Organic-inorganic (hybrid) lead halide perovskites are taking the lead among the emerging photovoltaics technologies, thanks to the demonstration of power conversion efficiencies exceeding 20 %. Hybrid perovskites have a wide spectrum of desirable properties; they are direct bandgap semiconductors with very high absorption coefficients, high and balanced hole and electron mobility, and large diffusion length. A unique feature of these materials is their versatility in terms of bandgap energy, which can be tuned by simple exchange of their components. In this paper we present vacuum and hybrid deposition routes for the preparation of different organic-inorganic lead perovskite thin films, and their incorporation into efficient solar cells. The influence of the type of organic semiconductors used as hole/electron transport layer in p-i-n solar cells will be presented. We also discuss their electroluminescence properties, either for applications in light-emitting diodes or as a diagnostic tool of the optical and electronic quality of perovskite thin films. Finally, the effect of additives and dopants in the perovskite absorber as well as in the charge selective layers will be described.
In this Proceedings paper, we report on the synthesis of a family of polythiophene-based conjugated polyelectrolytes, both homopolymers and random copolymers varying in the building block ratio and counter ions, toward a better fundamental understanding of the structure-property relations of these ionic derivatives in organic photovoltaics. One of the ionic homopolymers was successfully implemented as a donor material in fully solution-processed efficient bi-layer solar cells (up to 1.6% PCE in combination with PC71BM) prepared by the low impact meniscus coating technique. On the other hand, these imidazolium-substituted polythiophenes were also applied as materials for electron transport layers (ETLs), boosting the I-V properties of PCDTBT:PC71BM solar cell devices up to average PCE values of 6.2% (~20% increase), which is notably higher than for previously reported ETL materials. Advanced scanning probe microscopy techniques were used to elucidate the efficiency enhancing mechanism.
Photoluminescence (PL) spectroscopy has been performed in-situ on iridium(III) ionic transition metal complex (iTMC)-
based sandwich-type light-emitting electrochemical cells (LECs) during device operation and after switch-off. It is
demonstrated that driving the device leads to a considerable decrease of the PL intensity of the active layer. Two
different time regimes for this decrease have been identified. The first one is characterized by a complete recovery of the
PL after the device is turned off corroborating the existence of dynamically formed doped regions also in iTMC-based
LECs. In the second regime the PL does not completely recover which is attributed to a permanent degradation of the
active layer that is the main source for the low lifetime of the devices.
Additionally, it is demonstrated how to externally stabilize the dynamic configuration leading to a half lifetime in excess
of 1000 hours at simultaneous high brightness of more than 1000 cd/m2 and fast turn-on of less than one second.
Neat bi-layer solar cells of a fullerene acceptor and a cyanine dye donor were prepared using meniscus coating.
Meniscus coating is very material efficient and leads to high quality pinhole-free films. The cells exhibit high open
circuit voltages of 1 volt, only 0.8 eV below the band gap of the cyanine dye. This is one of the smallest differences
reported for organic solar cells and illustrates an almost optimal donor-acceptor energy level alignment.
Typically high efficient OLED device structures are based on a multitude of stacked thin organic layers prepared by
thermal evaporation. For lighting applications these efficient device stacks have to be up-scaled to large areas which is
clearly challenging in terms of high through-put processing at low-cost. One promising approach to meet cost-efficiency,
high through-put and high light output is the combination of solution and evaporation processing. Moreover, the
objective is to substitute as many thermally evaporated layers as possible by solution processing without sacrificing the
device performance. Hence, starting from the anode side, evaporated layers of an efficient white light emitting OLED
stack are stepwise replaced by solution processable polymer and small molecule layers. In doing so different solutionprocessable
hole injection layers (= polymer HILs) are integrated into small molecule devices and evaluated with regard
to their electro-optical performance as well as to their planarizing properties, meaning the ability to cover ITO spikes,
defects and dust particles. Thereby two approaches are followed whereas in case of the "single HIL" approach only one
polymer HIL is coated and in case of the "combined HIL" concept the coated polymer HIL is combined with a thin
evaporated HIL. These HIL architectures are studied in unipolar as well as bipolar devices. As a result the combined HIL
approach facilitates a better control over the hole current, an improved device stability as well as an improved current
and power efficiency compared to a single HIL as well as pure small molecule based OLED stacks. Furthermore,
emitting layers based on guest/host small molecules are fabricated from solution and integrated into a white hybrid stack
(WHS). Up to three evaporated layers were successfully replaced by solution-processing showing comparable white
light emission spectra like an evaporated small molecule reference stack and lifetime values of several 100 h.
A new, but archetype compound [Ir(ppy-F2)2Me4phen]PF6, where ppy-F2 is 2-(2',4'-
fluorophenyl)pyridine and Me4phen is 3,4,7,8-tetramethyl-1,10-phenanthroline, was synthesized and used
to prepare a solid-state light-emitting electrochemical cell (LEC). This complex emits blue light with a
maximum at 476 nm when photoexcited in a thin film, with a photoluminescence quantum yield of 52 %.
It yields an efficient single-component solid-state electroluminescence device with a current efficiency
reaching 5.5 cd/A and a maximum power efficiency of 5.8 Lm/Watt. However, the electroluminiscence
spectrum is shifted with respect to the photoluminiscence spectrum by 80 nm resulting in the emission of
green light. We demonstrate that this unexpected shift in emission spectrum is not originating from the
way of excitation, nor from the presence of large concentrations of ions, but is related to the concentration
of the ionic transition metal complex in the thin film. The origin of the concentration dependent emission
is extensively commented and argued to be related to the population of either 3LC π-π* or 3MLCT triplet
states, in diluted and concentrated films, respectively. Using quantum chemical calculations we
demonstrate that three low-energy triplet states are present with only 0.1 eV difference in energy and that
their associated emission wavelengths differ by as much as 60 nm from each other.
Current-voltage characteristics of polyspiroblue SB -based light-emitting diodes with the structure:
ITO/PEDOT:PSS/SB/cathode have been analyzed. Several cathodes were used (Al, LiF with different thicknesses, and
Ba) in order to change the barrier for electron injection. As expected, the inclusion of a thin (0.5-1 nm) LiF layer
between SB and Al, or the use of Ba, modifies the electron barrier as derived from the increment in the turn-on voltage
(related to the built-in potential) with respect to that observed for Al cathode. For hole-only devices (Au cathode) J-V
characteristics are interpreted in terms of bulk-limited SCLC transport with hole mobility of the order of 10-6 cm2/V s.
When J-V characteristics obtained using different cathodes are compared the current level observed are consistent with
the mobility observed for the hole only device. This implies that the device operation is mainly determined by the hole
conduction. However, the electroluminescence observed for these devices employing different cathodes differs over four
orders of magnitude. Our results suggest that the electron mobility is much smaller than the hole mobility and that the
recombination process is confined to a thin layer near the cathode. Additionally, the results obtained from simple device
modeling are also presented.
A novel class of bottom emission electroluminescent device is described in which a metal oxide is used as the electron
injecting contact. The preparation of such a device is simple, and consists of the deposition of a thin layer of a metal
oxide on top of an indium tin oxide covered glass substrate, followed by the solution processing of the light emitting
layer and subsequently the deposition of a high workfunction (air stable) metal anode. This architecture allows for a low
cost electroluminescent device as no rigorous encapsulation is required. Electroluminescence with a high brightness level
reaching 6500 cd/m2 is observed at voltages as low as 8 V, demonstrating the potential of this new approach to OLED
devices. Unfortunately the device efficiency is rather low caused by the high current density flowing through the device.
We show that the device only operates after the insertion of an additional hole injection layer in between the light
emitting polymer and the metal anode. A simple model that explains the observed experimental results and provides
avenues for further optimization of these devices is described. It is based on the idea that the barrier for electron injection
is lowered by the formation of the space charge field over the metal oxide-light emitting polymer interface due to the
build up of holes in the light emitting polymer layer.
Charge injection in organic light emitting diodes (OLEDs) is studied by impedance spectroscopy on a solution processable polymer based OLED (PLED) using different metallic cathodes. A negative capacitance is observed in organic light-emitting diodes (OLEDs) at low frequencies which can be explained using a detailed kinetic model based on sequential injection through surface states at the metal/organic interface. In this paper the methodology used to derive this model and its application to experimental data is presented.
The performance of blue emitting OLED devices, using a polyspiro as blue light emitting polymer, were studied as a function of the conductivity of a novel hybrid hole injection material. The hole injection material is based on a polyarylamine using a molecular magnet as oxidant. The charge density and the luminance of the devices changed considerably with increasing conductivity of the hole injection layer. The change in device performance can be attributed to a change from a hole limited device to a balanced charge carrier device and eventually to an electron limited device. The performance of the optimized device configuration is significantly improved with respect to a device making use of PEDOT:PSS as the hole injection layer reaching efficacies of 3.5 cd/A at 5000 cd/m2.
An overview of the requirements for full color passive matrix displays and their implications for the light emitting materials will be presented. Using the performance of light emitting polymers tested in Philips devices the status of the light emitting polymers is reviewed. It will be shown that the performance of light emitting polymers is at the edge of being acceptable for practical applications. Red and green light emitting polymers can already be used for certain monochrome applications. However, for the high-resolution displays used in mobile telecom applications the efficacy for red and the lifetime for green are still somewhat low. Optimization routes for further improvement in terms of efficacies and lifetimes for red and green are identified. The peformance of blue light emitting polymers has rapidly improved over the last year, but the lifetime is still too short for full color applications. Improvement routes for the blue light emitting polymers and its device structure are outlined.
Two novel photorefractive polymers are presented, based on the charge transport molecule N,N'-diphenyl-N,N'- bis(3-methylphenyl)-{1,1'-biphenyl]-4,4'-diamine (TPD). In one polymer the TPD unit is chemically modified so that it can function both as charge transport and as electro-optic molecule. In the other polymer the TPD is incorporated into the polymeric backbone and provides the charge transport and functions as a host for the dispersed electro-optic molecules. In both types of polymers the trap density is very low, which causing a 900 phase shift between the refractive index grating and the illumination pattern and a rather small photorefractive performance. The trap density can in the case of the bifunctional molecule based polymer be increased by adding small amounts of N,N,N',N'-tetramethyl-paraphenylene diamine (TMPD) which has a lower ionization energy than the bifunctional molecule. This results in a strong increase of photorefractive performance and simultaneously in a lowering of the phase-shift. The ionization energy of some molecules used in photorefractive polymers is determined using gas-phase ultraviolet photoelectron spectroscopy and cyclovoltammetry. Using these ionization energies the process of the space-charge field formation can be understood on the basis of the components of the photorefractive polymer.
In this paper we discuss the space charge field formation process in poly(N-vinylcarbazole)-based photorefractive polymers and more specifically its relation to charge transport. In the steady state, the experimental results are found to be in qualitative agreement with the predictions of the standard model. A large saturation field, that corresponds to a trap density of the order of 5 multiplied by 1016 cm-3 is estimated. In the transient regime however, the space charge field departs from its expected behavior: this is shown to arise due to the influence of disorder on the charge transport process.
A novel photorefractive polymer is presented, based on a bifunctional molecule which is a derivative of the well known charge transport molecule N,N'-diphenyl-N,N'-bis(3- methylphenyl)-[1,1'-biphenyl]-4,4'-diamine (TPD). In this material the low intrinsic tap density causes the rather low value for the gain coefficient as well as the 90 degree phase shift between the refractive index grating and the illumination pattern. The trap density can effectively be modified by adding small amounts of 1,4-bis-(N,N- dimethylamino)benzene, resulting in a large increase in gain coefficient and a lower phase shift.
The transient behavior of photorefractive gratings in the polymer composite poly(N-vinyl carbazole) (PVK), 2,4,7-trinitro-9-fluorenone doped with the electro-optic molecules 4- (hexyloxy)nitrobenzene or N,N-diethyl-para-nitroaniline is presented. It is shown that despite the dispersive character of charge transport in polymers, information that allows the estimation of the hole drift mobility is obtained. The change in the hole drift mobility for samples with various trap densities, induced by 4-(diethylamino)benzaldehyde diphenylhydrazone, was measured.
Modification of the trap density of the photorefractive polymer composite poly(N-vinyl carbazole), 2,4,7-trinitro-9-fluorenone, and N,N-diethyl-para-nitrozniline is achieved with the addition of 4-(diethylamino)bensaldehyde diphenylhydrazone (DEH). Measurements of the response time and the phase shift of the photorefractive gratings indicate that at low concentrations DEH acts as a trap, while at higher concentrations a new charge transport pathway through hopping between DEH molecules is established. The transient behavior of these gratings further supports this picture.
We report on the synthesis of two novel photorefractive polymers: one host-guest material based on the well known charge transport molecule TPD and one fully functionalized polymer with extended transparency over the visible. Preliminary results of photorefractive measurements are reported.
Photorefractivity, or reversible photoinduced refractive index change, was first observed about twenty-five years ago in inorganic crystals. The photorefractive effect involves generation, transport and trapping of charges and a change of the refractive index through the electro-optic effect. We have synthesized a photorefractive crosslinked polymer material in which the active components, derivatives of diethylaminobenzaldehyde diphenylhydrazone and para- nitroaniline, are chemically linked into the polyurethane network. During the crosslinking of the polyurethane the para-nitroaniline groups were aligned (poled) by an external electric field, which resulted in a non-centrosymmetric polymer material. This material was shown to be photorefractive by the two beam coupling experiment, without the application of an external electric field.
We have synthesized silicon-based donor-acceptor compounds that are transparent in the visible and have moderate values of the first hyperpolarizability, (beta) , which are measured with Hyper-Rayleigh Scattering (HRS). The spectroscopic properties (UV-VIS) are studied by investigating the influence of the donor and acceptor strength and the chain length on the absorption maxima and (lambda) cutoff values. We will focus the perfluorobutylsulfonyl in studies concerning functionalization and incorporation into a polymer matrix.
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