An efficient inverted organic solar cell with improved ZnO and gold contact layers

This paper presents a high efficiency (～3.8%) inverted organic photovoltaic devices based on a P3HT:PCBM bulk heterojunction (BHJ) blend with improved electron- and hole-selective contact layers. Zinc oxide (ZnO) nanoparticle films with different thicknesses are deposited on the transparent electrodes as a nano-porous electron-selective contact layer. A thin gold film is used between the BHJ photoactive layer and the poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), which improves the wettability and significantly enhances the stability of the device (>50 days of air exposure). Photovoltaic device parameters such as power conversion efficiency (PCE) and external quantum efficiency (EQE) are systematically examined for inverted devices with different thicknesses of ZnO and gold layers in comparison to the non-inverted and reference inverted devices with no contact layers. The optimized organic devices with ZnO and Au contact layers show exceptional short circuit currents (in excess of 13 mA/cm²), in comparison to the reference devices, which is related to increased quantum efficiency of the device observed in measured EQE experiments. These results are important for development of high efficiency and stable all-printed organic solar cells and point out the role of contact layers, in particular, ZnO conductivity and morphology in the device performance.     

Charge transport and recombination in heterostructure organic light emitting transistors

Light-emitting field effect transistors (LEFETs) are a class of organic optoelectronic device capable of simultaneously delivering the electrical switching characteristics of a transistor and the light emission of a diode. We report on the temperature dependence of the charge transport and emissive properties in a model organic heterostructure LEFET system from 300 K to 135 K. We study parameters such as carrier mobility, brightness, and external quantum efficiency (EQE), and observe clear thermally activated behaviour for transport and injection. Overall, the EQE increases with decreasing temperature and conversely the brightness decreases. These contrary effects can be explained by a higher recombination efficiency occurring at lower temperatures, and this insight delivers new knowledge concerning the optimisation of both the transport and emissive properties in LEFETs.     

Highly enhanced light extraction from organic light emitting diodes with little image blurring and good color stability

We report a highly enhanced light extraction from a top emission organic light emitting diode with little image blurring and color variation with viewing angle. Direct integration of a high refractive index micro lens array on the top of the transparent indium zinc oxide top electrode of a green phosphorescent OLED showed a significant enhancement of light extraction to get EQE of 44.7% from 27.6%, the power efficiency of 134.7 lm/w from 85.9 lm/W and the current efficiency of 217.2 cd/A from 120.7 cd/A without image blurring. In addition, the device showed excellent color stability on viewing angle with Commission Internationale de l’Eclairage (CIE) coordinate of Δx = 0.01, Δy = 0.01 as the viewing angle varied from 0° to 60°.     

Evidences of photocurrent generation by hole–exciton interaction at organic semiconductor interfaces

The charge–exciton interaction at the donor/acceptor interface plays a significant role in the exciton dissociation processes, and thus influences the performance of organic solar cells. In this work, the evidences of photocurrent generation via hole–exciton interaction (HEI) at the organic semiconductor interface in organic solar cells, which is the counterpart of photocurrent generated by electron–exciton interaction, is demonstrated. A heterojunction, composed of copper phthalocyanine (CuPc) and fullerene (C₆₀), is used to provide free holes that interact with the excitons supplied by perfluorinated hexadecafluorophthalo-cyaninatozinc (F16ZnPc). The fact that photocurrent generation via HEI is well evidenced by: (1) a short circuit current of 0.38 mA cm⁻²; (2) the jump of an external quantum efficiency (EQE) around 800 nm after adding a bias light; (3) the EQE variations under bias light of different wavelengths and light intensities; and (4) the superlinear dependence of the photocurrent on the light intensity.     

Cadmium-free quantum dots based violet light-emitting diodes: High-efficiency and brightness via optimization of organic hole transport layers

Bright and efficient violet quantum dot (QD) based light-emitting diodes (QD-LEDs) with heavy-metal-free ZnSe/ZnS have been demonstrated by choosing different hole transport layers, including poly(4-butyl-phenyl-diphenyl-amine) (poly-TPD), poly[9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine] (TFB), and poly-N-vinylcarbazole (PVK). Violet QD-LEDs with maximum luminance of about 930 cd/m², the maximum current efficiency of 0.18 cd/A, and the peak EQE of 1.02% when poly-TPD was used as HTL. Higher brightness and low turn-on voltage (3.8 V) violet QD-LEDs could be fabricated when TFB was used as hole transport material. Although the maximum luminance could reach up to 2691 cd/m², the devices exhibited only low current efficiency (∼0.51 cd/A) and EQE (∼2.88%). If PVK is used as hole transport material, highly efficient violet QD-LEDs can be fabricated with lower maximum luminance and higher turn-on voltages compared with counterpart using TFB. Therefore, TFB and PVK mixture in a certain proportion has been used as HTL, turn-on voltage, brightness, and efficiency all have been improved greatly. The QD-LEDs is fabricated with 7.39% of EQE and 2856 cd/m² of maximum brightness with narrow FWHM less than 21 nm. These results represent significant improvements in the performance of heavy-metal-free violet QD-LEDs in terms of efficiency, brightness, and color purity.     

High-efficiency low color temperature organic light emitting diodes with solution-processed emissive layer

Low color temperature (CT) lighting provides a warm and comfortable atmosphere and shows mild effect on melatonin suppression. A high-efficiency low CT organic light emitting diode can be easily fabricated by spin coating a single white emission layer. The resultant white device shows an external quantum efficiency (EQE) of 22.8% (34.9 lm/W) with CT 2860 K at 100 cd/m², while is shown 18.8% (24.5 lm/W) at 1000 cd/m². The high efficiency may be attributed to the use of electroluminescence efficient materials and the ambipolar-transport host. Besides, proper device architecture design enables excitons to form on the host and allows effective energy transfer from host to guest or from high triplet guest to low counterparts. By decreasing the doping concentration of blue dye in the white emission layer, the device exhibited an orange emission with a CT of 2280 K. An EQE improvement was observed for the device, whose EQE was 27.4% (38.8 lm/W) at 100 cd/m² and 20.4% (24.6 lm/W) at 1000 cd/m².     

Fluorene derivatives for highly efficient non-doped single-layer blue organic light-emitting diodes

Diphenylamino- and triazole-endcapped fluorene derivatives which show a wide energy band gap, a high fluorescence quantum yield and high stability have been synthesized and characterized. Single-layer electroluminescent devices of these fluorene derivatives exhibited efficient deep blue to greenish blue emission at low driving voltage. The single-layer OLED of PhN-OF(1)-TAZ shows a maximum current efficiency of 1.54 cd/A at 20 mA cm⁻² with external quantum efficiency (EQE) of 2.0% and CIE coordinates of (0.153, 0.088) in deep blue region, while the single-layer device of oligothienylfluorene PhN-OFOT-TAZ shows a maximum brightness of 7524 cd/m² and a maximum current efficiency of 2.9 cd/A with CIE coordinates of (0.20, 0.40) in greenish blue.     

Hole transfer from PbS nanocrystal quantum dots to polymers and efficient hybrid solar cells utilizing infrared photons

Polymer/inorganic-nanocrystals bulk heterojunction solar cells, where inorganic semiconductor nanocrystals such as CdSe, CdS, CdTe, ZnO, TiO₂, and silicon, replace the fullerene molecules as the electron acceptors, typically exhibit a power conversion efficiency (PCE) below 3% even after tremendous engineering efforts to optimize the nanocrystal size, shape, and nanoscale morphology. One promising feature of polymer hybrid solar cells is the ability to sensitize conjugated polymers, which on their own absorb only in the visible part of solar spectrum, into the infrared spectral range using infrared-active lead salt nanocrystal quantum dots (NQDs). Here we observed for the first time hole transfer from PbS NQDs to polymers as evidenced by the quenching of the PbS photoluminescence (PL), a sign of the presence of charge separating type II heterojunction. The type II band-offset at the NQD/polymer heterojunction enables efficient hole extraction from NQDs and leads to a record PCE of 3.80%, realized in a planar junction configuration under simulated air mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm². The photocurrent has an extended spectral range spanning from the ultraviolet (UV) to the infrared (IR). Contributions from the polymer and PbS to the photocurrent were identified. Infrared photons (>700 nm) contribute about 30% of the photocurrent and yield a high external quantum efficiency (EQE) of 20% at 1050 nm.     

High sensitivity organic photodiodes with low dark currents and increased lifetimes

Organic semiconductors hold the promise for large-area, low-cost image sensors and monolithically integrated photonic microsystems. This requires the availability of photodiodes offering at the same time high quantum efficiency, low noise and long lifetimes. Although published structures of organic photodiodes offer high external quantum efficiencies (EQE) of up to 76% [F. Padinger, R.S. Rittberber, N.S. Sariciftci, Effects of postproduction treatment on plastic solar cells, Advanced Functional Materials 13 (2003) 1, P. Schilinsky, C. Waldauf, C.J. Brabec, Recombination loss analysis in polythiophene based bulk heterojunction photodetectors, Applied Physics Letters 81 (20) (2002) 3885], [1], [2] they normally suffer from short lifetimes of only a few hundred hours as well as large dark currents. In our work the lifetime of a poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) heterojunction photodiode structure was increased to several thousand hours by omitting the widely used poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) anode layer. In addition, a simple model of optical interference and absorption effects was used to find the optimum thickness that combines high quantum efficiency with low dark current. As a result, we report on organic photodiodes with state-of-the-art EQE of 70% at 0 V bias, an on/off current ratio of 10⁶ at −1 V and 40 mW/cm² illumination, dark current densities below 10 nA/cm² at −1 V, and a lifetime of at least 3000 h.     

High efficiency and non-color-changing orange organic light emitting diodes with red and green emitting layers

We report a high performance orange organic light-emitting diode (OLED) where red and green phosphorescent dyes are doped in an exciplex forming co-host as separate red and green emitting layers (EMLs). The OLED shows a maximum external quantum efficiency (EQE) of 22.8%, a low roll-off of efficiency with an EQE of 19.6% at 10,000 cd/m², and good orange color with a CIE coordinate of (0.442, 0.529) and no color change from 1000 to 10,000 cd/m². The exciplex forming co-host system distributes the recombination zone all over the EMLs and reduces the triplet exciton quenching processes.     

Low dark current inverted organic photodetectors employing MoOx:Al cathode interlayer

We report low dark current small molecule organic photodetectors (OPDs) with an inverted geometry for image sensor applications. Adopting a very thin MoO_x:Al cathode interlayer (CIL) in the inverted OPD with a reflective top electrode results in a remarkably low dark current density (J_d) of 5.6 nA/cm² at reverse bias of 3 V, while maintaining high external quantum efficiency (EQE) of 56.1% at visible wavelengths. The effectiveness of the CIL on the diode performance has been further identified by application to inverted OPDs with a semi-transparent top electrode, leading to a significantly low J_d of 0.25 nA/cm², moderately high EQE_{540 nm} of 25.8%, and subsequently high detectivity of 8.95 × 10¹² Jones at reverse bias of 3 V. Possible origins of reduced dark currents in the OPD by using the MoO_x:Al CIL are further described in terms of the change of interfacial energy barrier and surface morphology.     

Theoretical model for the external quantum efficiency of organic light-emitting diodes and its experimental validation

An optical energy loss mechanism including the surface plasmon polariton (SPP) loss, wave guide (WG) mode and substrate mode in organic light-emitting diodes (OLEDs) is introduced based on CPS theory. The theoretical calculations of both the out-coupling efficiency (OCE) and the external quantum efficiency (EQE) of OLEDs are proposed. MATLAB tools are applied to simulate the optical model and provide the results of the two efficiencies. It is demonstrated that, the OCE and the EQE in a green phosphorescence OLED with optimized device structure can reach up to 20% and 27%, respectively (intrinsic quantum efficiency q = 90% assumed). The simulation results based on the theoretical model are further validated experimentally.     

Efficient planar organic solar cells with the high near-infrared response

Efficient planar organic solar cells extending the response into the near-infrared (NIR) were fabricated using the highly ordered Titanyl phthalocyanines (TiOPc) films as the donor layer. This type of films obtained through the weak epitaxy growth (WEG) method presents good continuity and integrity with the low density of grain boundaries. More importantly the films own a strong absorption in the NIR (750–950 nm) and a broad absorption spectrum from 550 to 950 nm. Meanwhile the high external quantum efficiency (EQE) is obtained in the NIR with the peak value over 38% and the EQE is over 18% in the entire response range, which could benefit from the long exciton diffusion length and the high carrier mobility of the highly ordered films. Thereby the fabricated planar solar cells achieve a high short-circuit current density (J_sc) of 9.26 mA cm^?2 and a power conversion efficiency (PCE) of 2.67%.     

Enhancement of spectral stability and efficiency on blue light-emitters via introducing dibenzothiophene-S,S-dioxide isomers into polyfluorene backbone

Dibenzothiophene-S,S-dioxide isomer (FSO) monomers were copolymerized with extensively employed 9,9-dioctyl-2,7-fluorene monomer by Suzuki polycondensation. By introducing FSO unit into polyfluorene backbone, the spectral stability and efficiency of the blue-emitting polyfluorenes are significantly improved. All of the obtained copolymers and their devices exhibit stable photoluminescence (PL) and electroluminescence (EL) spectra, respectively, upon change of thermal annealing temperature and current densities. Furthermore green emission which is usually associated with excimer/aggregation or defects is absent in PL and EL spectra. In fact, the FSO unit acts as a deep trap for electron in the polyfluorene backbone, which could suppress the long wavelength emission. Moreover, the FSO unit lowers LUMO energy levels of the polyfluorenes, thus can maintain a balanced charge carrier injection and transport in the device based on the polymers, and therefore improves the device efficiencies. The device based on PF-2,8FSO1 and PF-3,7FSO5 show an external quantum efficiency (EQE) of 3.6% and a luminance efficiency (LE) of 3.7 cd/A with CIE coordinate of (0.16, 0.07), and an EQE of 3.8% and a LE of 4.6 cd/A with CIE coordinate of (0.15, 0.12), respectively. The results indicate that poly (dibenzothiophene-S,S-dioxide-co-9,9-dioctyl-2,7-fluorene)s could be a promising candidate for blue-emitting polymers with spectral stability and high efficiency.     

Highly efficient two component phosphorescent organic light-emitting diodes based on direct hole injection into dopant and gradient doping

A series of two component phosphorescent organic light-emitting diodes (PHOLEDs) combing the direct hole injection into dopant strategy with a gradient doping profile were demonstrated. The dopant, host, as well as molybdenum oxide (MoO₃)-modified indium tin oxide (ITO) anode were investigated. It is found that the devices ITO/MoO₃ (0 or 1 nm)/fac-tris(2-phenylpyridine)iridium [Ir(ppy)₃]:1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi) (30 → 0 wt%, 105 nm)/LiF (1 nm)/Al (100 nm) show maximum external quantum efficiency (EQE) over 20%, which are comparable to multi-layered PHOLEDs. Moreover, the systematic variation of the host from TPBi to 4,7-diphenyl-1,10-phenanthroline (Bphen), dopant from Ir(ppy)₃ to bis(2-phenylpyridine)(acetylacetonate)iridium [Ir(ppy)₂(acac)], and anodes between ITO and ITO/MoO₃ indicates that balancing the charge as well as controlling the charge recombination zone play critical roles in the design of highly efficient two component PHOLEDs.     

Ionic self-assembled monolayer for low contact resistance in inkjet-printed coplanar structure organic thin-film transistors

To reduce the contact resistance in inkjet-printed organic thin-film transistors (OTFTs), the use of a newly synthesized ionic self-assembled monolayer (SAM) consisting of an anchoring group, a linker group, and an ionic functional group, is investigated. According to the gated transmission line method (TLM) measurements of a series of OTFT devices, where one type has no charge injection layer, another type having a pentafluorobenzenethiol (PFBT) injection layer, and a third type containing a (6-mercaptohexyl)trimethylammonium bromide (MTAB) ionic SAM, the latter exhibits the lowest contact resistance value of ∼3.1 K Ω cm. The OTFTs without charge injection layer and with the PFBT SAM have relatively higher contact resistance values of ∼6.4 K Ω cm and ∼5.0 K Ω cm, respectively. The reduced contact resistance in the OTFTs with ionic SAMs is attributed to the large charge carrier density induced by the ionic SAM, which allows sufficient tunneling-assisted injection of the carriers from the metal electrode to the polymer semiconductor. These results suggest that the use of appropriate ionic SAM injection layer is an effective way to reduce the contact resistance, hence improving the charge transport characteristics of inkjet-printed OTFTs.     

Enhancing the efficiency of simplified red phosphorescent organic light emitting diodes by exciton harvesting

High efficiency red phosphorescent organic light emitting diode (PHOLED) employing co-doped green emitting molecule bis(2-phenylpyridine)(acetylacetonate)iridium(III) [Ir(ppy)₂(acac)] and red emitting molecule bis(2-methyldibenzo[f,h]quinoxaline)(acetylacetonate)iridium(III) [Ir(MDQ)₂(acac)] into 4,4′-bis(carbazol-9-yl)biphenyl (CBP) host in a simplified wide-bandgap platform is demonstrated. The green molecule is shown to function as an exciton harvester that traps carriers to form excitons that are then efficiently transferred to the Ir(MDQ)₂(acac) by triplet-to-triplet Dexter energy transfer, thereby significantly enhancing red emission. In particular, a maximum current efficiency of 37.0 cd/A and external quantum efficiency (EQE) of 24.8% have been achieved without additional out-coupling enhancements. Moreover, a low efficiency roll-off with the EQE remaining as high as 20.8% at a high luminance of 5000 cd/m² is observed.     

Organic light-emitting diode-based plausibly physiologically-friendly low color-temperature night light

Light sources with lower color temperature (CT) show markedly less suppression effect on the secretion of melatonin, an oncostatic hormone. Light sources with higher color rendering index (CRI) provide better visual comfort. In this report, we demonstrate the design and fabrication of low CT, high CRI fluorescent organic light-emitting diode (OLED) with five-band emitting from a single emissive layer. The best performed device exhibits a CT of 1773 K, much lower than that of candles (1800–2000 K) or incandescent bulbs (2000–2500 K), 87 CRI, a beyond theoretical limit external quantum efficiency (EQE) 6.4%, and 11.9 lm/W at 100 cd/m². One major reason for having the ultra-low CT and relative high CRI may be attributed to the significantly intensive deep red emission. The comparatively high efficacy and EQE may be attributed to the employment of a smooth stepwise energy-level structure, enabling low injection barriers and balance carrier injection.     

All-solution-processed inverted polymer solar cells on granular surface-nickelized polyimide

In this study, we prepared all-solution-processed inverted polymer solar cells (PSCs) incorporating two solution-processed electrodes – surface-nickelized polyimide films (NiPI films) as cathodes and high-conductivity poly(3,4-ethylenedioxythiophene)/poly(styrene-sulfonate) (PEDOT:PSS) films as anodes – and an active layer with a bulk heterojunction morphology of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-buytyric acid methyl ester (PCBM). The granular Ni thin films, which exhibited good adhesion and high-conductivity (ca. 2778 S cm^?1) on the polyimide (PI) substrates and possessed a work function different from that of pure Ni metal (WF, 5.4 eV). Using ultraviolet photoelectron spectroscopy, we determined that the WF of the NiPI films was ca. 3.9 eV. Prior to the coating of the photoactive layer, the surface of the NiPI films were treated with titanium(diisopropoxide)bis(2,4-pentanedionate) (TIPD) solution to facilitate the deposition of high-quality active layer and further as a hole blocking layer. The solution processed anodes (solvent-modified PEDOT:PSS films) were further coated and subjected to mild oxygen plasma treatment on the active layer. Short exposure (5 s) to the plasma improved the quality of the surface of the active layer for PEDOT:PSS deposition. These inverted PSCs on flexible granular NiPI films provided a power conversion efficiency of 2.4% when illuminated under AM 1.5 conditions (100 mW cm^?2). The phenomenon of light absorption enhancement in those inverted PSCs was observed as indicated in reflective UV–vis, haze factor and external quantum efficiency (EQE) responses. The resulting fill factor (FF) of 0.43 is still significantly lower than the FF of 0.64 for standard devices. When compared to the planar structure, the improvement of absorbance of light and good haze factors was obtained for granular structure which suggests NiPI as a better back contact electrode through enhancing the light trapping and scattering in inverted PSCs.