Vous êtes sur la page 1sur 5

Discussion on hole traps of amorphous films

of N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-
biphenyl)-4,4′-diamine (α-NPD) deposited at
different substrate temperatures
Cite as: Appl. Phys. Lett. 114, 173301 (2019); https://doi.org/10.1063/1.5089269
Submitted: 18 January 2019 . Accepted: 19 April 2019 . Published Online: 03 May 2019

Yu Esaki, Toshinori Matsushima, and Chihaya Adachi

ARTICLES YOU MAY BE INTERESTED IN

Large photovoltaic response in rare-earth doped BiFeO3 polycrystalline thin films near
morphotropic phase boundary composition
Applied Physics Letters 114, 173901 (2019); https://doi.org/10.1063/1.5090911

Acoustically modulated optical emission of hexagonal boron nitride layers


Applied Physics Letters 114, 171104 (2019); https://doi.org/10.1063/1.5093299

Experimental demonstration of energy harvesting from the sky using the negative illumination
effect of a semiconductor photodiode
Applied Physics Letters 114, 161102 (2019); https://doi.org/10.1063/1.5089783

Appl. Phys. Lett. 114, 173301 (2019); https://doi.org/10.1063/1.5089269 114, 173301

© 2019 Author(s).
Applied Physics Letters ARTICLE scitation.org/journal/apl

Discussion on hole traps of amorphous films of


N,N0-di(1-naphthyl)-N,N0-diphenyl-(1,10-biphenyl)-4,
40-diamine (a-NPD) deposited at different substrate
temperatures
Cite as: Appl. Phys. Lett. 114, 173301 (2019); doi: 10.1063/1.5089269
Submitted: 18 January 2019 . Accepted: 19 April 2019 .
Published Online: 3 May 2019

Yu Esaki,1,2 Toshinori Matsushima,1,2,3 and Chihaya Adachi1,2,3,a)

AFFILIATIONS
1
Center for Organic Photonics and Electronics Research (OPERA), Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395, Japan
2
Japan Science and Technology Agency (JST), Exploratory Research for Advanced Technology (ERATO), Adachi Molecular Exciton
Engineering Project, 744 Motooka, Nishi, Fukuoka 819-0395, Japan
3
International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, 744 Motooka, Nishi,
Fukuoka 819-0395, Japan

a)
Author to whom correspondence should be addressed: adachi@cstf.kyushu-u.ac.jp. Tel.: þ81-92-802-6920. Fax: þ81-92-802-6921

ABSTRACT
The hole current in amorphous films of N,N0 -di(1-naphthyl)-N,N0 -diphenyl-(1,10 -biphenyl)-4,40 -diamine (a-NPD) strongly depends on
substrate temperature during vacuum deposition (Tsub) and is the highest at a Tsub value of around 275 K. However, the reason for this
enhancement of hole current at this Tsub is not clearly understood. In this study, we performed thermally stimulated current (TSC)
measurements, which is a versatile method used to obtain information about carrier traps, on a-NPD films. The TSC results revealed that hole
traps were uniformly distributed throughout the films and that hole traps were the shallowest for films fabricated at a Tsub value of around
275 K. Thus, the shallowest hole traps at this Tsub are believed to be one reason for the highest hole current for a-NPD films. This is the
demonstration of how Tsub affects carrier traps, contributing to a better understanding of the underlying physics in organic amorphous films.
Published under license by AIP Publishing. https://doi.org/10.1063/1.5089269

Intensive studies on organic light-emitting diodes (OLEDs) are Recently, we found that the hole current and air stability of amor-
now in progress because they can be used for next-generation displays phous films of N,N0 -di(1-naphthyl)–N,N0 -diphenyl-(1,10 -biphenyl)–4,
and lighting with the advantages of flexibility, light weight, easy emis- 40 -diamine (a-NPD, see Fig. 1 for the molecular structure), a typical
sion color tunability, and processability. Most OLEDs are composed of hole-transporting material in OLEDs, are the highest when Tsub during
several organic films vacuum-deposited on substrates. Vacuum depo- vacuum deposition is about 275 K.5 The enhanced hole current and air
sition is a slower process to grow organic films than solution-based stability of the films deposited at a Tsub value of about 275 K can be
processes, allowing organic molecules to have enough time to find attributed to their higher density and thermal stability compared to
stable positions. As a result, vacuum-deposited organic films have those of films fabricated at other Tsub values. However, there is a possi-
higher thermal stability and density and anisotropic molecular orienta- bility that other factors also affect electrical properties. In this study, we
tion compared to spin-coated films.1 These film parameters can be fur- measure the thermally stimulated currents (TSCs) of a-NPD films fab-
ther tuned by deposition conditions, such as the substrate temperature ricated at various Tsub values. TSC measurements have been used to
(Tsub) and deposition rate.2–5 It has been reported that the efficiency estimate the density and depth of carrier traps in inorganic materials,
and operational durability of phosphorescence-based OLEDs are polymers, and small-molecule organic materials.7,8 Analyzing our TSC
clearly improved by controlling Tsub.6 Considering the importance of results reveals that hole traps exist in bulk films and are the shallowest
film engineering in OLED fabrication, it is necessary to clarify how when films are fabricated at the optimized Tsub value of around 275 K.
deposition conditions affect the film structures and electrical proper- For measurements of electrical properties and TSCs, we fabri-
ties of vacuum-deposited amorphous films. cated hole-only devices (HODs) with an a-NPD transport layer. The

Appl. Phys. Lett. 114, 173301 (2019); doi: 10.1063/1.5089269 114, 173301-1
Published under license by AIP Publishing
Applied Physics Letters ARTICLE scitation.org/journal/apl

molecules with appropriate kinetic mobility can find stable positions


during deposition.5 This value 0.75 Tg,bulk is slightly smaller com-
pared to the reported Tsub values at which the highest film density was
obtained (0.85Tg,bulk).2–4 The reason for this difference is still
unclear. We need a further study to clarify the reason.
For TSC measurements, an HOD was biased at low temperature
to fill hole traps with injected holes. After trap filling, the HOD was
heated at a certain heating rate (b) under a collecting voltage (Vc). The
holes were released by thermal activation during heating. When
trapped holes existed in the bulk film, the same amount of negative
charges was induced at the electrodes. The released holes drifted to the
electrode(s) along the electric potential, resulting in the gradual change
in the amount of induced negative charges on each electrode, which
was detected as a TSC. Because the trapped holes formed a concave-
shaped electric potential [Fig. S3(a) in the supplementary material],
some of the released holes drifted to one electrode and other released
holes drifted to the opposite electrode when Vc was small.7,8 This led
to the coexistence of positive and negative signals in TSC profiles, as
shown in Fig. S4 (supplementary material), which indicates that the
FIG. 1. Plot of current densities at an electric field of 1.0  105 V/cm as a function origin of the TSC is carrier traps in the bulk film rather than at the sur-
of substrate temperature during deposition (Tsub) for HODs fabricated at Tsub ¼ 246, face. Increasing Vc is effective for obtaining an electric potential with a
273, 299, and 328 K. The dashed line is a guide to the eye. The inset shows the monotonic slope, where all the released holes drifted to one electrode,
molecular structure of a-NPD. leading to the appearance of only positive or negative signals in TSC
profiles [Fig. S3(b) in the supplementary material]. Under these
device structure of the HODs was glass substrate/indium tin oxide “saturated” conditions, the detected TSC comes from the induced
(ITO) anode (100 nm)/a-NPD (300 nm)/MoO3 (30 nm)/Al cathode charge at only one electrode. To estimate the total amount of trapped
(50 nm). The use of ITO and MoO3 with high work functions facili- carriers, we need to measure TSCs at sufficiently large Vc in both bias
tated hole injection and suppressed electron injection from the electro- directions and collate TSC signals. The detailed measurement condi-
des.9,10 Vacuum deposition of a-NPD was conducted at Tsub from 240 tions and theoretical background are summarized in the supplemen-
to 330 K, whereas the MoO3 and Al layers were vacuum-deposited at tary material.
room temperature (299 K) substrates. The detailed fabrication and Figure 2 presents TSC curves measured with various Vc values
electrical measurement conditions for the HODs are summarized in for a HOD fabricated at Tsub ¼ 246 K. When Vc was 1.4 to 2.0 V
the supplementary material. [Fig. 2(a)], negative signals completely disappeared and only positive
We first discuss how Tsub affected hole transport in the a-NPD signals were obtained, meaning that the applied Vc was sufficiently
films. Current density–electric field curves of films fabricated with large to move released carriers to one electrode. Conversely, when Vc
different Tsub values are shown in Fig. S1 (supplementary material). was 0.8–1.4 V, positive signals completely disappeared and only nega-
Current densities taken from these curves at an electric field of tive signals were obtained [Fig. 2(b)]. A slight peak shift observed at
1.0  105 V/cm are plotted vs Tsub in Fig. 1. Similar plots at other high Vc for both signals was caused by the lowering of the energy
electric fields of 5.0  104 and 1.5  105 V/cm are shown in Fig. S2 barrier, which is discussed later. Similar behavior was observed in TSC
(supplementary material). At every electric field, current densities curves of all the HODs fabricated here (Figs. S5 and S6).
strongly depended on Tsub and were the highest at a Tsub value of All TSC curves lacked signals below 85 K and over 115 K because
around 275 K, consistent with our previous report.5 A Tsub value of 85 K was the lower limit of temperature for our TSC system and
around 275 K correspond to 0.75 Tg,bulk, where Tg,bulk is the glass current was injected from an electrode above 115 K. To compensate
transition temperature of ordinary glass (362 K for a-NPD),4 on which for the lack of signals, we fitted the TSC curves with a pseudo-Voigt

FIG. 2. TSC curves of a HOD fabricated


at Tsub ¼ 246 K and measured at (a) neg-
ative (1.4, 1.6, and 2.0 V) and (b)
positive (0.8, 1.0, 1.2, and 1.4 V) collecting
voltages (Vc).

Appl. Phys. Lett. 114, 173301 (2019); doi: 10.1063/1.5089269 114, 173301-2
Published under license by AIP Publishing
Applied Physics Letters ARTICLE scitation.org/journal/apl

FIG. 3. (a) Relationship between the


amount of charges estimated from positive
and negative signals in TSC curves (Q1
and Q2, respectively) and collecting volt-
age (Vc) for HODs fabricated at various
Tsub values and (b) Tsub dependence of
hole trap density calculated from the total
amount of charges (Qtot). The dashed
lines are guides to the eye.

function [the details of the fitting conditions and the results are sum- where k is the Boltzmann constant and s0 is a constant. We measured
marized in the supplementary material (Fig. S7)]. The amount of TSC curves under saturated Vc conditions with different b values
charge Q was calculated by dividing an area of a fitting curve by b. We ranging from 0.04 to 0.16 K/s. The b dependence of TSC curves for a
plotted Q values as a function of Vc for each HOD fabricated at various HOD deposited at 246 K is shown in Fig. 4(a). Tm shifted to higher
Tsub values [Fig. 3(a)] (plots of Q vs collecting field Fc are shown in temperature as b increased because of the delay of carrier release.
Fig. S8 in the supplementary material). The positive Q1 and negative HODs fabricated at other Tsub exhibited similar behavior (Figs. S10
Q2 values in this figure were obtained from TSC curves measured and S11 in the supplementary material). We performed a linear fitting
under negative and positive Vc, respectively. Q1 and Q2 were indepen- for ln(Tm2/b) vs 1/Tm plots to calculate dt (Fig. S12 in the supplemen-
dent of Vc, as shown in Fig. 3(a), indicating the saturated measurement tary material). These dt values need to be calibrated to estimate the
conditions at these Vc values. The sum of Q1 and Q2 is equal to the true trap depth because they include the influence of energy barrier
total amount of charges Qtot, which corresponds to the amount of lowering induced by the external electric field formed by Vc. The
trapped holes in the films. The calculated values of xav/d, where xav is calibration was performed considering the Poole–Frenkel effect.
the average distance between trapped holes and d is the film thickness, The calibration procedure is summarized in the supplementary
were about 0.5 for all the HODs (the theory of TSC measurements is material and Table S1. The calibrated trap depth (dt,cal) is plotted vs
described in the supplementary material, and xav/d values are pre- Tsub in Fig. 4(b). The dt,cal values showed a concave-shaped trend
sented in Fig. S9). This means that the hole traps homogeneously exist against Tsub, with the minimum dt,cal at a Tsub value of around
throughout the a-NPD films. The hole trap density Nt was calculated 275 K (0.75Tg,bulk). We performed photoelectron spectroscopy
by (AC-3, RIKEN KEIKI) to estimate ionization energies (hole trans-
Nt ¼ Qtot =eSd; (1) port levels) of a-NPD films deposited at Tsub ¼ 246 and 299 K.
Although these films have different current densities and hole trap
where e is the elementary charge and S is the device area. Figure 3(b) depths, the estimated ionization energies seem to be similar (Fig.
displays the relationship between Nt and Tsub. Nt decreased monotoni- S13 in the supplementary material).
cally as Tsub increased. One reason for enhanced current density (Fig. 1) is better
To estimate the hole trap depth dt, we used an equation consider- carrier hopping between neighboring molecules in films with
ing the relationship between b and the temperature at a TSC peak Tm higher density as we reported in Ref. 5. Another reason could be
(Refs. 8 and 11) the smaller hole trap depth as can be seen in Fig. 4(b). However,
!   there is no clear interplay between the current density and the
dt Tm 2 k
¼ ln þ ln ; (2) hole trap density [Fig. 3(b)]. Perhaps, the positive effect of better
kTm b s0 dt carrier hopping and the smaller hole trap depth more strongly

FIG. 4. (a) TSC curves of a HOD fabri-


cated at Tsub ¼ 246 K at a heating rate
(b) of 0.04–0.16 K/s and (b) Tsub depen-
dence of the calibrated trap depth dt.cal
estimated from positive and negative TSC
signals. The dashed line in (b) is a guide
to the eye.

Appl. Phys. Lett. 114, 173301 (2019); doi: 10.1063/1.5089269 114, 173301-3
Published under license by AIP Publishing
Applied Physics Letters ARTICLE scitation.org/journal/apl

affect current density than the change in hole trap density does. See supplementary material for the sample fabrication and analy-
Further, there is a possibility that other unknown parameters, sis; the J–V, TSC, and photoelectron yield spectroscopy results; and
which modulate current density, exist in these devices. the TSC theory.
Many types of impurities exist in vacuum-deposited films, such
as water, oxygen, and other materials deposited previously.12–15 In
addition, impurities generated by thermal decomposition in a heated REFERENCES
1
deposition source are included in vacuum-deposited films, and the M. Shibata, Y. Sakai, and D. Yokoyama, J. Mater. Chem. C 3, 11178 (2015).
2
amount of impurities is larger in films fabricated at lower Tsub.16 In S. F. Swallen, K. L. Kearns, M. K. Mapes, Y. S. Kim, R. J. Mcmahon, M. D.
Ediger, T. Wu, L. Yu, and S. Satija, Science 315, 353 (2007).
contrast, vacuum-deposited amorphous films intrinsically contain 3
Y. Z. Chua, M. Ahrenberg, M. Tylinski, M. D. Ediger, and C. Schick, J. Chem.
molecular disorder, which impedes carrier transport. Molecular disor- Phys. 142, 054506 (2015).
der is likely minimized for a-NPD films fabricated at a Tsub value of 4
S. S. Dalal, D. M. Walters, I. Lyubimov, J. J. de Pablo, and M. D. Ediger, Proc.
around 275 K because they have the highest film density and thermal Natl. Acad. Sci. 112, 4227 (2015).
5
stability.5 Impurities and molecular disorder are expected to behave as Y. Esaki, T. Komino, T. Matsushima, and C. Adachi, J. Phys. Chem. Lett. 8,
hole traps in our a-NPD films. However, the true origin of the hole 5891 (2017).
6
J. R. Ribe, P. A. Will, C. H€anisch, M. G. Silveira, S. Lenk, J. R. Viejo, and S.
traps is still unclear and is currently under investigation in our Reineke, Sci. Adv. 4, eaar8332 (2018).
laboratory. 7
T. Hino, IEEE Trans. Electr. Insul. EI-15, 301 (1980).
In summary, to investigate the reason why the maximum hole 8
M. Iwamoto and D. Taguchi, Jpn. J. Appl. Phys. 57, 03EA04 (2018).
9
current is obtained when a-NPD films are vacuum-deposited at M. Kr€ oger, S. Hamwi, J. Meyer, T. Riedl, W. Kowalsky, and A. Kahn, Org.
around 275 K, hole traps were estimated by analyzing TSCs. Our Electron. 10, 932 (2009).
10
TSC results indicated the homogeneous distribution of hole traps in J. Meyer, S. Hamwi, M. Kr€ oger, W. Kowalsky, T. Riedl, and A. Kahn, Adv.
Mater. 24, 5408 (2012).
bulk a-NPD films. While the trap density decreased monotonically 11
R. Chen, J. Electrostat. 3, 15 (1977).
as Tsub increased, the trap depth displayed a concave-shaped trend, 12
H. Fujimoto, M. Yahiro, S. Yukiwaki, K. Kusuhara, N. Nakamura, T. Suekane, H.
with a minimum value at Tsub of around 275 K. The hole current was Wei, K. Imanishi, K. Inada, and C. Adachi, Appl. Phys. Lett. 109, 243302 (2016).
13
higher at Tsub where the trap depth was shallower. Previously, we H. Fujimoto, T. Suekane, K. Imanishi, S. Yukiwaki, H. Wei, K. Nagayoshi, M.
attributed the current enhancement to the decreased molecular dis- Yahiro, and C. Adachi, Sci. Rep. 6, 38482 (2016).
14
tance and narrowing of the density-of-state in high-density amor- F. W€ olzl, I. R. de Moraes, B. L€ussem, S. Hofmann, K. Leo, and M. C. Gather,
Org. Electron. 15, 3251 (2014).
phous films.5 In this study, we found that the change in the carrier 15
T. Ikeda, H. Murata, Y. Kinoshita, J. Shike, Y. Ikeda, and M. Kitano, Chem.
traps by Tsub is an additional possibility for the current Phys. Lett. 426, 111 (2006).
enhancement. 16
Y. Esaki, T. Matsushima, and C. Adachi, Org. Electron. 67, 237 (2019).

Appl. Phys. Lett. 114, 173301 (2019); doi: 10.1063/1.5089269 114, 173301-4
Published under license by AIP Publishing