole injection capacity as a result of larger barrier height at ITO/
(e-MoOx as HIL) at the same voltage. The promoted hole injection NPB interface. This obviously accounts for the fact that e-MoOx
better favors carrier balance in the emitting layer and thereby pro- behaves slightly inferior hole injection capacity to s-MoOx.
moting luminance. The s-MoOx based OLED reaches a luminance To further investigate the hole injection capability of s-MoOx,
of 22344 cd/m2 at 8 V, which almost doubles that (11281 cd/m2) the following series of hole-only devices (HODs) are fabricated
of e-MoOx based device (see Table 1). Typical s-MoOx based OLED for I-V measurements and impedance spectroscopy analysis.
Table 1
Performance summary of OLEDs with different HILs.
Fig. 5. (a) The I-V curves of HODs with different HILs. Inset: Schematic structure of HODs. (b) the Z-V, (c) u-V and (d) C-V transition characteristics of HODs with different HILs.
Q. Zheng et al. / Optics and Laser Technology 101 (2018) 85–90 89
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