Top illuminated organic photodetectors with dielectric/metal/dielectric transparent anode

The top illuminated organic photodetectors (OPDs) with a Dielectric/Metal/Dielectric (DMD) transparent anode are fabricated. The transparent electrode is composed of molybdenum trioxide (MoO₃)/silver (Ag)/MoO₃ layers and zinc oxide (ZnO)/aluminum (Al) is used for bottom cathode. The optimized DMD electrode has an optical transmittance of 85.7% at the wavelength of 546 nm and sheet resistance of ∼6 Ω/sq. The fabricated OPDs exhibit a high detectivity and wide range linearity.     

Low resistive transparent and flexible ZnO/Ag/ZnO/Ag/WO3 electrode for organic light-emitting diodes

Transparent electrodes cannot easily be created with high transmittance and low sheet resistance simultaneously, although some optoelectronic devices, such as large organic light-emitting diode (OLED) displays and lightings, require very low resistive transparent electrodes. Here, we propose a very low resistive transparent electrode (～1.6 Ω/sq) with a high transmittance (～75%) for OLED devices, the transmittance level of which represents the highest reported value to date given such a low sheet resistance level. It consists of a stacked silver (Ag)/zinc oxide (ZnO)/Ag multilayer covered by high refractive index dielectric layers. The proposed multilayer electrode with optimal layer thicknesses has a high and wide spectral transmittance peak due to interference. The low sheet resistance is a result of two Ag layers connected via the sandwiched ZnO layer. In addition to its low sheet resistance coupled with high transmittance, the proposed multilayer electrode has good flexibility. An OLED with an anode of the stacked Ag/ZnO/Ag multilayer shows performance comparable to that of an anode of indium tin oxide.     

Solution-processed annealing-free ZnO nanoparticles for stable inverted organic solar cells

We report the development and application of high-quality zinc oxide nanoparticles (ZnO NPs) processed in air for stable inverted bulk heterojunction solar cells as an electron extraction layer (EEL). The ZnO NPs (average size ∼11 nm) were dispersed in chloroform and stabilized by propylamine (PA). We demonstrated that the ZnO NP dispersion with 4 vol.% of PA as stabilizer can be used in air directly and remains clear up to one month after preparation. Our inverted solar cells consisted of a blade-coated poly(N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole (PCDTBT) and [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) (1: 4 by weight) active layer sandwiched between a ZnO electron extraction layer and a MoO₃/Ag anode. All solar cells with ZnO films fabricated in air using PA-stabilized ZnO dispersions prepared within a time window of one month exhibited power conversion efficiencies (PCE) above 4%. In contrast, if the ZnO film was prepared in air using regular un-stabilized ZnO NP dispersion, the PCE would drop to 0.2% due to poor film quality. More interestingly, X-ray photoelectron spectroscopy and nuclear magnetic resonance measurements indicated that the PA ligands were not covalently bonded to ZnO NPs and did not exist in the deposited ZnO films. The spin-cast ZnO thin films (without any thermal treatment) are insoluble in organic solvents and can be directly used as an EEL in solar cells. This feature is beneficial for fabricating organic solar cells on flexible polymer substrates. More importantly, our non-encapsulated inverted solar cells are highly stable with their PCEs remaining unchanged after being stored in air for 50 days.     

Transparent Al/WO3/Au film as anode for high efficiency organic light-emitting diodes

A transparent Al/WO₃/Au anode is introduced to fabricate high efficiency organic light-emitting devices (OLEDs). By optimizing the thicknesses of each layers of the Al/WO₃/Au structure, the transmittance of Al(7 nm)/WO₃(3 nm)/Au(13 nm) has reached over 55%. Concerning the performance of OLEDs using the optimized anode, the electroluminescence (EL) current efficiency and brightness are enhanced and the EL spectrum is greatly narrowed as compared to the OLEDs using indium-tin-oxide (ITO) as the anode. The results indicate that the metal/metal oxide/metal transparent electrode is a good structure for the anode of high performance OLEDs. In addition, Al/WO₃/Au can function as a composite transparent electrode for top-emitting OLEDs.     

Highly efficient green top-emitting organic light-emitting devices with metal electrode structure

In this work, the electrical and optical characteristics of top-emitting organic light-emitting device (TEOLED) using metal Ag as anode with different thicknesses have been investigated. The emission peak of fabricated TEOLED is 512 nm for a full-width at half-maximum (FWHM) of 48 nm in forward direction. The TEOLED turns on at 3 V with luminance of 2.38 cd/m² and reaches 16,300 cd/m² at 9 V. The maximum of current efficiency is 5.2 cd/A at 7 V, corresponding to the external quantum efficiency of 1.72%.     

Colored reflective organic light-emitting device without bias

Under white ambient illumination and without bias, a reflective organic light-emitting device (ROLED) comprising a microcavity cathode exhibited various colors for static information display applications by means of internal interference and absorption effects. The configuration of this microcavity cathode was a metal/organometallic/metal structure of Al (10 nm)/Ag (15 nm)/Ag nanoparticles doped inside tris(8-hydroxyquinolinato) aluminum (Alq₃) (x nm)/Al (100 nm) with excellent conductivity. The thickness of the Ag:Alq₃ played a crucial role in determining the reflection color; for example, varying it from 20, 40, 60, 80 and 100 nm yielded the colors light yellow, light orange, reddish purple, greenish blue, and light green, respectively. In the dark, this ROLED can be used to display information with an ultra-high contrast ratio by applying on a small bias, like conventional OLED displays. Hence, this ROLED is a highly promising candidate for applications in energy-saving electronic fixed-pattern signs, logos, indicators, and manual information displays.     

Color-saturated and angle-stable blue top-emitting organic light-emitting diodes based on semitransparent bilayer cathode: Theory and experiment

Based on a modified electromagnetic theory, a bilayer metal cathode consisting of an electron injection layer and a silver (Ag) layer is designed to improve the color chromaticity in blue top-emitting organic light-emitting diodes (TEOLEDs). The effects of the complex refractive index of the electron injection material on the reflectivity and transmittivity of the bilayer cathode are investigated in detail, and then samarium (Sm) is selected as the electron injection material due to its proper refractive index of ～1.22 + 1.12i and work function of ～2.7 eV. Then, the emission peak wavelength, the full width at half maximum, and the Commission International de L’Eclairage coordinates of the blue TEOLEDs with different Sm/Ag bilayer cathodes are calculated and discussed. According to the theoretical results, a blue TEOLED with the optimized bilayer cathode of Sm (15 nm)/Ag (5 nm) is fabricated. The measurement results indicate that the blue TEOLED possesses an excellent chromaticity which is even better than that of a bottom-emitting organic light-emitting diode. Besides, the excellent angle stability is observed in the blue TEOLED even with a large viewing angle change of 0–75°.     

Fabrication of Ag nanoparticle/ZnO thin films using dual-plasma-enhanced metal-organic chemical vapor deposition (DPEMOCVD) system incorporated with photoreduction method and its application

We report a novel method to grow silver nanoparticle/zinc oxide (Ag NP/ZnO) thin films using a dual-plasma-enhanced metal-organic chemical vapor deposition (DPEMOCVD) system incorporated with a photoreduction method. The crystalline quality, optical properties, and electrical characteristics of Ag NP/ZnO thin films depend on the AgNO₃ concentration or Ag content and annealing temperature. Optimal Ag NP/ZnO thin films have been grown with a AgNO₃ concentration of 0.12 M or 2.54 at%- Ag content and 500 °C- rapid thermal annealing (RTA); these films show orientation peaks of hexagonal-wurtzite-structured ZnO (002) and face-center-cubic-crystalline Ag (111), respectively. The transmittance and resistivity for optimal Ag NP/ZnO thin films are 85% and 6.9×10⁻⁴ Ω cm. Some Ag NP/ZnO transparent conducting oxide (TCO) films were applied to InGaN/GaN LEDs as transparent conductive layers. The InGaN/GaN LEDs with optimal Ag NP/ZnO TCO films showed electric and optical performance levels similar to those of devices fabricated with indium tin oxide.     

Electrical and thermal stability of Ag ohmic contacts for GaN-based flip-chip light-emitting diodes by using an AgAl alloy capping layer

We have investigated Ag(200 nm)/AgAl(100 nm) ohmic contacts to p-type GaN for near-UV (405 nm) flip-chip light-emitting diodes (LEDs). It is shown that the use of an AgAl alloy capping layer (with 8 at% Al) results in better electrical and optical properties as compared to single Ag contacts when annealed at 430 °C. For example, Ag/AgAl (8 at% Al) contacts give specific contact resistance of 4.6×10^–4 Ω cm² and reflectance of 90% at a wavelength of 405 nm. However, use of an AgAl (with 50 at% Al) layer is not effective. LEDs fabricated with the Ag/AgAl (8 at% Al) reflectors produce higher light output as compared with the ones with single Ag reflectors. Ohmic mechanisms of the Ag/AgAl (8 at% Al) contacts are described and discussed.     

Comparison of the photocatalytic degradation of trypan blue by undoped and silver-doped zinc oxide nanoparticles

Zinc oxide (ZnO) and silver doped zinc oxide (ZnO:Ag) nanoparticles were prepared using nitrates of zinc and silver as oxidizers and ethylene diaminetetraacetic acid (EDTA) as a fuel via low-temperature combustion synthesis (LCS) at 500 °C. X-ray diffraction (XRD) pattern indicates the presence of silver in the hexagonal wurtzite structure of ZnO. Fourier transform infrared (FTIR) spectrum indicates the presence of Ag–Zn–O stretching vibration at 510 cm⁻¹. Transmission electron microscopy (TEM) images shows that the average particle size of ZnO and ZnO:Ag nanoparticles were found to be 58 nm and 52 nm, respectively. X-ray photoelectron spectroscopy (XPS) data clearly indicates the presence of Ag in ZnO crystal lattice. The above characterization techniques indicate that the incorporation of silver affects the structural and optical properties of ZnO nanoparticles. ZnO:Ag nanoparticles exhibited 3% higher photocatalytic efficiency than pure ZnO nanoparticles. ZnO:Ag nanoparticles show better photocatalytic activity for the degradation of trypan blue (TrB) compared to undoped ZnO nanoparticles.     

Bright and efficient white stacked organic light-emitting diodes

High brightness and efficient white stacked organic light-emitting diodes have been fabricated by connecting individual blue and red emissive units with the anode–cathode layer (ACL) consisting of LiF (1 nm)/Ca (25 nm)/Ag (15 nm). Use 1,3-bis(carbazol-9-yl)benzene (mCP):bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl) iridium III (FirPic) as the blue emitter and tris(8-hydroxy-quinolinato)aluminium (Alq₃):4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran (DCJTB) as the red emitter, white light emission with CIE coordinates of (0.32, 0.38) was obtained at a driving voltage of 26 V with a luminance of 40,000 cd/m². By replacing the red fluorescent emitter with a phosphorescent one, the color coordinates were improved to (0.33, 0.31). The peak external quantum efficiency was enhanced from 5.3% (at 28.2 mA/cm²) to 10.5% (at 1.4 mA/cm²) as well.     

High-performance inverted top-emitting green electrophosphorescent organic light-emitting diodes with a modified top Ag anode

Green electrophosphorescent inverted top-emitting organic light-emitting diodes with a Ag/1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile (HAT-CN) anode are demonstrated. A high current efficacy of 124.7 cd/A is achieved at a luminance of 100 cd/m² when an optical outcoupling layer of N,N′-di-[(1-naphthyl)-N,N′-diphenyl]-1,1′-biphenyl-4,4′-diamine (α-NPD) is deposited on the anode. The devices have a low turn-on voltage of 3.0 V and exhibit low current efficacy roll-off through luminance values up to 10,000 cd/m². The angle dependent spectra show deviation from Lambertian emission and color change with viewing angle. Hole-dominated devices with Ag/HAT-CN electrodes show current densities up to three orders of magnitude higher than devices without HAT-CN.     

Fluorene trimers with various 9,9′-substituents: The synthesis,characteristics, condensed state structures,and electroluminescence properties

The four fluorene-based trimers with various aromatic and alkyl substituents (T1–T4) are synthesized and characterized. These oligomers show the similar electronic absorption and emission characteristics (e.g., absorption peak at 351 nm, and highly efficient deep blue emission at 394 nm in solution), indicating that the major electronic properties of the core chromophore are essentially independent of the substituents. However, the condensed state structures and thermal properties of four trimers are found to be different from each other, from crystalline (full alkyl (T1) or full aromatic (T2) substituted trimers) to amorphous (mixed aromatic and alkyl (T4) substituted trimers). The effect of different condensed state structures on electroluminescence device properties is presented: The blue light-emitting devices with accordant structure of ITO/PEDOT:PSS/TCTA (40 nm)/trimers (40 nm)/BCP (10 nm)/Alq₃ (20 nm)/LiF/Al exhibit different EL efficiency (2.9% of T2, 1.8% of T3 and 2.7% of T4). Using amorphous T4, the white light-emitting device of ITO/TCTA (40 nm)/rubrene (0.1 nm)/T4 (8 nm)/Alq₃(52 nm)/LiF/Al is fabricated with high efficiency (6.15 cd A⁻¹), high brightness (9500 cd m⁻²) and good white light CIE coordinates (0.32, 0.37).     

Highly efficient and high transmittance semitransparent polymer solar cells with one-dimensional photonic crystals as distributed Bragg reflectors

We demonstrate that one-dimensional photonic crystals as distributed Bragg reflectors can effectively improve the performance of semitransparent polymer solar cells (PSCs) based on the blend of P3HT:ICBA. The one dimensional distributed Bragg reflectors (1D DBRs) are composed of N pairs of WO₃/LiF which are thermally evaporated on Ag anode. Due to its photonic bandgap, 1D DBRs can reflect the light totally back into the PSCs when the high reflectance range of 1D DBRs is well matched with absorption spectrum of the active layer. A maximum power conversion efficiency (PCE) of 4.12%, a highest transmittance of 80.4% at 660 nm and an average transmittance of 55.6% in the wavelength range of 600–800 nm are obtained in the case of N = 8, corresponding enhancement of 24.1% in PCE when compared with the device without the 1D DBRs.     

Tin naphthalocyanine complexes for infrared absorption in organic photovoltaic cells

In this work, we examine the optical properties of tin naphthalocyanine dichloride (SnNcCl₂), and its performance as an electron donor material in organic photovoltaic cells (OPVs). As an active material, SnNcCl₂ is attractive for its narrow energy gap which facilitates optical absorption past a wavelength of λ = 1100 nm. We demonstrate a power conversion efficiency of η_P = (1.2 ± 0.1)% under simulated AM1.5G solar illumination at 100 mW/cm² using the electron donor–acceptor pairing of SnNcCl₂ and C₆₀ in a bilayer device architecture. While some phthalocyanines have been previously used to improve infrared absorption, this is often realized through the formation of molecular dimers. In SnNcCl₂, the infrared absorption is intrinsic to the molecule, arising as a result of the extended conjugation. Consequently, it is expected that SnNcCl₂ could be utilized in bulk heterojunction OPVs without sacrificing infrared absorption.     

Influence of cathode roughness on the performance of F8BT based organic–inorganic light emitting diodes

Hybrid light emitting diodes (HyLED) with a structure of FTO/ZnO/F8BT/MoO₃/Au/Ag is fabricated and the influence of surface roughness of cathode (FTO/ZnO) is investigated. The roughness of FTO could be decreased from 9.2 nm to 2.2 nm using a mild polishing process. The ZnO film, deposited by spray pyrolysis, functions as an electron injection layer. The roughness of the FTO/ZnO surface is found also highly dependent on the ZnO thickness. For thin ZnO films (20 nm), polishing results in better efficacy and power efficiency of LED devices, with nearly a two times improvement. For thick ZnO films (210 nm), the overall FTO/ZnO roughness is almost independent of the FTO roughness, hence both polished and unpolished substrates exhibit identical performance. Increasing ZnO thickness generally improves the electron injection condition, leading to lower turn on voltage and higher current and power efficiencies. However, for too large ZnO thickness (210 nm) the ohmic loss across the film dominates and deteriorates the performance. While the polished substrates show less device sensitivity to ZnO thickness and better performance at thin ZnO layer, best performance is obtained for unpolished substrates with 110 nm ZnO thickness. Larger interface area of ZnO/F8BT and enhanced electric filed at sharp peaks/valleys could be the reason for better performance of devices with unpolished substrates.     

Uniform 3D hydrothermally deposited zinc oxide nanorods with high haze ratio

We present low cost hydrothermally deposited uniform zinc oxide (ZnO) nanorods with high haze ratios for the a-Si thin film solar cells. The problem of low transmittance and conductivity of hydrothermally deposited ZnO nanorods was overcome by using RF magnetron sputtered aluminum doped zinc oxide (ZnO:Al ~300 nm) films as a seed layer. The length and diameters of the ZnO nanorods were controlled by varying growth times from 1 to 4 h. The length of the ZnO nanorods was varied from 1 to 1.5 µm, while the diameter was kept larger than 300 nm to obtain various aspect ratios. The uniform ZnO nanorods showed higher transmittance (~89.07%) and haze ratio in the visible wavelength region. We also observed that the large diameters (>300 nm) and average aspect ratio (3–4) of ZnO nanorods favored the light scattering in the longer wavelength region. Therefore, we proposed uniformly deposited ZnO nanorods with high haze ratio for the future low cost and large area amorphous silicon thin film solar cells.     

MoO3/Au/MoO3–PEDOT:PSS multilayer electrodes for ITO-free organic solar cells

The effect of the MoO₃–PEDOT:PSS composite layer in the MoO₃/Au/MoO₃–PEDOT:PSS multilayer electrode on the power conversion efficiency of ITO-free organic solar cells (OSCs) was evaluated. The MoO₃ (30 nm)/Au(12 nm)/MoO₃–PEDOT:PSS (30 nm)/PEDOT:PSS structure showed ~7% more optical transmittance than the MoO₃ (30 nm)/Au (12 nm)/MoO₃(30 nm)/PEDOT:PSS structure at 550 nm wavelength. The OSCs using MoO₃/Au/MoO₃–PEDOT:PSS multilayer electrodes as anodes showed a considerable improvement in power conversion efficiency (PCE), from 1.84% to 2.81%, comparable to ITO based OSCs with PCE of 2.89%. This improvement is attributed to the suppression of MoO₃ dissolution by the acidic hole transport layer (HTL) PEDOT:PSS on the MoO₃/Au/MoO₃–PEDOT:PSS multilayer electrode, resulting in high J_sc, V_oc and FF of the OSCs. This composite based multilayer electrode was shown to be a promising replacement in ITO-free flexible optoelectronic devices.     

Interfacial layer material derived from dialkylviologen and sol–gel chemistry for polymer solar cells

Sol–gel processible organosilicate material based on dialkylviologen (1,1-(bis-trimethoxysilane)-[4,4′]bipyridium dibromide (bis-trimethoxypropylsilane)-yl-viologen, PV-Si) was synthesized and used as an interfacial layer material for polymer solar cells based on poly(3-hexylthiophene): [6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM). PV-Si is very good soluble in polar protic solvents because of two pyrinium bromide salts and PV-Si pre-polymer can be easily prepared by sol–gel chemistry under the mild acidic conditions. From the ultraviolet spectroscopy (UPS) study, the reduction of the work function of Al and ITO is observed by the formation of interface dipole, which is induced by the thin film of thermally cured PV-Si pre-polymer (cPV-Si) at 180 °C. The open circuit voltage (V_oc) of conventional type polymer solar cell (CPSC) with a structure of ITO/active layer (P3HT:PCBM)/cPV-Si(<5 nm)/Al is 0.58 V, which is higher than the CPSC without cPV-Si (0.55 V). This indicates that the favorable interface dipole is generated by the thin film of cPV-Si. Besides, the power conversion efficiency (PCE) of CPSC with cPV-Si reaches at 2.90%, which is higher than that of the device without cPV-Si (2.69%). Surprisingly, the PCE and the short circuit current (J_sc) of inverted type polymer solar cell (IPSC) with a structure of ITO/cPV-Si (<5 nm)/active layer/WO₃/Ag are 2.83% and ?9.19 mA/cm², respectively, which are higher than those of the device with ZnO (2.51% and ?8.63 mA/cm²) as an electron transporting/injecting layer. This is due to that the work function of ITO is also reduced by the formation of interface dipole. The IPSC with cPV-Si as an interfacial layer (IFL) shows very good rectification and a contact property as well. From the results, the thin layer of cPV-Si is potential material for an IFL for either CPSC or IPSC. Especially, ZnO can be replaced by cPV-Si because of their improved device performances and pretty low processing temperature.     

Effect of pH on the properties of electrochemically prepared ZnO thin films

Zinc Oxide (ZnO) thin films have been electrochemically deposited on fluorine doped tin oxide (FTO) coated glass substrates from an aqueous electrolyte. Deposition potential −0.96 V was optimized by cyclic voltammetry experiment for slow scan rate 5 mV/s with moderate agitation of electrolyte. The effect of pH on the electrodeposition of ZnO is studied by cyclic voltammetry, X-ray diffraction (XRD), scanning electron microscopy (SEM), optical spectroscopy and photoelectrochemical I-t transient characteristics. It is revealed that the pH of the electrolyte has significant influence on the surface morphology and structural properties. Highly crystalline ZnO layers with hexagonal crystal structure deposited for all pH of the solutions. A systematic shift observed in the reflections (002) and (101) is correlated with an effective tensile strain developed in the crystal lattice. A remarkable improvement in the crystallinity was noticed in the as-deposited ZnO samples with increasing pH and upon heat treatment. Optical direct band gap ~ 3.26–3.33 eV and transmittance ~70 −80% was measured by optical spectroscopy. PL measurement showed the band edge emission at 375–382 nm and a visible light emission at 410–550 nm. The intensities of emission peaks are found to be affected by the pH of bath. The compact, densely packed and well adherent thin films of ZnO electrodeposited in zinc nitrate bath for pH 2.0, 3.5 and 6.0. The surface morphology has been changed from granular to disc shaped and finally a large hexagonal sheets were obtained with an increase in the pH of bath. Nearly stoichiometric ZnO thin films are electrodeposited at −0.96 V versus Ag/AgCl reference electrode for pH 6.0. The photoelectrochemical (PEC) measurement (I-t transient curve) shows the enhancement in photocurrent with increasing the pH of zinc nitrate solution. After heat treatment the photocurrent is increased by 54%, 98% and 130% in the samples deposited from 2.0, 3.5 and 6.0 pH of the bath. I-V measurements were further confirmed the current enhancement in all samples after heat treatment.