Effective hole-injection layer for non-doped inverted top-emitting organic light-emitting devices

Non-doped inverted top-emitting organic light-emitting diode with high efficiency is demonstrated through employing an effective hole-injection layer composed of MoO_x. One reason for high efficiency lies on the energy-level matching between MoO_x and hole-transport, and another is due to the Ohmic contact formed between MoO_x and Ag. Both of them lead to an improvement of the hole-injection capability from Ag top anode. Moreover, the symmetrical current of “hole-only” device with MoO_x shows better hole-injection capability, which is independent of the deposition sequence. The optimized device with MoO_x hole-injection layer exhibits maximum current efficiency of 3.7 cd/A at a raised luminance level of 14,900 cd/m² and a maximum luminance of 47,000 cd/m² under 18 V.     

PEDOT修饰对Ag/P3HT/ITO样品载流子注入特性的改善

通过分析Ag/P3HT/ITO结构样品的载流子注入特性,研究了PEDOT(3,4-Ethylene-dioxythiophene thiophene)的界面修饰对样品薄膜注入特性的影响,其中,P3HT(Poly(3-hexyl-thiophene))薄膜采用旋涂法制备,P3HT溶液浓度为30mg/ml(氯仿为溶剂)。测试结果表明:1)P3HT的退火温度对其本身性能影响很大,退火温度越高,导电性能越差,在373K时,性能达到最佳,单位面积电流可达0.092A/cm2;2)PEDOT的界面修饰作用使Ag与P3HT功函数不匹配的问题得到明显改善。实验结果与理论分析基本吻合,样品注入特性改善比在1.15～1.30之间。同样的样品在退火温度为373K时性能达到最佳,单位面积电流可达0.106A/cm2。     

Performance enhancement in organic photovoltaic devices using plasma-polymerized fluorocarbon-modified Ag nanoparticles

In this work, Ag nanoparticles were modified by an ultra-thin plasma-polymerized fluorocarbon film (CF_X) to form a composite CF_X-modified Ag nanoparticles/indium tin oxide (ITO) anode for application in organic photovoltaic (OPV) devices. A CF_X-modified Ag nanoparticles/ITO anode exhibited a superior surface work function of 5.4 eV suited for application in OPV devices. The performance of zinc phthalocyanine:fullerene-based OPV devices showed a significant improvement when the structural identical cells are made with the CF_X-modified Ag nanoparticles/ITO. This work yielded a promising power conversion efficiency of 3.5 ± 0.1%, notably higher than that with a bare ITO anode (2.7 ± 0.1%).     

Enhanced performance of inverted organic solar cell by a solution-based fluorinated acceptor doped P3HT:PCBM layer

An inverted organic solar cell based on strong electron acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) doped poly (3-hexylthiophene) P3HT: [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) was fabricated to figure out the p-type doping effect on the device performance. It was found that the doping concentration played a critical role on the electrical output of the devices. An enhanced power conversion efficiency (PCE) of 4.22% was achieved, in comparison of PCE of 3.68% for the device based on pristine P3HT:PCBM. The topography morphology of the active film, the hole mobility, the ultraviolet–visible absorption spectrum, the photoluminescence (PL) lifetime and the Fermi energy level of P3HT film with and without F4-TCNQ doping were characterized to investigate the doping effect. The measured results indicated that the hole mobility and absorption of P3HT film was slightly modified with F4-TCNQ doping. On the contrary, the active film morphology, the PL lifetime and the Fermi energy level of P3HT changed dramatically with doping. It was found that F4-TCNQ preferred to approach to the air/liquid interface during the solvent dry process, leading to F4-TCNQ-rich upper layer due to its low surface energy. The layer with proper thickness between anode and active layer dramatically improve the interface contact, resulting in the enhanced device performance.     

Organic solar cells using plasmonics of Ag nanoprisms

We demonstrate plasmonic effects in bulk heterojunction organic solar cells (OSCs) consisting of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) by incorporating silver (Ag) triangular shaped nanoparticles (nanoprisms; NPSs) into a poly(3,4-ethylenedioxythiophene) buffer layer. The optical absorption and geometric characteristics of the Ag NPSs were investigated in terms of their tunable in-plane dipole local surface plasmon resonance (LSPR) bands. The photovoltaic characteristics showed that the power conversion efficiency (PCE) of the plasmonic OSCs was enhanced by an increase of short circuit current (J_sc) compared to that of the reference cells without any variation in electrical properties. The enhanced J_sc is directly related to the enhancement of optical absorption efficiency by the LSPR of the Ag NPSs. We measured the photovoltaic characteristics of the plasmonic OSCs with various distances between the Ag NPSs and the P3HT:PCBM active layer, in which the PCEs of the plasmonic OSCs decreased with increasing distance. This suggests that the increase of photocurrent and optical absorption was due to near field enhancement (i.e., intensified incident light on the active layer) by the LSPR of the Ag NPSs.     

Enhancement of hole injection with an ultra-thin Ag2O modified anode in organic light-emitting diodes

The interface between the organic layer and the Indium Tin Oxide (ITO) layer of an organic light-emitting diode (OLED) is crucial to the performance of the device. An ultra-thin Ag₂O film, used as an anode modification layer, has been employed on ITO surface through the UV-ozone treatment of Ag films. The insertion of this thin film with higher work function enhances the hole injection in the organic light-emitting diode and improves the performance of the devices effectively. The maximum electroluminescence (EL) efficiency of the device with the Ag₂O film is 4.95 cd/A, it is about 60% higher than that of the device without it.     

Lowering the Operational Voltage of Single-Layer Polymer Electroluminescent Devices by Using CuOx Modifying Indium-Tin Oxide Electrode

In this study it is demonstrated that oxygen-plasma-generated CuOx can enhance the holes injection from ITO anode into polymer layer in single-layer polymer EL devices. The possible reason for this enhancement is because the ITO anode modified with CuOx possesses much higher work function than pure ITO anode, which reduces the barrier for hole-injection and further lowers the operational voltage of the polymer EL devices. The work function shift is probable due to the oxygen-plasma-generated CuOx can store more releasable oxygen, and the releasable oxygen in turn changes the oxygen concentration just near ITO surface, which will shift the work function of ITO anode.     

Lowering the Operational Voltage of Single-Layer Polymer Electroluminescent Devices by Using CuOx Modifying Indium-Tin Oxide Electrode

In this study it is demonstrated that oxygen-plasma-generated CuOx can enhance the holes injection from ITO anode into polymer layer in single-layer polymer EL devices. The possible reason for this enhancement is because the ITO anode modified with CuOx possesses much higher work function than pure ITO anode,which reduces the barrier for hole-injection and further lowers the operational voltage of the polymer EL devices. The work function shift is probable due to the oxygen-plasma-generated CuOx can store more releasable oxygen,and the releasable oxygen in turn changes the oxygen concentration just near ITO surface,which will shift the work function of ITO anode.     

ITO-free flexible organic light-emitting diode using ZnS/Ag/MoO3 anode incorporating a quasi-perfect Ag thin film

The multi-layer electrode (ZnS/Ag/MoO₃) was optimized by investigating the formation of a continuous Ag thin film according to the base layer. The aggregation of the Ag atom was strictly limited on the ZnS layer, which showed the best thermal stability for Ag. The thermally evaporated 7-nm-thick Ag film with surface coverage of 99.6% was achieved on the ZnS layer. We fabricated the ZnS (25 nm)/Ag (7 nm)/MoO₃ (5 nm) (Z25A7M5) multi-layer electrode, optimized through the numerical calculation. The transmittance of 83% at λ = 550 nm and sheet resistance of 9.6 Ohm/sq were recorded from the Z25A7M5 electrode. These results were mainly attributed to the uniform film-like morphology of the Ag thin film. The flexible OLEDs, based on the Z25A7M5 anode also showed feasible I–V–L characteristics compared to those of ITO-based devices.     

Correlation Between Structural and Optical Properties of Composite Polymer/Fullerene Films for Organic Solar Cells

We investigate thin poly(3‐hexylthiophene‐2,5‐diyl)/[6,6]‐phenyl C₆₁ butyric acid methyl ester (P3HT/PCBM) films, which are widely used as active layers in plastic solar cells. Their structural properties are studied by grazing‐incidence X‐ray diffraction (XRD). The size and the orientation of crystalline P3HT nanodomains within the films are determined. PCBM crystallites are not detected in thin films by XRD. Upon annealing, the P3HT crystallinity increases, leading to an increase in the optical absorption and spectral photocurrent in the low‐photon‐energy region. As a consequence, the efficiency of P3HT/PCBM solar cells is significantly increased. A direct relation between efficiency and P3HT crystallinity is demonstrated.     

Simple synthesis of solution-processable oxygen-enriched graphene as anode buffer layer for efficient organic solar cells

Interface material is a must for highly efficient and stable organic solar cells (OSCs) and has become a significant part of OSC research today. Here, low-cost and oxygen functionalized graphene (FG) was synthesized via a simple two-step method for applications in OSCs as anode buffer layer. The FG shows excellent dispersion in aqueous solution and great process compatibility with spin coating process. The introduction of work-function-tunable FG can effectively improve short current density of the devices. The power conversion efficiency of FG-based devices (4.13%, 4.49%, and 7.11% for P3HT:PC₆₁BM, P3HT:PC₇₁BM and PBDTTT-C:PC₇₁BM, respectively) outperforms PEDOT:PSS-based devices (3.67%, 4.17%, and 6.46%, respectively). Moreover, the stability of the devices was improved with FG as anode buffer layer compared to PEDOT:PSS. The results indicate that simple synthesized FG is a promising solution-processed anode buffer layer material for high-efficiency and stable OSCs.     

Inverted polymer solar cells with a solution-processed cesium halide interlayer

We demonstrate the utility of a low-cost cesium iodide interlayer spun from an aqueous or 2-ethoxyethanol solution on ITO in inverted polymer solar cells of the structure ITO/CsI/P3HT:PCBM/MoO₃/Al, where P3HT is poly(3-hexylthiophene) and PCBM is [6,6]-phenyl-C₆₀-butyric acid methyl ester. The power conversion efficiency (PCE) of optimized cells was ～3.4%, comparable to that we obtained for inverted cells with Cs carbonate. The thickness of the CsI film was adjusted by varying the solution concentration. The concentration affected the surface morphology of P3HT:PCBM and the density of fractal-like aggregates (possibly related to the presence of Cs and film fabrication conditions) formed near the anode, as revealed by scanning electron microscopy. Auger analysis indicated a P3HT-rich surface. Optimization of the cells was achieved also by varying the thickness of the MoO₃ and the drying/annealing conditions of the active layer, as was evident from the current–voltage characteristics, external quantum efficiency spectra, and PCE. The cells with the CsI interlayer were compared additionally to cells with CsCl or CsF interlayers (with a PCE of up to ～2.7%), which were inferior to the comparable cells with Cs₂CO₃ or CsI. The surface concentrations of Cs and the halide on ITO were monitored using X-ray photoelectron spectroscopy. The iodine level was low with the Cs:I ratio exceeding 8:1. In contrast, the Cs:Cl ratio was ～1.4:1 and the Cs:F ratio was ～1:1; the Cs₂CO₃ decomposed partially, as expected. Therefore, for CsI, as is the case for Cs₂CO₃ but not for CsF, Cs–O bonds are formed at the surface. Such bonds on ITO are important in modifying the ITO work function, improving the cell performance. The results indicate that spin coating solutions of the high polarity CsI is a promising and easy approach to introduce Cs–O on ITO in inverted structures for increased electron extraction from PCBM and possibly hole extraction from the P3HT-rich surface at the anode.     

Highly efficient ITO-free organic light-emitting diodes employing a roughened ultra-thin silver electrode

We investigated an efficient organic light-emitting diodes (OLEDs) using an ultra-thin silver (Ag) anode, whereas Ag was deposited on a roughened glass substrate by laser patterning method. The thin-film property of this roughened silver anode exhibited an optical transmittance of more than 65% in visible light at 532 nm and a low electrical sheet resistance of 3.2 Ω/sq, which is superior to standard indium-tin-oxide (ITO) glass. Therefore, we report an ITO-free, exciplex-forming phosphorescent OLED showing Lambertian emission with a luminance of 128,000 cd/m² at 8 V, and maximum current efficiency of 92.3 cd/A (external quantum efficiency of ∼24.5%) at 100 cd/m². We also observed the improvement in hole-injection efficiency at the interface of the Ag anode/di-[4-(N,N-ditolyl-amino)-phenyl]cyclohexane due to the modification in the worfunction of roughened Ag anode from 4.6 to 5.4 eV.     

Enhanced efficiency and brightness in organic light- emitting devices with MoO3 as hole-injection layer

The organic light-emitting devices (OLEDs) using 4,4’,4’’-tris{N-(3-methylphenyl)-N-phenylamin}triphenylamine (m-MTDATA) and MoO3 or 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-tetrachloride (TAPC) and MoO3 as the hole-injection layer (HIL) were fabricated. MoO3 can be expected to be a good injection layer material and thus enhance the emission performance of OLED. The highest occupied molecular (HOMO) of MoO3 is between those of m-MTDATA or TAPC and N,N’-bis-(1-naphthyl)-N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB), which reduces the hole-injection barrier and improves the luminance of the OLEDs. The current efficiency is improved compared with that of the device without the MoO3 layer. The highest luminous efficiency of the device with 2-nm-thick MoO3 as HIL is achieved as 5.27 cd/A at 10 V, which is nearly 1.2 times larger than that of the device without it. Moreover, the highest current efficiency and power efficiency of the device with the structure indium-tin oxide (ITO)/TAPC (40 nm)/MoO3 (2 nm)/TcTa:Ir(ppy)3 (10%, 10 nm)/ tris-(8-hydroxyquinoline) aluminium (Alq) (60 nm)/LiF (1 nm)/Al are achieved as 37.15 cd/A and 41.23 lm/W at 3.2 V and 2.8 V, respectively.     

In situ growth of columnar MoO3 buffer layer for organic photovoltaic applications

Columnar MoO₃ in situ growth prepared from direct converting soluble Mo-containing precursor during active layer thermal annealing was utilized as anode buffer layer to fabricate organic bulk heterojunction photovoltaics. The columnar morphology could improve the interface contact between active layer and buffer layer. The structure and phase of in situ formed MoO₃ were studied by X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). We demonstrated that the organic photovoltaic devices based on P3HT:PC₆₁BM using in situ formed columnar MoO₃ as anode buffer layer presented a high open-circuit voltage and fill factor leading to an efficiency of 3.92%, which is higher than the controlled PEDOT:PSS-based devices.     

Enhancement of the field-effect mobility of poly(3-hexylthiophene)/functionalized carbon nanotube hybrid transistors

With the aim of enhancing the field-effect mobility of poly(3-hexylthiophene) (P3HT) field-effect transistors (FETs), we added functionalized multiwalled carbon nanotubes (CNTs) to the P3HT solution prior to film formation. The nanotubes were found to be homogeneously dispersed in the P3HT films because of their functional groups. We found that at the appropriate CNT concentration (up to 10 wt% CNT), the P3HT FETs have a high field-effect mobility of 0.04 cm² V⁻¹ s⁻¹, which is an improvement by a factor of more than 10. This remarkable increase in the field-effect mobility over that of the pristine P3HT film is due to the high conductivity of the CNTs which act as conducting bridges between the crystalline regions of the P3HT film, and the reduction in the hole-injection barrier due to the low work function of CNTs, which results in more efficient carrier injection.     

Efficient Polymer Solar Cells Based on Poly(3‐hexylthiophene):Indene‐C70 Bisadduct with a MoO3 Buffer Layer

Polymer solar cells (PSCs) with poly(3‐hexylthiophene) (P3HT) as a donor, an indene‐C₇₀ bisadduct (IC₇₀BA) as an acceptor, a layer of indium tin oxide modified by MoO₃ as a positive electrode, and Ca/Al as a negative electrode are presented. The photovoltaic performance of the PSCs was optimized by controlling spin‐coating time (solvent annealing time) and thermal annealing, and the effect of the spin‐coating times on absorption spectra, X‐ray diffraction patterns, and transmission electron microscopy images of P3HT/IC₇₀BA blend films were systematically investigated. Optimized PSCs were obtained from P3HT/IC₇₀BA (1:1, w/w), which exhibited a high power conversion efficiency of 6.68%. The excellent performance of the PSCs is attributed to the higher crystallinity of P3HT and better a donor–acceptor interpenetrating network of the active layer prepared under the optimized conditions. In addition, PSCs with a poly(3,4‐ethylenedioxy‐thiophene):poly(styrenesulfonate) (PEDOT:PSS) buffer layer under the same optimized conditions showed a PCE of 6.20%. The results indicate that the MoO₃ buffer layer in the PSCs based on P3HT/IC₇₀BA is superior to that of the PEDOT:PSS buffer layer, not only showing a higher device stability but also resulting in a better photovoltaic performance of the PSCs.     

Incorporation of SiO2 dielectric nanoparticles for performance enhancement in P3HT:PCBM inverted organic solar cells

It is well known that organic solar cells (OSCs) with inverted geometry have not only demonstrated a better stability and longer device life time but also have shown improved power conversion efficiency (PCE). Recent studies exhibit that incorporation of metal and/or semiconducting nanoparticles (NPs) can further increase the PCE for OSCs. In this present work, we have synthesized SiO₂ NPs of various sizes (25, 50, 75 and 100 nm) using the modified Stober method and incorporated them into P3HT:PCBM photoactive layer and ZnO based electron transport layer (ETL) in order to investigate the light trapping effects in an OSC. Absorption studies have shown a considerable increase in photo absorption in both cases. The fabricated devices demonstrated 13% increase in the PCE when SiO₂ NPs are incorporated in P3HT:PCBM photoactive layer, whereas PCE was increased by 20% when SiO₂ NPs are incorporated in ZnO based ETL. Mott–Schottky analysis and impedance spectroscopy measurements have been carried out to determine the depletion width and global mobility for both the devices. The possible reason for PCE enhancement and the role of SiO₂ NPs in active layer and ZnO ETL are explained on the basis of the results obtained from Mott–Schottky analysis and impedance spectroscopy measurements.     

CdSe-sensitized inorganic–organic heterojunction solar cells: The effect of molecular dipole interface modification and surface passivation

CdSe-sensitized heterojunction solar cells composed of mesoscopic TiO₂/CdSe/P3HT (poly-3-hexylthiophene) were constructed, and the negative molecular dipole of 4-methoxybenzenethiol (MBT) and the ZnS passivation layer were used as interface modifiers to improve device performance. Through the interface modification between TiO₂/CdSe and P3HT using MBT and by ZnS surface passivation, the power conversion efficiency of the modified solar cell was greatly enhanced from 1.02% to 1.62% under 1 sun illumination.     

Electric-field controlled light-emissive characteristics in nanoscale for polymer/fullerene organic solar cells

Bulk-hetero-junction (BHJ) organic photovoltaic cells (OPVCs) consisting of a poly(3-hexylthiophene) (P3HT) as a donor and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) as an acceptor were fabricated and their light-emissive characteristics as a function of applied bias were investigated. The nanoscale luminescence spectra at different positions on the P3HT/PCBM based photovoltaic cells were measured using a laser confocal microscope (LCM) with a high spatial resolution. For the P3HT/PCBM OPVCs with a relatively thin active layer, the light-emissive characteristics were changed considerably with varying applied bias. We observed that the luminescence intensity increased with increasing reverse bias under light illumination, this result was confirmed by the LCM photoluminescence mapping images. This result originates from the increase of free charges due to the de-trapping effect of trapped charge transfer excitons near the interface, through the external electric-field and incident light.