Organic light-emitting diodes (OLEDs) have been established as versatile light sources that allow for easy integration in large-area surfaces and flexible substrates. In addition, the low fabrication cost of OLEDs renders them particularly attractive as general lighting sources. Current methods for the fabrication of white-light OLEDs rely on the combination of multiple organic emitters and/or the incorporation of multiple cavity modes in a thick active medium. These architectures introduce formidable challenges in both device design and performance improvements, namely, the decrease of efficiency with increasing brightness (efficiency roll-off) and short operational lifetime. Here we demonstrate, for the first time, white-light generation in an OLED consisting of a sub-100 nm thick blue single-emissive layer coupled to the photonic Bragg modes of a dielectric distributed Bragg reflector (DBR). We show that the Bragg modes, although primarily located inside the DBR stack, can significantly overlap with the emissive layer, thus efficiently enhancing emission and outcoupling of photons at selected wavelengths across the entire visible light spectrum. Moreover, we show that color temperature can be tuned by the DBR parameters, offering great versatility in the optimization of white-light emission spectra.
Organic light-emitting diodes (OLEDs) have been established as versatile light sources that allow for easy integration in large-area surfaces and flexible substrates. In addition, the low fabrication cost of OLEDs renders them particularly attractive as general lighting sources. Current methods for the fabrication of white-light OLEDs rely on the combination of multiple organic emitters and/or the incorporation of multiple cavity modes in a thick active medium. These architectures introduce formidable challenges in both device design and performance improvements, namely, the decrease of efficiency with increasing brightness (efficiency roll-off) and short operational lifetime. Here we demonstrate, for the first time, white-light generation in an OLED consisting of a sub-100 nm thick blue single-emissive layer coupled to the photonic Bragg modes of a dielectric distributed Bragg reflector (DBR). We show that the Bragg modes, although primarily located inside the DBR stack, can significantly overlap with the emissive layer, thus efficiently enhancing emission and outcoupling of photons at selected wavelengths across the entire visible light spectrum. Moreover, we show that color temperature can be tuned by the DBR parameters, offering great versatility in the optimization of white-light emission spectra.
Three decades ago, a twist in
the search of an efficient illumination source came from the demonstration
of a practical organic light-emitting diode (OLED).[1] Since then, OLEDs have been utilized in a plethora of optoelectronic
applications,[2,3] and the effort for improving their
efficiency constitutes one of the major trends in modern optoelectronics
research.[4−6] Owing to their low fabrication cost, exceptional
color rendering, and ease of deposition to large areas and flexible
substrates, OLEDs have attracted a lot of attention as general illumination
devices in which broadband and high-intensity white light is a key
requirement.[7,8] Although single-emitter OLEDs
have spectral bandwidth which predominantly covers only a part of
the visible spectrum, numerous demonstrations of white-emitting OLEDs
(WOLEDs) have been reported.[9−11]Generally, reported methods
for the realization of WOLEDs by materials
design can be categorized as follows: (1) WOLEDs consisting of multiple
vertically stacked emissive layers or horizontally striped structures.
White light in these architectures is created by a mixture of independently
emitting red, green, and blue OLEDs. While these strategies offer
stable electroluminescence and high device yields, the active area
is thick, which usually results in high operating current. Achieving
the desired color balance requires precise control over the thickness
and composition of each layer which makes the fabrication of such
WOLEDs complicated, rendering them incompatible as inexpensive solid-state
lighting sources.[11,12] (2) Single-emissive layer structures
in which white light is achieved via near-molecule energy transfer
(Förster or Dexter) between a matrix material and multiple
dopant emitters. These structures are easy to fabricate either by
vacuum deposition or solution processes. Major disadvantages of this
method are precise control of the dopant concentration and the operational
voltages required for reliable control of the electroluminescence
spectrum.[11,12] (3) Single-emissive layer with bimolecular
excited species, such as excimers and exciplexes.[13,14] While these species harvest the otherwise undesired losses in red-shifted
emission bands to generate white light, color tunability and high-power
stability remain challenges.In addition to the aforementioned
material optimization and device
engineering methods, white-light emission in OLEDs has been reported
by introducing a photonic design such as microcavities with multiple
resonances. There, cavity modes are confined in a thick active region
between highly reflective metallic mirrors, or a combination of metallic
and distributed Bragg reflector (DBR) mirrors. The emissive layer
has a broadband visible emission spectrum which is either Purcell-enhanced
or suppressed by the cavity modes.[15,16] Because the
color ratio of red, green, and blue is primarily defined by the optical
modes, the white-light spectrum is expected to be uninfluenced by
variations in doping, carrier competition, and other molecular emission
instabilities. Such photonic multiresonant structures are advantageous
because they can be designed to utilize emissive layer(s) from any
of the previously discussed categories. However, there are two main
challenges in such multimode WOLEDs: (a) While metal-clad microcavities
have a broad reflectivity band, and they can support multiple modes,
they suffer from emission losses as light has to exit a thick metallic
layer. (b) The increased cavity length (usually thicker than 3λ/2,
where λ is the wavelength of light) introduces additional lossy
waveguide. There, several modeling techniques can be employed to describe
the increase of emission efficiencies.[17,18] Also, thick
cavities result in an increased electron–hole propagation distance
which impedes efficient electron–hole recombination in OLEDs
and can also lead to efficiency roll-off due to increased bimolecular
annihilation processes,[19] with the exception
of the recent breakthrough by Matsushima et al.[20] Another approach for producing white electroluminescence
is the hybridization of a single cavity mode with a Tamm plasmon–polariton
resonance.[21] These hybrid modes can strongly
outcouple electroluminescence at two different colors, resulting in
white light. While this light outcoupling strategy allows for independent
optimization between electrical and optical efficiency, the mode hybridization
makes the device design complicated.[22]Here, we present a proof-of-concept experimental demonstration
of a device architecture to convert monochromatic blue fluorescent
OLEDs to WOLEDs efficiently. We observed broadband white-light emission
from a blue OLED by utilizing Bragg modes, which are Fabry–Pérot
modes in the DBR slab, with resonances at red, green, and blue colors.
We demonstrate that although the Bragg modes primarily reside inside
the DBR stack, they can significantly overlap with the emissive layer,
thus enhancing emission and outcoupling of photons at selected wavelengths
over the entire visible spectrum. In our device architecture, the
dielectric DBR is directly deposited on a top-emitting, single-emissive
layer OLED. Instead of usage as a cavity, the photonic stopband of
the DBR is designed to block unwanted ultraviolet electroluminescence.
We call this novel device design a “Bragg converter”.
The DBR stopband and the Bragg modes can be independently designed
as the former depends on the period of the stack and the latter on
its total thickness. Importantly, the Bragg modes which are determined
by the DBR stack thickness are broad and do not require high-quality
DBRs with precisely controlled layer thicknesses. To our knowledge,
this is the only WOLED device design wherein the internal quantum
efficiency can be optimized independently of the color temperature.
WOLED
Device
A schematic of our WOLED is shown in Figure a. It consists of a 50 nm layer
of 2,7-bis
[9,9-di(4-methylphenyl)-fluoren-2-yl]-9,9-di(4-methylphenyl) fluorene
(TDAF) sandwiched between a 70 nm Al bottom anode with a 5 nm MoO3 hole-injecting layer and a 10 nm LiF/Al cathode with a 20
nm 4,7-diphenyl-1,10-phenanthroline (BPhen) hole-blocking layer. The
DBR consisting of 6 alternating layers of SiO2 and Ta2O5 was directly sputtered on top of the Al cathode,
thus providing encapsulation of the organic materials (Figure S2). TDAF was chosen as the single-emissive
layer material due to its pure-hydrocarbon structure (family of oligofluorenes)
which contains the sp3-hybridized C-9 of fluorene. This
gives TDAF high thermal and morphological stability so that it can
withstand aggressive processing steps such us the sputtering of the
dielectric DBR top-mirror. Moreover, TDAF has ambipolar nature, rendering
it capable of electroluminescence.[23] In
the past few years, TDAF has enabled the observation of nonequilibrium
polariton condensation at room temperature.[24−26]
Figure 1
(a) Schematic of the
Bragg WOLED concept. Electroluminescence from
a 50 nm TDAF emissive layer occurs through the Bragg modes of a dielectric
DBR mirror (6-pair SiO2/Ta2O5). The
asymmetric alignment of the layers represents the work functions of
the materials. (b) Schematic illustration of the white-light generation
mechanism, which we call Bragg conversion, in our devices. On the
left, a simplified diagram of electronic states and transitions that
produce photons in molecular semiconductors is shown. The arrows pointing
down represent the radiative transitions, and their thicknesses illustrate
the transition rates (thicker arrow means larger rate leading to more
photons). On the right, the reflectivity of a Bragg converter is depicted.
Its high-reflectivity photonic stopband acts as a long pass filter,
blocking ultraviolet radiation (grayed-out area), while the transparency
Bragg modes, located out of the photonic stopband, are resonant with
the molecular transitions that radiate visible photons (Bragg mode
blue, green, and red; or BMB, BMG, and BMR, respectively). (c) CIE
map, together with the corresponding CIE coordinates. Device dimensions
are 3 × 3 mm2.
(a) Schematic of the
Bragg WOLED concept. Electroluminescence from
a 50 nm TDAF emissive layer occurs through the Bragg modes of a dielectric
DBR mirror (6-pair SiO2/Ta2O5). The
asymmetric alignment of the layers represents the work functions of
the materials. (b) Schematic illustration of the white-light generation
mechanism, which we call Bragg conversion, in our devices. On the
left, a simplified diagram of electronic states and transitions that
produce photons in molecular semiconductors is shown. The arrows pointing
down represent the radiative transitions, and their thicknesses illustrate
the transition rates (thicker arrow means larger rate leading to more
photons). On the right, the reflectivity of a Bragg converter is depicted.
Its high-reflectivity photonic stopband acts as a long pass filter,
blocking ultraviolet radiation (grayed-out area), while the transparency
Bragg modes, located out of the photonic stopband, are resonant with
the molecular transitions that radiate visible photons (Bragg mode
blue, green, and red; or BMB, BMG, and BMR, respectively). (c) CIE
map, together with the corresponding CIE coordinates. Device dimensions
are 3 × 3 mm2.Figure b illustrates
our concept for converting a blue-emitting OLED to a WOLED. After
electrical injection of electron and hole carriers, the exciton formation
and relaxation results in radiation of photons with different rates
as illustrated by downward pointing arrows in the left panel of Figure b. The incorporation
of cavity modes or other near-field modes that are resonant with the
molecular transitions results in an increase of the radiation rate
at the resonant frequencies and suppression of other radiation paths.
The effect of the Bragg converter is demonstrated in Figure c where the Commission Internationale
de l’Eclairage (CIE) map shows the coordinates and pictures
of our OLED devices before the DBR encapsulation [blue OLED, CIE (0.19,
0.15)] and after. Different thicknesses of the SiO2 and
Ta2O5 alternating layers result in shifting
of the Bragg modes and tuning of the color temperature. As an example,
a 6-pair DBR with 43 nm SiO2 and 41 nm Ta2O5 (WOLED 1) thickness produced white electroluminescence with
temperature 6007 K (daylight), and 53 nm SiO2 and 42 nm
Ta2O5 (WOLED 2) thickness produced white light
with temperature 4450 K (cool white).
Bragg Converter
DBR is a superlattice structure consisting of two alternating layers
of low and high refractive index materials and is generally used as
a high-reflectivity nonabsorbing narrow-band mirror. The desired band
of reflection, called stopband, is a result of constructive interference
of light reflected from the layer boundaries. Outside the photonic
stopband spectral range, one can identify a succession of high-transparency
modes, called Bragg modes, that appear with a period of 2LDBRneff/λvac, where LDBR is the thickness, neff is the effective refractive index of the
superlattice, and λvac is the vacuum wavelength of
the light. Unlike cavity modes, the Bragg mode field antinodes do
not concentrate in the central region of an optical cavity, namely,
the spacer layer in between two highly reflective mirrors. Instead,
Bragg modes are localized mostly inside and at the surfaces of the
superlattice slab. This is clearly shown in Figure a,b where we used a typical transfer-matrix
method[27] to calculate the electric field
antinodes of a DBR sandwiching the blue top-emitting OLED.
Figure 2
(a) Transfer-matrix
simulation of reflectivity (pink axis on the
left) and electric field intensity (background contour map) as a function
of the wavelength and position inside the WOLED 1 structure. Reflectivity
and electric field were calculated at normal incidence angle. On the
right is shown a schematic of the simulated structure WOLED 1; the
colors denote different materials as defined in Figure a. The right axis, position (nm), refers
to the thickness of the layers in the device where the 0 nm position
refers to the top-side of the WOLED device. The black lines show the
refractive index change for a propagating plane wave with λ
= 441 nm. (b) Simulated reflectivity of the Bragg converter, top-570
nm thick layers, and electric field intensity map in the electroluminescent
region of the WOLED (from 563 to 637 nm), highlighted with a brown
dashed-line rectangular box. (c) Reflectivity measurements of the
Bragg converter on glass (black) and as a WOLED (passive structure,
no current injection) (red). Note the perfect match of simulated (a,
pink line) and measured (c) modes. (d) Normal incidence top-side electroluminescence
(EL) from the designed device WOLED 1 (red) and a second WOLED device
with different DBR layer content (53 nm SiO2/42 nm Ta2O5), denoted WOLED 2 (blue).
(a) Transfer-matrix
simulation of reflectivity (pink axis on the
left) and electric field intensity (background contour map) as a function
of the wavelength and position inside the WOLED 1 structure. Reflectivity
and electric field were calculated at normal incidence angle. On the
right is shown a schematic of the simulated structure WOLED 1; the
colors denote different materials as defined in Figure a. The right axis, position (nm), refers
to the thickness of the layers in the device where the 0 nm position
refers to the top-side of the WOLED device. The black lines show the
refractive index change for a propagating plane wave with λ
= 441 nm. (b) Simulated reflectivity of the Bragg converter, top-570
nm thick layers, and electric field intensity map in the electroluminescent
region of the WOLED (from 563 to 637 nm), highlighted with a brown
dashed-line rectangular box. (c) Reflectivity measurements of the
Bragg converter on glass (black) and as a WOLED (passive structure,
no current injection) (red). Note the perfect match of simulated (a,
pink line) and measured (c) modes. (d) Normal incidence top-side electroluminescence
(EL) from the designed device WOLED 1 (red) and a second WOLED device
with different DBR layer content (53 nm SiO2/42 nm Ta2O5), denoted WOLED 2 (blue).By using the measured material parameters (see the Methods section), we can design a DBR such that its stopband
acts as an ultraviolet radiation inhibitor while emission of photons
occurs through the Bragg modes. At visible wavelengths, the effective
thickness (dispersive refractive index of SiO2 and Ta2O5) of our Bragg converter exhibits Bragg modes
that perfectly match the blue, green, and red wavelengths (450, 540,
and 640 nm), while their broad line width is essential for broadband
white-light generation. Moreover, the Bragg mode spectrum changes
negligibly when we incorporate the thin OLED in the Bragg converter
design. This can be seen in the simulation in Figure a,b and the reflectivity experiment in Figure c. In Figure a,b, electric field was calculated
with a resolution of 1 nm. The thin emitter layer between the metal
and the DBR does not have any cavity modes within the DBR stopband
(where reflectivity is 1.0); we focus solely on the use of the Bragg
modes that are spectrally outside the stopband. Note that the
Bragg modes have regions of high field intensity overlapping with
the emitter layer, Figure a. Therefore, by simply controlling the DBR effective thickness,
Bragg modes can be designed to have desired wavelengths and to significantly
overlap with the emitter layer so that electroluminescence is efficiently
coupled into these modes.The astounding conversion performance
of the Bragg modes is shown
in Figure d presenting
the generation of white electroluminescence from a blue OLED. Here,
we see that the WOLED 1 produced daylight white (6007 K) electroluminescence
with main peaks at three of the Bragg modes predicted by the transfer-matrix
simulation and measured in reflectivity. We also demonstrate the tunability
of our Bragg converter by another device (WOLED 2) with different
DBR layer content, producing cool white (4450 K) electroluminescence.
In the past years, many works have focused on demonstrating white
electroluminescence through high-quality multiresonant cavity modes.
While high-quality cavity modes are the key elements for amplification
and lasing and can provide narrow emission,[15,16] they also suppress emission from nonresonant states, which reduces
the external quantum efficiency and increases internal thermal losses
and efficiency roll-off. Another advantage of our Bragg converter
is that the Bragg modes are insensitive to DBR layer imperfections,
such as thickness variations and interface roughness. Moreover, the
Bragg modes can be tuned independently of the stopband by changing
the total thickness of the DBR, thus allowing for simultaneous optimization
of stopband and Bragg mode designs.To comprehend the electroluminescence
mechanism in our WOLEDs,
we studied the emission properties of the top-emitting blue OLEDs
(part of our WOLEDs) without the DBR. A schematic and measured
photoluminescence of the OLED are shown in Figure a. Electroluminescence from our OLEDs occurs
from the top-side and is inhomogeneous and spectrally broad (full-width
at half-maximum from 420 to 520 nm) with a central peak at 450 nm, Figure b. We used a ∼7
nm thick top Al cathode to avoid absorption losses when the OLED is
integrated to the Bragg converter. At 7 nm thickness the Al films
showed more than 50% transparency while still being conductive. Similar
OLEDs with thicker top cathode (32 nm) have shown ultrastrong coupling[24] and electroluminescence from the lower polariton
branch.[28] The shape of the emission is
strongly influenced by the interface of the top Al/LiF and air that
creates a cavity effect (half-wavelength in the 100 nm size of the
emitter layer, with refractive index around two, corresponds to roughly
400 nm emitted light), as is confirmed by the transfer-matrix simulation
of the transmission. By performing a current-dependent electroluminescence
measurement of the OLED, we observed that the shape of the spectra
remained unchanged upon increasing current and power (Figure S3). Therefore, for the studied range
of injection currents (power), the electroluminescence mechanism was
not influenced by emission from power-induced excitonic species.
Figure 3
(a) Left:
schematic of the OLED before its encapsulation with the
DBR. Right: the photoluminescence (PL) spectra are identical for bare
TDAF film and a half OLED structure (a multilayer of TDAF, BPhen,
LiF, and 7 nm Al). (b) Comparison between normalized photoluminescence
from a half OLED (red line, half-OLED PL) and a blue OLED before (black,
blue OLED EL) and after its integration to the Bragg converter and
conversion to WOLED 2 (WOLED 2 EL). The electroluminescence was obtained
at 35 mA/cm2. The dashed line shows the calculated transmission
(electroluminescence) for the blue OLED. (c) Rate-equation simulation.
The dashed lines present the input weights of blue, green, and red
colors. The initial weights at time 0 s are obtained from the photoluminescence
spectrum of the bare TDAF film by fitting three Gaussian profiles
at wavelengths 427, 490, and 592 nm (red solid line in part d). The
normalized output color weights are shown by the solid lines. (d)
Rate-equation simulation results after the steady-state has been reached.
The steady-state intensities are illustrated with three Gaussians
centered at wavelengths 427, 490, and 592 nm (blue solid line). The
black line represents the simulated spectrum without relaxation processes
included. The dashed lines present the measured TDAF photoluminescence
(red) and WOLED 2 electroluminescence (blue) for comparison.
(a) Left:
schematic of the OLED before its encapsulation with the
DBR. Right: the photoluminescence (PL) spectra are identical for bare
TDAF film and a half OLED structure (a multilayer of TDAF, BPhen,
LiF, and 7 nm Al). (b) Comparison between normalized photoluminescence
from a half OLED (red line, half-OLED PL) and a blue OLED before (black,
blue OLED EL) and after its integration to the Bragg converter and
conversion to WOLED 2 (WOLED 2 EL). The electroluminescence was obtained
at 35 mA/cm2. The dashed line shows the calculated transmission
(electroluminescence) for the blue OLED. (c) Rate-equation simulation.
The dashed lines present the input weights of blue, green, and red
colors. The initial weights at time 0 s are obtained from the photoluminescence
spectrum of the bare TDAF film by fitting three Gaussian profiles
at wavelengths 427, 490, and 592 nm (red solid line in part d). The
normalized output color weights are shown by the solid lines. (d)
Rate-equation simulation results after the steady-state has been reached.
The steady-state intensities are illustrated with three Gaussians
centered at wavelengths 427, 490, and 592 nm (blue solid line). The
black line represents the simulated spectrum without relaxation processes
included. The dashed lines present the measured TDAF photoluminescence
(red) and WOLED 2 electroluminescence (blue) for comparison.Comparing the OLED emission before and after conversion
to WOLED
2, we see that (Figure b) the Bragg converter vastly modified the emission. The most striking
effect is the 10-fold increase of electroluminescence at the red color
(630 nm). This further highlights that the existence of Bragg modes
and their strong field intensity overlapping with the emitter layer
greatly improves the outcoupling. To confirm that the red-shifted
emission resulted from efficient Bragg outcoupling and not from sample
contamination, we used a 200 fs pulsed laser at 360 nm to optically
excite the top-half of the blue OLED. As shown in the right panel
of Figure a, photoluminescence
of a pristine TDAF film and a multilayer of TDAF, BPhen, LiF, and
7 nm Al is identical, verifying that radiation in our devices occurred
from a single-emissive layer, the TDAF.We have devised a heuristic
rate-equation model to describe the
observed electroluminescence spectrum of the WOLED. The model assumes
three bands at different energies, corresponding to the Bragg modes
at red, green, and blue wavelengths. The bands have different lifetimes
(outcoupling rates) and relaxation rates from higher-energy bands
toward lower-energy bands. We used lifetimes based on the quality
factors of the simulated Bragg modes. Initial weights of population
in the modes were taken from the bare TDAF photoluminescence. See
the Supporting Information for details
of the model. The relaxation rates were essentially fitting parameters,
determined by a comparison to the experiment. Assuming that the relaxation
is slightly more efficient toward lower energies, we can reproduce
the measured WOLED electroluminescence spectrum, see Figure d. The time evolutions of the
input (dashed lines) and the output (solid lines) bands
are presented in Figure c. The steady-state values show that the initial weighting
of colors has changed drastically, such that in the end red and green
wavelengths are highly intensified with respect to blue. For comparison,
we present in Figure d also the spectrum for the case without any relaxation. Thus, the
model suggests that relaxation effects are essential, in addition
to the efficient outcoupling by the Bragg modes. Such relaxation mechanisms
are known to take place under high electrical excitation; for instance,
the electric field modifies the potential landscape between molecular
species creating intermolecular excited states (electroplexes) and
low-lying triplet states.[29] Understanding
the role of relaxation mechanisms in our results is an important topic
of future research since it provides one more way to improve the device
performance.
Conversion Performance and Chromaticity
Remarkably, by comparing the external quantum efficiency of the
blue OLED and Bragg-converted WOLEDs as a function of injection current,
we observed a 20% increase above 40 mA/cm2. Our photonic
structures can also be combined with emitters with high internal quantum
efficiency, as long as the spectrum of the emitter is similar to TDAF.
As shown in Figure a, the low external quantum efficiency of the blue OLED reaches a
plateau value at ∼10 mA/cm2 while the external quantum
efficiency of the WOLED continues to increase. This shows that the
relaxation processes to red-shifted wavelengths and outcoupling by
the Bragg modes improve the overall efficiency of the WOLED. The increase
of external quantum efficiency partially comes from relaxation to
the less absorbing spectral region of the WOLED (Figure S5), but it could be also attributed to the efficient
outcoupling of emission from bimolecular excited states formed in
the interface of TDAF and BPhen.[30,31] Note that
the Bragg converter concept can also be potentially utilized in other
contexts, such as for harvesting energy from long-lived triplet states
either through strong coupling[32−34] (Figure S4) or by typical photon upconversion or phosphorescence mechanisms.[35,36] In addition to the improved external quantum efficiency, the
encapsulation of the OLED in the dielectric Bragg converter results
in a more than 30-fold increase of on-shelf lifetime compared to nonencapsulated
OLED (Figure S2). Figure b shows the WOLED 2 current-dependent electroluminescence
intensity at three main spectral locations 450, 500, and
600 nm. The chromaticity of the WOLEDs remained stable for the measured
range of applied powers. Even when our WOLEDs are multilayer structures,
the color temperature remained stable for detection angles up to ∼25°
(Figure c). For detection
angles >25°, electroluminescence from our WOLEDs becomes increasingly
blue, and the color temperature might not apply. Figure d shows the measured angle-dependent
chromaticity of the WOLED 2 device by collecting momentum-resolved
images from −7° to 78°. A transfer-matrix simulation
of the angle-dependent reflectivity of the WOLED 2 is shown in the
Supporting Information, Figure S8.
Figure 4
(a) External
quantum efficiency (EQE) comparison between the OLEDs
before and after encapsulation in the Bragg converter. Error bars
here are standard deviations from the average value of three different
devices measured three times each. (b) Current-dependent electroluminescence
(EL) intensity at the three main spectral locations 450,
500, and 600 nm of the WOLED 2 device. (c) CIE map of WOLED 2 electroluminescence
at incidence angles of 0°, 22°, 46°, and 73°,
with a detection half angle of 5°. The CIE coordinates from top
to bottom correspond to color temperatures 4450, 6214, 8669, and 9886
K. (d) Angle-resolved electroluminescence map of WOLED 2. This map
was used to determine the CIE values in part c.
(a) External
quantum efficiency (EQE) comparison between the OLEDs
before and after encapsulation in the Bragg converter. Error bars
here are standard deviations from the average value of three different
devices measured three times each. (b) Current-dependent electroluminescence
(EL) intensity at the three main spectral locations 450,
500, and 600 nm of the WOLED 2 device. (c) CIE map of WOLED 2 electroluminescence
at incidence angles of 0°, 22°, 46°, and 73°,
with a detection half angle of 5°. The CIE coordinates from top
to bottom correspond to color temperatures 4450, 6214, 8669, and 9886
K. (d) Angle-resolved electroluminescence map of WOLED 2. This map
was used to determine the CIE values in part c.
Conclusions
We have experimentally demonstrated the conversion of a single-emissive
layer OLED from blue to white by utilizing the Bragg modes of a dielectric
distributed Bragg reflector (DBR). In our novel concept of single-emitter
WOLEDs, the reflectivity stopband of the DBR was used for suppressing
emission in the ultraviolet, while electroluminescence outcoupling
was tailored by utilizing the Bragg modes. The experimental
findings were supported by theoretical analysis. Transfer-matrix simulations
showed that the Bragg modes can be localized in the emissive layer
and reach high field intensities, which is in agreement with the efficient
outcoupling. A rate-equation model reproduced the Bragg-conversion
concept and indicated that relaxation processes play a role in the
white-light generation. Color temperature tuning in our WOLEDs was
achieved by changing the thicknesses of the alternating superlattice
layers and thereby the size of the DBR. Moreover, the WOLED devices
showed a 20% increase of external quantum efficiency and 30-fold increase
of on-shelf lifetime, as compared with the nonconverted blue OLED.
Our device architecture does not depend on the substrate and incorporates
metallic contacts instead of indium tin oxide films which are difficult
to control and contain the scarce material indium. The Bragg modes
do not require precise layer thicknesses which means low-quality,
low-cost DBRs such as all-plastic ones can be used.[37,38] Importantly, the color temperature depends on the DBR while the
internal quantum efficiency depends on the preconversion OLED. Naturally,
changing the emitter to something other than TDAF can also affect
the color temperature. The internal quantum efficiency and color temperature
can therefore be optimized independently; thus, our Bragg conversion
mechanism offers prospects for utilizing highly efficient and stable
blue thermally activated delay fluorescent (TADF) materials.[39,40] Also, the use of a sub-100 nm thick single-emissive layer can enable
the suppression of losses from waveguided modes while allowing for
efficient recombination of electrons and holes. Our result essentially
shows that efficient and high-quality broadband white-light generation
does not require high-quality cavity modes. Therefore, we believe,
our Bragg converter concept is the most promising method for suppressing
the efficiency roll-off in WOLEDs. Moreover, the ability to create
multiple modes with high field intensities in the emissive layer offers
prospects for strong coupling studies, with potential applications
in harvesting precious triplet energy from existing low-cost and stable
organic emitters.
Methods
Device Fabrication
The OLED part of the devices was
fabricated by standard vacuum evaporation methods (Edwards E306).
All the films were deposited at a base pressure of ∼10–6 mbar and deposition rate of 2 Å/s. We used square
15 × 15 mm quartz substrates on which we patterned 4 square OLEDs
with dimensions 3 × 3 mm. To avoid deposition shadowing effects,
500 μm thick aluminum shadow masks were directly in contact
with the substrates. Fabrication of the OLEDs was performed in two
stages that involved venting to atmospheric conditions and mask exchange.
We first deposited the bottom Al anode and MoO3 hole injection
layer using e-beam deposition. For the deposition of the second half
of the OLED we utilized resistive thermal sources for the organic
TDAF and BPhen layers and e-beam sources for the LiF and Al layers.
To encapsulate the OLEDs with the Bragg converter, we vented in atmospheric
conditions and transferred the devices to a sputtering deposition
system (Kurt J. Lesker). A 6-pair superlattice of SiO2 and
Ta2O5 was directly sputtered on top of the OLED.
SiO2 films were produced by RF sputtering from a SiO2 target while Ta2O5 films were reactively
sputtered from a Ta target using a 20:10 sccm Ar:O2 gas-flow
ratio. A combination of ellipsometry (J.A. Woollam M2000) and profilometry
(Bruker DektakXT) was used to obtain the film thicknesses and optical
constants.
Characterization
Schematics of the
optical and electrical
setups are shown in Figure S1. We used
a power source meter (Keithley 2602B) for the electrical characterization
of the devices and an absolute calibrated 2D CCD camera (Pixis 400)
coupled to a spectrometer (Acton SpectrPro 2500) to measure the forward
emission (electroluminescence and photoluminescence) from the devices.
Current-dependent electroluminescence was obtained by focusing the
image of the device on the spectrometer slit with a detection half
angle θ = 15° and magnification M = 2.5.
Angle-resolved electroluminescence and photoluminescence were collected
by rotating the sample with a goniometer at the optical axis of an
objective (10×, 0.3 numerical aperture, NA), and back focal plane
images were focused to the 200 μm entrance slit of the spectrometer.
A vacuum microchamber that allows the rotation of the devices was
developed in house. All measurements were performed at a base pressure
of ∼10–1 mbar. By using the measured spectrally
integrated electroluminescence distribution for varying the collection
angle, we calculated the total photon number emitted from the top
surface of the devices. The external quantum efficiency is then simply
the ratio between externally radiated photons and injected electrons.
Normal incidence reflectivity was performed with a reflection
probe fiber (200 μm cores, 6 light-fibers, 1 read fiber) coupled
to a calibrated miniature spectrometer (OceanOptics USB2000). All
the setups were automatized by using the previously developed data-acquisition
code in LabVIEW.[41]
Authors: Sebastian Reineke; Frank Lindner; Gregor Schwartz; Nico Seidler; Karsten Walzer; Björn Lüssem; Karl Leo Journal: Nature Date: 2009-05-14 Impact factor: 49.962
Authors: Konstantinos S Daskalakis; Aaro I Väkeväinen; Jani-Petri Martikainen; Tommi K Hakala; Päivi Törmä Journal: Nano Lett Date: 2018-03-26 Impact factor: 11.189