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Organic Electronics 15 (2014) 3052–3060

Contents lists available at ScienceDirect

Organic Electronics
journal homepage: www.elsevier.com/locate/orgel

Metal deposition for optoelectronic devices using a low vacuum


vapor phase deposition (VPD) system
Francisco F. Navarro a, Peter I. Djurovich b, Mark E. Thompson a,b,⇑
a
Department of Chemical Engineering & Materials Science, University of Southern California, Los Angeles, CA 90089, United States
b
Department of Chemistry, University of Southern California, Los Angeles, CA 90089, United States

a r t i c l e i n f o a b s t r a c t

Article history: A vapor phase deposition (VPD) system has been used to deposit magnesium and zinc films
Received 10 July 2014 and prepare optoelectronic devices under low vacuum conditions, i.e. 1 torr. An analysis of
Received in revised form 16 August 2014 the metal films via SEM, AFM, XRD and four-point probe resistivity measurements revealed
Accepted 25 August 2014
comparable characteristics to metal films deposited in a vacuum thermal evaporation
Available online 10 September 2014
(VTE) system. Magnesium cathodes were fabricated for organic light emitting diodes
(OLEDs) and organic photovoltaic (OPV) devices. OLEDs were fully made in either the
Keywords:
VPD or VTE system employing aluminum tris-(8 hydroxyquinoline) [Alq3] as the green
OLED
OPV
fluorescent emitter or fac-tris(2-phenylpyridine)iridium [Ir(ppy)3] as the green emitting
PHOLED phosphor. Analysis of the OLED devices made in the VPD system showed external quantum
Metal films efficiencies (EQE = 0.9 ± 0.1%) and (EQE = 7.6 ± 0.6%) at a luminance of 100 cd/m2 for the
Magnesium fluorescent and phosphorescent devices, respectively. In addition, organic photovoltaics
Zinc (OPVs) were fully fabricated by both methods employing copper phthalocyanine (CuPc)
and C60 as the donor/acceptor materials. Analysis of the OPV devices made in the VPD sys-
tem showed a power efficiency of 0.5 ± 0.1%, an open circuit voltage of 0.45 ± 0.05% and a
fill factor of 0.50 ± 0.05%.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction vacuum (i.e., 6105 torr), inefficient utilization of materi-


als, poor film conformality and the high expense incurred
Thin metal films have been used widely as cathodes and when deposition is applied on large substrates [3]. High
anodes for optoelectronic devices such as organic light vacuum is required to achieve long mean free paths and
emitting diodes (OLEDs), organic photovoltaics (OPVs) thereby allow the metal atoms to reach the substrate
and thin film transistors (TFTs) to inject/extract charges without colliding, thus realizing smooth, uniform films.
from such devices [1,2]. The most commonly used tech- However, deposition using VTE occurs along a ballistic
niques to deposit metals are electrodeposition and physi- (directional line-of-sight) trajectory preventing the
cal vapor deposition (PVD); among the latter, vacuum formation of conformal films on nonuniform substrates.
thermal evaporation (VTE), a high vacuum method, is Therefore, interest has developed towards non-line-of-
extensively utilized to deposit thin metal films for OLEDs, sight deposition techniques such as chemical vapor deposi-
OPVs and TFTs. The disadvantages of high vacuum meth- tion (CVD) and atomic layer deposition (ALD) [4].
ods are long pump down times needed to achieve high In this paper, a new technique involving a vapor phase
deposition (VPD) as a non-line-of-sight method is utilized
to fabricate thin metal films. VPD relies on a carrier gas
⇑ Corresponding author at: Department of Chemistry, University of
under laminar flow (fluid flow without lateral mixing) to
Southern California, Los Angeles, CA 90089, United States.
E-mail address: met@usc.edu (M.E. Thompson). transport metal vapor onto a cooled substrate by forced

http://dx.doi.org/10.1016/j.orgel.2014.08.049
1566-1199/Ó 2014 Elsevier B.V. All rights reserved.
F.F. Navarro et al. / Organic Electronics 15 (2014) 3052–3060 3053

convection. Laminar and turbulent flows are predicted the material sublimes and ultimately condenses onto the
using the dimensionless Reynolds number (Re), defined substrate is controlled by both the temperature of the
as the ratio of inertia forces with respect to viscous forces source boat and the flow rate of the inert gas, which
[5]. The Reynolds numbers calculated for VPD systems enhances control over the deposition process and the mor-
(Re 6 30) are well below values needed to achieve laminar phology of the films [8–10]. However, while VPD processes
flow in a tube (Re 6 2300). Moreover, in contrast to the have been used to deposit molecular organic materials,
VTE methods used to deposit metal films for organic elec- forming high efficiency OLEDs [11–16], OPVs [17–20] and
tronic applications, which involve vacuums ranging from TFTs [9,21–26], the method has not been used for the
104–1010 torr, the VPD system employs a comparatively deposition of metal films needed to complete fabrication
low vacuum ranging from 0.1 to 10 torr. Other methods to of the device.
deposit metals at low pressure (103–760 torr), such as
sputtering, metal–organic chemical vapor deposition
2. Results and discussion
(MOCVD) or ALD, have limitations that make them unsuit-
able for fabricating organic electronic devices. Sputtering
2.1. Deposition parameters
relies on plasma to produce charged ions and high speed
electrons that can potentially damage organic thin films.
A series of metals were considered for use in the VPD,
MOCVD requires a hot substrate (P100 °C) in order to
including calcium, zinc, cadmium, magnesium, antimony,
decompose the metal–organic to produce a thin metal film.
bismuth, indium and manganese, among others. Of these,
The heated substrate will, in turn, disrupt morphology of
magnesium (Mg) and zinc (Zn) were selected to fabricate
the organic films, particularly in multilayer heterostruc-
metal films and devices, as they have sublimation enthal-
tures. Further, MOCVD can cause organic contamination,
pies that are comparable to organic materials commonly
also known as parasitic deposition, during the decomposi-
used for OLEDs and OPVs (see Table 1) [8,27–29]. Both
tion of the metal–organic compound. ALD typically
metals exhibit low toxicity and have been used as elec-
requires the successive application of precursor com-
trodes to inject charge into OLEDs [2,30,31]. The effective
pounds in the gas phase, necessitating lengthy growth
volatility of both metals was evaluated by calculation of
times for thicker films such as those needed for OLEDs,
molar flow rates (r) using Eq. (1) below [8]; where V_ is
OPVs and TFTs (1–2 h for 100 nm films) [6]. In addition,
the volumetric flow velocity of the carrier gas,
ALD requires high substrate temperatures (P100 °C) to
promote the successive reactions on the substrate surface P org=met
to deposit metals, consequently degrading organic films r ¼ V_  ð1Þ
RT cell
and/or causing parasitic deposition.
The VPD technique is an adaptation from the organic R is the ideal gas constant, Tcell is the temperature of the
vapor phase deposition (OVPD) method. Since its inception source boat and Porg/met is the vapor pressure of the
from 1995 to date, OVPD has been demonstrated to be a organic/metal. The calculations show that Mg and Zn can
versatile, reliable and efficient method to make organic have molar flow rates comparable to values obtained for
thin films [7]. Specifically, the OVPD was designed for organics with high sublimation temperatures, such as CuPc
organic materials that have low sublimation temperatures. and C60 (Table 1). In a laminar flow regime, the diffusion of
Upon sublimation, the material is transported by an inert organics and metals within the carrier gas stream plays an
carrier gas through a hot-wall vessel to avoid unwanted important role in determining the transport efficiency of
deposition prior to condensation on a cooled substrate, the material. Diffusion coefficients for Mg and Zn were cal-
thereby achieving high material usage. The rate at which culated using the Chapman–Enskog theory (Eq. (2)); where

Table 1
Chapman–Enskog diffusion coefficients and sublimation enthalpies for Zn, Mg, CuPc, C60, Alq3 and NPD.

Compound Enthalpy of sublimation Vapor pressure Molar flow rate Diffusion coefficient Molar mass Average collision
(KJ/mol) a,b,c (atm)b,d,* (mol/s) (cm2/s) (g/mol) diameter (Å)**
Nitrogen – – – – 28.0 4.2
Zinc 130.4 ± 0.4a 7.4E03d 8.0E01 614.7 65.4 2.8
Magnesium 147.1 ± 0.8a 3.9E04d 4.2E02 497.6 24.3 4.4
CuPc 211.1 ± 0.1b 1.7E03b 1.8E01 51.9 576.1 18.1
C60 219.6 ± 0.1b 3.9E06b 4.2E04 118.5 720.6 10.5
Alq3 137.7 ± 0.1b 1.1E04b 1.5E02 45.5 459.4 15.2
NPD 139.0 ± 0.3c – – 23.7 588.7 22.6

Calculations of molar flow rates and diffusion coefficients were performed at a pressure of 1 torr. The collision integral (X) was taken as unity given that it
has values between 0.96 and 1.03 for temperatures between 300 K and 1000 K.
*
Temperatures used to calculate vapor pressures of Zn, Mg, CuPc, and C60 was 823 K and 623 K for Alq3 and NPD.
**
Average collision diameter, r1: N2 and r2: Zn, Mg, CuPc, C60, Alq3 and NPD were measured using Titan 1.0.7 software (Van der Waals surfaces used to
determine diameters).
a
Ref. [28].
b
Ref. [27].
c
Ref. [8].
d
Ref. [29].
3054 F.F. Navarro et al. / Organic Electronics 15 (2014) 3052–3060

T is temperature, M is the molar mass, p is pressure, X is temperature. In addition, during initial attempts at fabri-
the temperature cating metal films we found that a water/ethylene glycol
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi (50/50) mixture cooled at 20 °C was incapable of keeping
1:858  103 T 3=2 1 þ M1 þ 1=M2 the substrate below 120 °C. While this temperature was
D¼ ð2Þ
qr212 X sufficient to promote metal deposition, the organic films
were not stable at these temperatures. Thus, we switched
dependence collision integral, r12 = (r1 + r2)/2 is the aver-
our cooling medium to N2 gas cooled to 185 °C. This last
age collision diameter, D is the diffusion coefficient, and 1
modification allowed us to reliably maintain substrate
and 2 are indices for the two molecules present in the gas-
temperatures below 50 °C during metal deposition, and
eous mixture. The calculated results are shown in Table 1.
thereby prepare good quality OLEDs and OPVs (vide infra).
The calculations reveal that the diffusivity of these metals
The above modifications to the VPD chamber (fused
are one order of magnitude greater than values determined
Pyrex wall) and cooling system support deposition rates
for typical OLED and OPV compounds. Such high diffusivi-
of 0.1–35.0 Å/s and enabled us to make metal films with
ties promote metal deposition in various regions of the
thicknesses ranging from 100 to 10,000 nm. However, the
sample chamber upstream from the source nozzles. These
elevated temperature of the system during metal deposi-
problems can potentially be averted by increasing the total
tion caused organics previously condensed on the shutters
flow of the carrier gas. However, an increase in carrier gas
to sublime, leading to cross contamination during fabrica-
flux can raise the operating pressure if the pumping system
tion of the cathode and subsequent device failure. To over-
is not suitable for large flows, thus affecting film morphol-
come this obstacle and avoid cross-contamination with
ogy and crystallinity. In our system, condensation was
organics during the fabrication of the cathode, the shutters
observed upstream on the rear flange of the VPD chamber
were cleaned prior to deposition of the metal.
when the pump did not maintain a pressure of 1 torr in
flows exceeding 60 standard cubic centimeters per minute
(sccm). The inability to pump at a higher velocity necessi- 2.2. Magnesium and zinc metal films
tated a modification in the deposition apparatus by insert-
ing a fused silica wall around the source tubes between For comparative purposes, thin films of Mg and Zn were
zone 3 and zone 4 of our system, seen in Fig. 1. This fused fabricated in both VPD and VTE systems on silicon and pat-
silica wall is unnecessary when depositing materials with terned ITO. Metal films were deposited at rates ranging
low diffusivity, such as organic compounds. from 4 to 8 Å/s and for VPD films, using substrate holder
During the sublimation of Mg and Zn, the VPD chamber temperatures of 20–25 °C and total flows of 60 sccm. Metal
was kept at 450 °C (zone 1) and 550 °C (zones 2–4) to pre- films made by both methods were reflective and glossy.
vent the metals from condensing on the chamber walls. Calibration of the quartz crystal monitor sensor for Mg
However, metals such as Mg and Zn exhibit high surface and Zn films, deposited in the VPD on patterned ITO, was
mobility and poor wettability, a problem that can be corre- accomplished using profilometry. The Mg and Zn films
lated to the critical density and critical temperature of the were analyzed to determine their morphology, roughness,
metals [32–37]. The critical density is a measure of the crystallinity and resistivity. Cross-sectional SEM images of
number of atoms striking 1 cm2/s needed to achieve con- Mg films deposited on silicon substrates using VPD and
densation on a substrate and is directly related to the sub- VTE (Fig. 2) show complete substrate coverage and a crys-
strate temperature [33,34] whereas the critical talline, rough surface morphology. Films made using VPD
temperature is reached when the probability of an atom display a loose packing of blade-like nanocrystals whereas
condensing on the substrate is unity [34]. The high temper- films made using VTE are more densely packed.
atures in the VPD chamber, along with the high surface Three dimensional AFM images (Fig. 3), confirmed the
mobility and poor wettability of Mg and Zn on a hot sub- results showing both films exhibit full substrate coverage
strate, requires efficient cooling to produce high quality and a rough surface texture. However, while the SEM and
films. Therefore, a liquid-cooled substrate holder was built AFM images of the VTE film appeared to have higher
using aluminum (thermal conductivity  220 W/mK) in peak-to-valley aspect ratios than the VPD film, the average
order to maintain adequate control of the substrate film roughness/uniformity of both films is similar (RMS

Zone 1 Zone 2 Zone 3 Zone 4


Source Boat
Crystal Monitor

Cooling Supply Substrate Holder

Shutters
Vacuum Fused
Pump Silica wall Carrier Gas
Zone 1 Zone 2 Zone 3 Zone 4

Fig. 1. Schematic of the modified VPD system.


F.F. Navarro et al. / Organic Electronics 15 (2014) 3052–3060 3055

(101)
VPD

200nm

(002)

(Silicon)
VPD

(100)
Intensity (a.u.)

(102)

(103)
(110)

(200)
(112)
(004)
Si Substrate

(202)
VTE
VTE

200nm
Si Substrate
30 40 50 60 70 80

Fig. 2. Cross-sectional SEM images of a 200 nm Mg film on a silicon


2θ (degree)
substrate made using either VPD (top  8.5 K) or VTE (bottom  55 K).
The VPD film was deposited at a substrate holder temperature of 20– Fig. 4. XRD patterns of 200 nm Mg films deposited on a silicon substrate
25 °C. using either VPD (top) or VTE (bottom) methods. Blue lines are reference
crystal planes of the hexagonal phase of Mg.

values for VPD = 36 ± 7 nm, VTE = 36 ± 8 nm and bare sili- deposition conditions (substrate temperature, chamber
con = 0.4 ± 0.1 nm). Grazing incidence XRD diffraction pat- pressure and carrier gas flow rates) [9,10], the VPD method
terns collected for the VPD and VTE films show peaks that should lead to films with identical crystal patterns to those
can be assigned to the hexagonal, P63/mmc (194) phase of made using VTE. Four-point probe resistivity measure-
Mg (Jade 9, PDF#03-065-3365), and the underlying Si sub- ments were carried out to examine the electrical proper-
strate (Fig. 4). The pattern of peak intensities of the VPD ties of the metal films. Resistivities of 1.8  107 X m and
film is similar to the expected powder pattern, indicating 8.4  108 X m were obtained for VPD and VTE Mg films,
that the Mg crystallites are randomly arranged on the sub- respectively. The observed increase in resistivity of films
strate during film growth. In contrast, the VTE film shows made using VPD can be attributed to grain boundaries,
the 0 0 2 peak is markedly higher intensity than expected (more pronounced in VPD metal films), and loose pack-
from the powder pattern indicating a preferred alignment ing/growth of the crystallites during deposition, which
of the Mg crystallites with the 0 0 2 planes parallel to the can enhance air/water diffusion and thus rapid oxidation
substrate. Further, the response from the silicon lattice of the film. In particular loose packing is associated with
plane is attenuated in the XRD data from the VTE film, crystal orientation of grains (crystallographic orientation)
indicating denser packing than the VPD film. However, and is known to play a role in the oxidation properties of
we believe that through appropriate modification of the metals, e.g., Mg and copper, by directly impacting the

VPD

VTE

Fig. 3. 3D AFM image of 200 nm Mg films deposited on a silicon substrate using either VPD (top) or VTE (bottom) methods.
3056 F.F. Navarro et al. / Organic Electronics 15 (2014) 3052–3060

atomic packing density and surface energy of the metals air for approximately 5 min during exchange of source
[38–40]. Further, these metals were shown to exhibit low boats, electrode mask placement and cleaning of the shut-
surface energy (high atomic packing density) and a an ters. Fluorescent and phosphorescent devices fabricated in
increased resistance to corrosion, in solution (Mg) and thin the VPD exhibited analogous electroluminescence spectra
films (Cu), with certain crystallographic orientations, e.g., to devices made in the VTE, due to Alq3 and Ir(ppy)3 emis-
0001 (Mg), 100 (Cu) and 110 (Cu). Regardless, while the sion, respectively.
resistivity is higher for films made using VPD, the value
is still low enough to make it suitable for use as a cath- 2.4. Organic photovoltaic devices
ode/anode in organic devices. Similarly, Zn films fabricated
in the VPD system and deposited on silicon substrates Organic photovoltaic devices using 200 nm thick Mg
show complete substrate coverage, but a rougher surface cathodes were fully made in either the VPD or VTE sys-
morphology than Mg films (RMS = 77 ± 3 nm), a resistivity tems. Organics and metals were deposited at a range of
of 4.6  106 X m and XRD pattern peaks that can be 1–4 Å/s and 4–8 Å/s, respectively. Devices prepared with
assigned to various crystal planes of the hexagonal phase the VPD system used substrate holder temperatures of
of Zn (see Figs. S4-S7 and Table S1 in SI). 60–65 °C for organics and 20–25 °C for metals and total
carrier gas flows of 60 sccm for both organics and metals.
2.3. Organic light-emitting devices with magnesium cathodes OPVs were initially fabricated on ITO using CuPc (40 nm)/
C60 (40 nm) and the most common material, bathocupro-
Fluorescent and phosphorescent OLEDs with Mg as the ine (BCP, 10 nm) as a buffer layer. While it has been estab-
cathode were fully fabricated using either the VPD or VTE lished that BCP is an effective buffer when aluminum is
(reference) methods. The deposition rates used in both used as a cathode in the same structure, non-rectifying
methods for organics and metals were 1–4 Å/s and current–voltage (IV) curves were obtained for analogous
4–8 Å/s, respectively. The fabrication of devices using the devices with Mg cathodes. Likewise, devices fabricated
VPD system was done at a substrate holder temperature without a buffer layer exhibited poor charge extraction
of 40–45 °C for organics and 20–25 °C for metals and total (gp = 0.16 ± 0.05%). Poor contact of the metal cathode with
carrier gas flows of 60 sccm. Fluorescent OLEDs, Fig. 5a, the acceptor layer (see S10–S11 in SI) was observed with
(ITO/NPD (40 nm)/Alq3 (40 nm)) made in both the VPD this device structure. However, working OPVs were
and VTE with 200 nm Mg cathodes exhibited similar obtained when a 10 nm buffer layer of 3,4,9,10 perylene-
turn-on voltages (Von = 2.7 V at 1 cd/m2) and external tetracarbonyl bisbenzimidazole (PTCBI) was employed in
quantum efficiencies (EQE = 0.9 ± 0.1% at 100 cd/m2). the device. Current–voltage curves and efficiency–wave-
Phosphorescent devices, Fig. 5b, (ITO/NPD (40 nm)/CBP– length characteristics for the devices can be seen in
Ir(ppy)3 7 wt% (30 nm)/BCP (10 nm)/Alq3 (40 nm)) made Fig. 6. OPVs fabricated in the VTE system have efficiencies
in the VPD had a higher turn-on voltage than devices made comparable to values obtained for devices using the same
in the VTE (Von at 1 cd/m2 = 4.1 and 3.3 V, respectively). A CuPc–C60 architecture and an aluminum cathode
lower efficiency was observed for devices made in the (gp = 0.75–1.3%) [46–49]. Devices made by either deposi-
VPD than for those made in the VTE (EQE = 7.6 ± 0.6 and tion method exhibited similar open circuit voltages
8.3 ± 0.5% at 100 cd/m2, respectively). The efficiencies of (Voc = 0.45 ± 0.06%) and fill factors (FF = 0.50 ± 0.06%).
fluorescent and phosphorescent devices are comparable However, devices made using VPD displayed a lower cur-
to values previously reported for devices with the same rent (Jsc = 2.2 ± 0.2 mA/cm2) than those using the VTE
architecture used here (EQE = 0.6-1.3% and EQE = 7.5-8.5% (Jsc = 4.6 ± 0.4 mA/cm2) thus rendering a lower power effi-
at 100 cd/m2, respectively) [41–45]. The current density ciency (gp = 0.5 ± 0.1%). The decrease in current density
vs voltage plots of OLEDs made by VPD and VTE are similar, from devices made using VPD can be ascribed to exposure
suggesting that the small differences in turn-on voltage to air (5 min) during electrode mask placement and
and EQE between PHOLED devices is due to exposure to cleaning of the shutters. To corroborate this hypothesis, a

1.2 10
104 104
Brightness (cd/m 2)

Brightness (cd/m2)

1.0 VPD 8 3
103 VPD 10
VTE
0.8 6 VTE
EQE (%)

102 102
EQE (%)

800
Current Density (mA/cm )

0.6 4
2

101
200
101
Current Density (mA/cm )
2

600
150

0.4 400
100 2 100 100
200
50
0.2 0 10-1 0
0
10-1
2 4 6 8 10 12
2 4 6 8 10 12
Voltage (V) Voltage (V)
0.0 10-2 -2 10-2
2 4 6 8 10 12 2 4 6 8 10 12
Voltage (V) (a) Voltage (V) (b)

Fig. 5. External quantum efficiency/brightness vs voltage characteristics of (a) fluorescent Alq3 and (b) phosphorescent Ir(ppy)3 OLEDs. Current density vs
voltage characteristics can be seen in the inset.
F.F. Navarro et al. / Organic Electronics 15 (2014) 3052–3060 3057

12 4. Experimental procedure
20 VPD Dark
VPD
VPD Light
Current Density (mA/cm 2)

15 VTE 4.1. Characterization of metal films


8 EQE (%) VTE Dark
10 VTE Light
Profilometer profiles were obtained with a Sloan Dektak
5
IIA stylus profilometer. Analysis of the Mg thin film profile
4
0 showed that the 200 nm fabricated film was soft, leaving a
400 500 600 700 800 900
Wavelength (nm) scratch mark during measurement, and had a thickness
0 between 160 nm and 180 nm. In addition, profiles were
acquired for 200 nm Mg thin films deposited in the VTE
system. Metal film morphology, roughness, crystallinity
-4 and resistivity was characterized using a JEOL JSM-7001F
scanning electron microscope (SEM), Digital Instruments
Dimension 3100 atomic force microscopy (AFM), Rigaku
-0.9 -0.6 -0.3 0.0 0.3 0.6
Ultima IV powder/thin film diffractometer (XRD) and a
Voltage (V) Signatone 4-point probe resistivity head connected to a
Keithley power source meter model 2400. XRD measure-
Fig. 6. Current vs voltage (IV) curves of CuPc/C60/PTCBI/Mg OPVs.
External quantum efficiency (%) can be seen in the inset. ments were performed at 4 degrees per minute, 0.1 step,
0.3 degrees gamma and a 10 mm slit.
device was made in the VTE system where the organic
films were exposed to air (5 min) prior to deposition of 4.2. OLED and OPV substrate preparation
the electrode. A reference device was concurrently pre-
pared where organic films were not subject to air during Patterned ITO substrates with a resistivity of 1:20 ± 5 X/
fabrication. Devices exposed to air displayed lower current sq and an ITO thickness of 2000 ± 50 Å were used for OLEDs
density (10%) and a 25% decrease in efficiency, compared and OPVs made in both the VPD and VTE systems. OLED
to the control device (see Fig. S12–S13 and Table S7 in SI). substrates were prepared/cleaned by scrubbing them with
Tergitol NP-9 (Sigma–Aldrich Co.)/DI solution followed by a
thorough rinse with DI water. The substrates were then
3. Conclusion
rinsed with acetone (Sigma–Aldrich Co.) followed by a blow
drying step with N2 gas. They were then placed for 10 min
In summary, we present a new low vacuum method to
in a ultra–violet ozone cleaning system, model T10X10/
deposit thin metal films using a vapor phase deposition
OES. Substrates were then transferred to either the VPD
(VPD) system. Characterization of Mg and Zn films via
or VTE systems for device fabrication. OPV substrates were
SEM, AFM, XRD and four-point probe resistivity indicate
prepared/cleaned by scrubbing them with Tergitol NP-9
thin metal films fabricated in the VPD and VTE systems
(Sigma–Aldrich Co.)/DI solution followed by a thorough
show complete substrate coverage and have comparable
rinse with DI water. The substrates were then rinsed with
roughness/uniformity, crystallinity and electrical conduc-
acetone (Sigma–Aldrich Co.) followed by a blow drying step
tivity. By adequately controlling deposition conditions
with N2 gas. They were then washed with tetrachloroethyl-
and substrate temperatures, a VPD system was used to
ene (J.T. Baker), acetone (Macron Chemical) and ethyl alco-
deposit Mg cathodes for optoelectronics devices. We suc-
hol anhydrous reagent (J.T. Baker). The wash consists of
cessfully fabricated fluorescent and phosphorescent OLEDs
placing the substrates, in the order mentioned above, inside
and OPVs with Mg cathodes, which perform similarly to
a beaker with each solvent for 10 min while heating the sol-
those prepared by VTE. This new method allows complete
vent to its boiling point. After washing, the substrates are
fabrication of optoelectronic devices at system pressures of
blow dried with N2 gas and placed in a ultra-violet ozone
1–10 torr. Further, low pumping times and high material
cleaning system, model T10X10/OES for 10 min. Substrates
utilization in the VPD system unlocks the opportunity to
were then transferred to either the VPD or VTE systems for
compete with high-volume high-vacuum production sys-
device fabrication.
tems for the manufacturing of optoelectronic devices.
Deposition of metals with higher sublimation tempera-
tures than magnesium and zinc, (e.g., aluminum and silver) 4.3. OLED and OPV device structure
in the VPD system should also be feasible. However, to
realize Al and Ag electrodes it’s important to consider that Fluorescent and phosphorescent OLED devices were
both metals have significantly higher enthalpies of subli- made in both the VPD and VTE systems. The green fluores-
mation (330 and 284 KJ/mol, respectively) than Mg and cent emitter device consists of N,N0 -Di-[(1-naphthyl)-N,N0 -
Zn [28]. Consequently, the need for higher deposition tem- diphenyl]-1,1 0 -biphenyl)-4,4 0 -diamine (NPD-40 nm),
peratures (P700 °C) would require using a vessel in the aluminum tris-(8 hydroxyquinoline) [Alq3-40 nm] and Mg
VPD system that can withstand higher temperatures (e.g., (Mg-200 nm). The Green phosphor emitter device consists
quartz or stainless steel). Moreover, additional cooling of N,N0 -Di-[(1-naphthyl)-N,N0 -diphenyl]-1,10 -biphenyl)-4,
would be necessary to maintain substrate temperatures 40 -diamine (NPD-40 nm), fac-tris(2-phenylpyridine)iridium
at values low enough (650 °C) to prevent damage to the (Ir(ppy)3) doped into 4,40 -Bis(N-carbazolyl)-1,10 -biphenyl
organic films and thus obtain working devices. (CBP-30 nm) @ 7% wt, Bathocuproine (BCP-10 nm),
3058 F.F. Navarro et al. / Organic Electronics 15 (2014) 3052–3060

aluminum tris-(8 hydroxyquinoline) [Alq3-40 nm] and Mg made. The Inficon crystal sensor was kept at 15 °C at all
(Mg-200 nm). Organic photovoltaic devices were also made times using a VWR 1140A chiller.
in both the VPD and VTE system. The OPV device structure By introducing the source boat into the hot zone the
consists of copper phthalocyanine (CuPC-40 nm), Fullerene organic/metal was evaporated into the inert gas stream
(C60-40 nm), 3,4,9,10 perylenetetracarboxylic bisbenzimi- (N2) which carried the organic compound to the cooled
dazole (PTCBI-10 nm) and magnesium (Mg-200 nm). The substrate where the organic/metal condensed onto the
organic materials NPD, CBP and Alq3 were obtained surface of the substrate. Organic and metal compounds
from Universal Display Corporation, BCP was purchased were deposited at a constant pressure of 1 torr, total gas
from MER corporation, fac-tris(2-phenylpyridine)iridium flow rates of 60 sccm and deposition rates of 1–4 Å/s and
(Ir(ppy)3) was synthesized according to literature [50], 4–8 Å/s, respectively. High and low sublimation tempera-
and fullerene (C60) and magnesium chips (Mg) were pur- ture gradients utilized in the VPD can be seen in Table 2.
chased from Sigma-Aldrich Co. All organic materials were Because the VPD has only four source boats, during the fab-
purified at least once via vacuum-train sublimation prior rication of phosphorescent devices two source boats, Alq3
to use in the VPD or VTE systems. and Mg, were exchanged for NPD and BCP in order to com-
plete the device. Further, VPD organic films were exposed
to air for approximately 5 min during exchange of source
4.4. Device fabrication using VPD boats and metal mask placement. Substrate holder temper-
ature during deposition of NPD, Alq3 and metals was
A general schematic of the VPD setup can be seen in between 40 and 45 °C while CuPc, C60 and PTCBI deposi-
Fig. 1, in which the VPD 400 Pyrex tube/reactor is housed tions occurred at a substrate holder temperature of 60–
in a Carbolite TVS 12/600/2416CG three zone (1–3) tube 65 °C. Organic/metal sublimation temperatures during
furnace. Preheating of the 4’’ Pyrex tube (Zone 4) is per- deposition are shown in Table 3.
formed with a 400  400 120 V, 1100 W Watlow mineral
insulated band heater. Temperature of the source boats, 4.5. Device fabrication using VTE
mineral insulated band heater and substrate holder was
measured and controlled with Omega type K thermocouple Reference devices were made in an evovac 800 VTE depo-
probes attached to Omega CN76000 temperature control- sition system attached to a glove box and an Inficon SQS-242
lers. Flow of inert gas for each individual source boat, four deposition software was used to control deposited material
in total, was measured using individual MKS mass flow thicknesses using a 6mhz Inficon quartz monitor gold
controllers (0–500 sccm) while pressure was measured coated crystal sensor. All films deposited in the VTE were
with a 10 torr Model 626A Baratron Pressure Transducer performed at pressures 6 4  104 Pa and with deposition
and adjusted to desire with a MKS Model 153D Smart rates ranging between 1 and 5 Å/s. Because the VTE system
Downstream Throttle Valve. All MKS instruments were is attached to a glove box, organic films were never exposed
monitored and controlled with a MKS Model 647C flow to ambient air. Proper calibration of the Inficon crystal sen-
channel controller box while vacuum was achieved with sor via spectroscopic ellipsometry was performed using a
a Varian IDP-3 Oil Free Dry Scroll Pump. The substrate J.A. Woollam Co., Inc. VASE variable-angle ellipsometer with
holder, made out of aluminum, its position approximately a VB-200 control module and a CVI instruments Digikrom
100 away from zone 1 and it can hold two 100  100 patterned 242 monochromator with a 75 W xenon light source to
substrates. The substrate holder has two shutters which ensure accurate thickness of films made
are utilized to control total thickness deposited onto each
individual substrate. The substrate holder was cooled 4.6. OLED and OPV testing
using N2 gas that was passed through a copper coil sub-
merged in liquid nitrogen. Substrate holder temperature OLED current–power and current–voltage curves, under
was controlled by adjusting the flow/volume of cold N2 applied forward bias of 0–12 V, were measured using a
gas by means of a needle valve. Material thickness was Keithley power source meter model 2400, a Newport
measured using a 6 MHz Inficon quartz monitor gold multi-function optical meter model 1835-C, a low power
coated crystal sensor attached to an Inficon XTC/2 thin film Newport silicon photodiode sensor model 818-UV and a
deposition controller. Proper calibration of the Inficon fiber bundle (used to direct the light into the photodiode).
crystal sensor via spectroscopic ellipsometry was per- The silicon diode was set to measure power/photons at an
formed using a J.A. Woollam Co., Inc. VASE variable-angle energy of 520 nm and was subsequently corrected during
ellipsometer with a VB-200 control module and a CVI data processing to the average electroluminescence wave-
instruments Digikrom 242 monochromator with a 75 W length for each individual device. Electroluminescence
xenon light source to ensure accurate thickness of films of OLEDs was collected with a photon technology

Table 2
Temperature gradient conditions for low/high sublimation materials in the VPD system.

Low sublimation temperature materials High sublimation temperature materials


Zone 1 Pre-substrate zone 300 °C Zone 1 Pre-substrate zone 450 °C
Zone 2 Hot zone 350 °C Zone 2 Hot zone 550 °C
Zone 3 Hot zone 350 °C Zone 3 Hot zone 550 °C
Zone 4 Pre-heating zone 350 °C Zone 4 Pre-heating zone 550 °C
F.F. Navarro et al. / Organic Electronics 15 (2014) 3052–3060 3059

Table 3 [4] N. Bahlawane, K. Kohse-Hoeinghaus, P.A. Premkumar, D. Lenoble,


Sublimation temperature conditions of organics/metals in the VPD system. Advances in the deposition chemistry of metal-containing thin films
using gas phase processes, Chem. Sci. 3 (2012) 929–941.
Compound Sublimation temperature (°C) [5] R.B. Bird, W.E. Stewart, E.N. Lightfoot, Transport Phenomena, Revised
second ed., John Wiley & Sons, Inc., 2006.
NPD 260–270
[6] B.S. Lim, A. Rahtu, R.G. Gordon, Atomic layer deposition of transition
Alq3 290–300
metals, Nat. Mater. 2 (2003) 749–754.
CuPc 440–480 [7] P.E. Burrows, S.R. Forrest, L.S. Sapochak, J. Schwartz, P. Fenter, T.
C60 500–530 Buma, V.S. Ban, J.L. Forrest, Organic vapor phase deposition: a new
PTCBI 500–530 method for the growth of organic thin films with large optical non-
Zn 430–520 linearities, J. Cryst. Growth 156 (1995) 91–98.
Mg 510–550 [8] M. Shtein, H.F. Gossenberger, J.B. Benziger, S.R. Forrest, Material
transport regimes and mechanisms for growth of molecular organic
thin films using low-pressure organic vapor phase deposition, J.
international QuantaMaster model C-60 fluorimeter at Appl. Phys. 89 (2001) 1470–1476.
several voltages, between 3 and 11 V, to ensure emission [9] M. Shtein, J. Mapel, J.B. Benziger, S.R. Forrest, Effects of film
morphology and gate dielectric surface preparation on the
characteristics remained constant.
electrical characteristics of organic-vapor-phase-deposited
OPV current density (J) as a function of applied voltage pentacene thin-film transistors, Appl. Phys. Lett. 81 (2002) 268–270.
(V) characteristics were measured in air at room tempera- [10] M. Baldo, M. Deutsch, P. Burrows, H. Gossenberger, M. Gerstenberg,
ture, in the dark and under spectral mismatch corrected V. Ban, S. Forrest, Organic vapor phase deposition, Adv. Mater. 10
(1998) 1505–1514.
100 mW/cm2 white light illumination from an AM-1.5G fil- [11] M.A. Baldo, V.G. Kozlov, P.E. Burrows, S.R. Forrest, V.S. Ban, B. Koene,
tered 300 W Xenon arc lamp (Newport Inc.) and a Keithley M.E. Thompson, Low pressure organic vapor phase deposition of
power source meter model 2635A. Routine spectral mis- small molecular weight organic light emitting device structures,
Appl. Phys. Lett. 71 (1997) 3033–3035.
match correction for ASTM G173-03 was performed using [12] T.X. Zhou, T. Ngo, J.J. Brown, M. Shtein, S.R. Forrest, Stable and
a filtered silicon photodiode, calibrated by the National efficient electrophosphorescent organic light-emitting devices
Renewable Energy Laboratory (NREL) to reduce measure- grown by organic vapor phase deposition, Appl. Phys. Lett. 86
(2005). 021107-1–021107-3.
ment errors. Frequency modulated monochromatic light [13] F. Lindla, Pv Gemmern, D. Keiper, M. Heuken, H. Kalisch, R.H. Jansen,
(250 Hz, 10 nm FWHM) and lock-in detection was used Hybrid white organic light-emitting diode with a mixed-host
to perform all spectral responsivity and spectral-mismatch interlayer processed by organic vapor phase deposition, J.
Photonics Energy 1 (2011) 011013.
correction measurements.
[14] M. Boesing, F. Lindla, C. Zimmermann, Pv Gemmern, D. Bertram, D.
Keiper, N. Meyer, M. Heuken, H. Kalisch, R.H. Jansen, Hybrid white
Acknowledgements organic light emitting diodes (OLED) processed by organic vapor
phase deposition, Mater. Res. Soc. Symp. Proc. 1212 (1212) (2010)
S03–S08.
The authors thank Professor Stephen R. Forrest, Dr. Ced- [15] M. Brast, F. Lindla, M. Boesing, D. Bertram, D. Keiper, M. Heuken, H.
ric Rolin and Garen Vartanian for helpful discussions of the Kalisch, A. Vescan, p-Type doping of small-molecule organic
OVPD system, Patrick Saris and John Facendola for provid- semiconductors using organic vapor phase deposition (OVPD),
Mater. Res. Soc. Symp. Proc. (2012) 1402.
ing organic compounds helpful for this project, Professor [16] M. Bösing, F. Lindla, M. Brast, D. Bertram, D. Keiper, M. Heuken, H.
William H. Steier and Hari Mahalingam for help with thin Kalisch, A. Vescan, Highly Efficient OVPD-Processed Resonant-Cavity
film measurements with the broadband spectroscopic OLED Comprising a Semitransparent Ag layer, Mater. Res. Soc. Symp.
Proc. (2012) 1402.
ellipsometer and profilometer profiles, Professor C. Zhou
[17] F. Yang, M. Shtein, S.R. Forrest, Controlled growth of a molecular
and Yang Song for help with AFM images, Yang Song for bulk heterojunction photovoltaic cell, Nat. Mater. 4 (2004) 37–
help with SEM images, Mr. Phillip Sliwoski for glasswork, 41.
[18] M. Rusu, S. Wiesner, T. M, H. Blei, N. Meyer, M. Heuken, M.Ch. Lux-
Mr. Donald Wiggins, Mr. Michael Cowan and Mr. Ramon
Steiner, K. Fostiropoulos, Organic donor, acceptor and buffer layers
Delgadillo for machinery work and Rebecca L. Pizzitola of small molecules prepared by OVPD technique for photovoltaics,
for assistance with editing. This work was funded by Uni- Renew. Energy 33 (2008) 254–258.
versal Display Corp., Grant No. UDC-0607 and Global Pho- [19] M. Rusu, J. G, S. Wiesner, N. Meyer, M. Heuken, K. Fostiropoulos, MCh
Lux-Steiner, Fine tailored interpenetrating donor–acceptor
tonic Energy Corp., Grant No. GPEC-2006. morphology by OVPD for organic solar cells, Thin Solid Films 516
(2008) 7160–7166.
[20] S. Axmann, M. Brast, N. Wilck, H. Windgassen, M. Heuken, H. Kalisch,
Appendix A. Supplementary material A. Vescan, Influence of OVPD parameters on the performance of
organic solar cells utilizing pentacene/PTCDI absorption layers,
Supplementary data associated with this article can be Mater. Res. Soc. Symp. Proc. (2012) 1390.
[21] Sung Hwan Kim, H.Y. C, Seung Hoon Han, Jin Jang, Sang Mi Cho,
found, in the online version, at http://dx.doi.org/10.1016/ Pentacene thin film with large grain on plastic substrate by organic
j.orgel.2014.08.049. vapor phase deposition, J. Korean Phys. Soc. 45 (2004) 760–762.
[22] C. Rolin, S. Steudel, K. Myny, D. Cheyns, S. Verlaak, J. Genoe, P.
Heremans, Pentacene devices and logic gates fabricated by organic
References vapor phase deposition, Appl. Phys. Lett. 89 (2006) 203502.
[23] C. Rolin, K. Vasseur, S. Schols, M. Jouk, G. Duhoux, R. Müller, J. Genoe,
[1] J.C. Scott, Metal–organic interface and charge injection in organic P. Heremans, High mobility electron-conducting thin-film
electronic devices, J. Vac. Sci. Technol. 21 (2003) 521–531. transistors by organic vapor phase deposition, Appl. Phys. Lett. 93
[2] M. Matsumura, T. Akai, M. Saito, T. Kimura, Height of the energy (2008) 033305.
barrier existing between cathodes and hydroxyquinoline–aluminum [24] C. Rolin, K. Vasseur, S. Steudel, P. Vicca, J. Genoe, P. Heremans, High-
complex of organic electroluminescence devices, J. Appl. Phys. 79 speed growth of pentacene thin films by in-line organic vapor phase
(1996) 264–268. deposition, Proc. SPIE 7417 (2009) 741712.
[3] S. Biswas, O. Shalev, M. Shtein, Thin-film growth and patterning [25] K. Vasseur, C. Rolin, S. Vandezande, K. Temst, L. Froyen, P. Heremans,
techniques for small molecular organic compounds used in A growth and morphology study of organic vapor phase deposited
optoelectronic device applications, Annu. Rev. Chem. Biomol. Eng. perylene diimide thin films for transistor applications, J. Phys. Chem.
4 (2013) 289–317. C 114 (2010) 2730–2737.
3060 F.F. Navarro et al. / Organic Electronics 15 (2014) 3052–3060

[26] C. Rolin, K. Vasseur, B. Niesen, M. Willegems, M. Robert, S. Soren, G. [40] Jie Gao, A. H., Ming Li, Dali Mao, Influence of crystal orientation on
Jan, H. Paul, Vapor phase growth of functional pentacene films at copper oxidation failure, Appl. Surf. Sci. 255 (2009) 5943–5947.
atmospheric pressure, Adv. Funct. Mater. 22 (2012) 5050–5059. [41] D.F. O’Brien, P.E. Burrows, S.R. Forrest, B.E. Koene, D.E. Loy, M.E.
[27] K. Yase, Y. Takahashi, N. Ara-kato, A. Kawazu, Evaporation rate and Thompson, Hole transporting materials with high glass transition
saturated vapor pressure of functional organic materials, Jpn. J. Appl. temperatures for use in organic light-emitting devices, Adv. Mater.
Phys. 34 (1995) 636–637. 10 (2014) 1108–1112.
[28] W. Plieth, Electrochemistry for Materials Science, 1 ed., Elsevier [42] M.-X. Yu, J.-P. Duan, C.-H. Lin, C.-H. Cheng, Y.-T. Tao,
Science, 2008, p. 420. Diaminoanthracene derivatives as high-performance green host
[29] CRC Handbook of Chemistry and Physics., 95th ed. Haynes, W.M., electroluminescent materials, Chem. Mater. 14 (2002) 3958–3963.
Ed.; CRC Press: Boca Raton, FL, 2014; Chapter 4, p126. [43] M. Cai, T. Xiao, R. Liu, Y. Chen, R. Shinar, J. Shinar, Indium-tin-
[30] C. Adachi, S. Tokito, T. Tsutsui, S. Saito, Organic electroluminescent oxide-free tris(8-hydroxyquinoline) Al organic light-emitting diodes
device with a three-layer structure, Jpn. J. Appl. Phys. 27 (1988) with 80% enhanced power efficiency, Appl. Phys. Lett. 99 (2011)
L713–L715. 153303.
[31] M. Stössel, J. Staudigel, F. Steuber, J. Simmerer, A. Winnacker, Impact [44] M.A. Baldo, S. Lamansky, P.E. Burrows, M.E. Thompson, S.R. Forrest,
of the cathode metal work function on the performance of vacuum- Very high-efficiency green organic light-emitting devices based on
deposited organic light emitting-devices, Appl. Phys. A 68 (1999) electrophosphorescence, Appl. Phys. Lett. 75 (1999) 4–6.
387–390. [45] C. Adachi, M.A. Baldo, S.R. Forrest, M.E. Thompson, High-efficiency
[32] G.W.C. Kaye, D. Ewen, The Sublimation of Metals at Low Pressures, organic electrophosphorescent devices with tris(2-
Proc. R. Soc. London Ser. A, Contain. Papers Math. Phys. Charact. 89 phenylpyridine)iridium doped into electron-transporting materials,
(1913) 58–67. Appl. Phys. Lett. 77 (2000) 904–906.
[33] R.W. Wood, Experimental determination of the law of reflexion of [46] P. Sullivan, S. Heutz, S.M. Schultes, T.S. Jones, Influence of
gas molecules, Philos. Mag. Ser. 6 (30) (1915) 300–304. codeposition on the performance of CuPc–C60 heterojunction
[34] M. Knudsen, Die Verdichtung von Metalldampfen an abgekuhlten photovoltaic devices, Appl. Phys. Lett. 84 (2004) 1210.
Korpern, Ann. Phys. 355 (1916) 472–488. [47] H. Lin, J.-S. Yu, J. Huang, Y.-D. Jiang, Film thickness effect on the
[35] I. Langmuir, The condensation and evaporation of gas molecules, performance of small molecular solar cell, Optoelectr. Lett. 4 (2008)
Proc. Natl. Acad. Sci. 3 (1917) 141–147. 321–323.
[36] J.D. Cockcroft, On phenomena occurring in the condensation of [48] Y.W. Kim, M.L. Monroe, J. Seol, N.T.N. Truong, S.M. Cho, T.J. Anderson,
molecular streams on surfaces, Proc. R. Soc. London Ser. A, Contain. C. Park, Optimization of organic bi-layer solar cell through
Papers Math. Phys. Charact. 119 (1928) 293–312. systematic study of anode treatment and material thickness,
[37] P. Benjamin, C. Weaver, The adhesion of evaporated metal films on Korean J. Chem. Eng. 25 (2008) 1036–1039.
glass, R. Soc. London Proc. Ser. A, Math. Phys. Sci. 261 (1961) 516–531. [49] C. Trinh, J.R. Bakke, T.P. Brennan, S.F. Bent, F. Navarro, A. Bartynski,
[38] Ming Liu, D. Q, Ming-Chun Zhao, Guangling Song, Andrej Atrens, The M.E. Thompson, Power losses in bilayer inverted small molecule
effect of crystallographic orientation on the active corrosion of pure organic solar cells, Appl. Phys. Lett. 101 (2012) 233903.
magnesium, Scr. Mater. 58 (2008) 421–424. [50] A.B. Tamayo, B.D. Alleyne, P.I. Djurovich, S. Lamansky, I. Tsyba, N.N.
[39] Kwang Seon Shinm, M.Z. B, Nguyen Dang Nam, Effects of Ho, R. Bau, M.E. Thompson, Synthesis and characterization of facial
crystallographic orientation on corrosion behavior of magnesium and meridional tris–cyclometalated iridium(III) complexes, J. Am.
single crystals, JOM 64 (2012) 664–670. Chem. Soc. 125 (2003) 7377–7387.