A highly conductive PEDOT:PSS film with the dipping treatment by hydroiodic acid as anode for organic light emitting diode

A highly conductive, transparent and uniform poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) film has been developed by dipping treatment with hydriodic acid (HI) solution. The HI-treated PEDOT:PSS film can reach a sheet resistance of 68 Ω per square and a transmittance of 87% at 550 nm. The conductivity enhancement for the HI-treated film is ascribed to the permeation of proton and iodine anion of HI into PEDOT:PSS film, resulting in the separation of PSS and PEDOT chains. The phase separation of PSS and PEDOT can provide more conductive pathways for carriers to improve conductivity of the film. Using the optimized HI-treated PEDOT:PSS film as anode, we have fabricated indium tin oxide (ITO)-free organic light emitting diode (OLED), which shows better performance than the device with ITO as anode. This proves that such PEDOT:PSS film with the dipping treatment by HI solution is a promising alternative to ITO for low cost, transparent and flexible OLED application.     

Buffer and anode-integrated WO3-doped In2O3 electrodes for PEDOT:PSS-free organic photovoltaics

We developed PEDOT:PSS-free organic solar cells (OSCs) using WO₃ and In₂O₃ (IWO) mixed electrodes acting as a buffer hole injection layer (HIL) and anode simultaneously. Through the co-sputtering and rapid thermal annealing (RTA) of WO₃ and In₂O₃, we achieved buffer and anode-integrated transparent electrodes with a sheet resistance of 17 Ohm/square, a transmittance of 90.32%, and a work function of 4.83 eV, all of which are comparable to values obtained with a conventional ITO anode. Due to the existence of WO₃ in the In₂O₃ matrix, OSCs fabricated on an IWO electrode with no acidic PEDOT:PSS buffer layer showed a PCE of 2.87%. Therefore, a transparent IWO electrode simultaneously acting as an HIL and anode layer can be considered a promising transparent electrode for cost-efficient and reliable OSCs because it could eliminate the use of acidic PEDOT:PSS buffer layer.     

Properties of In2O3 films obtained by thermal oxidation of sprayed In2S3

In₂S₃ thin films were grown by the chemical spray pyrolysis (CSP) method using indium chloride and thiourea as precursors at a molar ratio of S:In=2.5. The deposition was carried out at 350 °C on quartz substrates. The film thickness is about 1 µm. The films were then annealed for 2 h at 550, 600, 650 and 700 °C in oxygen flow. This process allows the transformation of nanocrystal In₂O₃ from In₂S₃ and the reaction is complete at 600 °C. X-ray diffraction spectra show that In₂O₃ films are polycrystalline with a cubic phase and preferentially oriented towards (222). The film grain size increases from 19 to 25 nm and RMS values increase from 9 to 30 nm. In₂O₃ films exhibit transparency over 70–85% in the visible and infrared regions due to the thickness and crystalline properties of the films. The optical band gap is found to vary in the range 3.87–3.95 eV for direct transitions. Hall effect measurements at room temperature show that resistivity is decreased from 117 to 27 Ω cm. A carrier concentration of 1×10¹⁶ cm^?3 and mobility of about 117 cm² V^?1 s^?1 are obtained at 700 °C.     

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.     

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.     

Transparent and flexible amorphous InZnAlO films grown by roll-to-roll sputtering for acidic buffer-free flexible organic solar cells

We report on transparent and flexible amorphous In–Zn–Al–O (a-IZAO) films prepared by roll-to-roll (RTR) sputtering for use as anodes in acidic buffer free flexible organic solar cells (FOSCs). The presence of Zn and Al structural stabilizers in the In₂O₃ matrix produced a completely amorphous structure with the high optical transmittance of 89.25% and the low resistivity of 2.123 × 10⁻³ Ω-cm, as well as the high work function of 5.14 eV, making the a-IZAO films suitable for use as flexible anodes for FOSCs. In addition, the a-IZAO films showed no change in resistance (ΔR) during outer and inner bending fatigue tests due to their good mechanical flexibility. Relative to the power conversion efficiency (1.944%) of a PEDOT:PSS-based FOSCs, a FOSC fabricated by using an a-IZAO anode and without the use of acidic PEDOT:PSS buffer showed greater power conversion efficiency (2.509%), owing to the absence of interfacial reactions between the acidic PEDOT:PSS and the a-IZAO anode.     

Flexible organic light-emitting diodes on a polyestersulfone (PES) substrate using Al-doped ZnO anode grown by dual-plasma-enhanced metalorganic deposition system

This study proposes flexible organic light-emitting diodes (OLEDs) grown on polyestersulfone (PES) using Al-doped zinc oxide (AZO) as the anode, fabricated by the dual-plasma-enhanced chemical vapor deposition (DPEMOCVD) system. The experimental results including crystalline structure, optical, and electrical characteristics indicate that the quality of AZO films grown on PES depends on the deposition temperature and Al content. The optimal deposition temperature and Al content for AZO film are 185  C and 2.88 at%, respectively. Further increasing or decreasing the deposition temperature and Al content degrades the quality of AZO films. The optimal AZO film deposited on the PES substrate was used as the anode for flexible OLED. It shows a similar performance compared to OLEDs using commercial indium–tin-oxide (ITO) as the anode on glass, and represents enhanced characteristics to that of the commercial ITO anode on a flexible polyethylene naphthalate (PEN) substrate. This indicates that the DPEMOCVD-deposited AZO film on the PES substrate can be the anode for flexible OLEDs.     

Fourfold power efficiency improvement in organic light-emitting devices using an embedded nanocomposite scattering layer

It has been demonstrated that internal extraction structures (IES) can be introduced in OLEDs to decrease the ratio of the waveguide mode and simultaneously increase the ratios of the substrate and radiation modes. In this study, titanium oxide (TiO₂) nanoparticles (NPs) combined with transparent photoresist (TPR) were utilized to form an embedded nanocomposite scattering layer between the indium-tin-oxide (ITO) and glass substrate, leading to a significant boost in the out-coupling efficiency of the OLEDs. Inside the nanocomposite scattering layer, NPs of different sizes served distinct functions. The 250 nm-TiO₂ particles were used to induce scattering and diminish the light reflection back to the ITO layer. On the other hand, the refractive index of the TPR can be increased by increasing the concentration of the 25 nm-TiO₂, which reduced the difference in the refractive index between the ITO and TPR and thus multiplied the amount of light entering into the scattering layer. By employing nanocomposite substrate with mixed dual-sized NPs, we obtained power efficiencies of the blue phosphorescent OLEDs that were about 4.3 times higher than that of the control device at the high luminance of 5 × 10³ cd/m².     

Functionalized terfluorene for solution-processed high efficiency blue fluorescence OLED and electrophosphorescent devices

A new multifunctional blue-emitting terfluorene derivative (TFDPA) featured with triphenylamine groups for hole-transportation and long alkyl chains for solution processability on the conjugation inert bridge centers was reported. TFDPA can give homogeneous thin film by solution process and exhibits high hole mobility (μ_h ≈ 10^?3 cm² V^?1 s^?1) and suitable HOMO for hole injection. Particularly, TFDPA performs efficient deep-blue emission with high quantum yield (～100% in solution, 43% in thin film) and suitable triplet energy (E_T = 2.28 eV), making solution-processed OLED devices of using TFDPA as blue emitter and as host for iridium-containing phosphorescent dopants feasible. The solution-processed nondoped blue OLED device gives saturated deep-blue electroluminescence [CIE = (0.17, 0.07)] with EQE of 2.7%. TFDPA-hosted electrophosphorescent devices performed with EQE of 6.5% for yellow [(Bt)₂Ir(acac)], 9.3% of orange [Ir(2–phq)₃], and 6.9% of red [(Mpq)₂Ir(acac)], respectively. In addition, with careful control on the doping concentration of [(Bt)₂Ir(acac)], a solution-processed fluorescence–phosphorescence hybrided two-color-based WOLED with EQE of 3.6% and CIE coordinate of (0.38, 0.33) was successfully achieved.     

Repeatability of indium oxide gas sensors for detecting methane at low temperature

A simple method for fabricating methane gas sensor of indium oxide (In₂O₃) transparent film was presented. Indium of 3 mg as a raw material was used to direct deposition of In₂O₃ film through a simplified thermal evaporation method. X-ray diffraction confirmed the cubic polycrystalline structure of the as prepared In₂O₃ film. The transmittance (T) of the film was recorded as high as 96%. The optical band gap (E_g) of the deposited film was found of 3.68 eV. The sensing properties of In₂O₃ film toward methane gas (CH₄) were investigated at various operating temperatures and various gas concentrations. The prepared film highly detected CH₄ gas at concentrations much lower than the explosive limit. Good performance (sensor response and stability) of the film for CH₄ gas was exhibited. The film exhibited a good repeatability with repeating the gas sensing measurements towards CH₄.     

Electrodeposition of CuIn1−xGaxSe2 solar cells with a periodically-textured surface for efficient light collection

The photoresponse of CuIn_1?xGa_xSe₂ (CIGS) solar cells is improved using a periodically-textured structure as an antireflection layer. The CIGS absorber layers were prepared by one-step electrodeposition from an aqueous solution containing 12 mM CuSO₄, 25 mM In₂(SO₄)₃, 28 mM Ga₂(SO₄)₃, and 25 mM SeO₂. The electrodeposited CIGS films exhibit the (112)-preferred orientation of the chalcopyrite structures and feature improved film stoichiometry after the selenization process. In addition, the lower bandgap value of 0.97 eV is caused by the discrepancy of the reduction potentials for each constituent, resulting in insufficient Ga content in the deposited films. Using self-assembled silica nanoparticles as the etching mask, periodically-textured structures can be easily formed on an indium tin oxide (ITO)-coated soda lime glass to achieve a low average reflection (<10.5%) in a wide wavelength and incident angle range. With the periodic textured structures suppressing light reflections from the front surface, the photogenerated current in the semi-transparent CIGS solar cells made with transparent conducting electrodes is 1.82 times higher than they otherwise would be.     

Fine tuning hole injection for high-performance polyfluorene-based blue emitting device by adjusting work function of anode via deposition of CFx layer with proper ionization potential on indium tin oxide

By introducing CF_x thin film as hole injection layer on top of indium tin oxide (ITO) anode via plasma polymerization of CHF₃, the device with poly(9,9-dioctylfluorene) (PFO) as emitting layer, ITO/CF_x(35 W)/PFO/CsF/Ca/Al, is prepared. At the optimal C/F atom ratio using the radio frequency power 35 W, the device performance is optimal having the maximum current efficiency 3.1 cd/A and maximum brightness 8400 cd/m². This is attributed to a better balance between hole and electron fluxes, resulting from a decrease in hole injection barrier as manifested by ultraviolet photoelectron spectroscopy and scanning surface potential microscopy.     

Characterization of solution processed,p-doped films using hole-only devices and organic field-effect transistors

We report a solution processed, p-doped film consisting of the organic materials 4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (MTDATA) as the electron donor and 2-(3-(adamantan-1-yl)propyl)-3,5,6-trifluorotetracyanoquinodimethane (F3TCNQ-Adl) as the electron acceptor. UV–vis–NIR absorption spectra identified the presence of a charge transfer complex between the donor and acceptor in the doped films. Field-effect transistors were used to characterize charge transport properties of the films, yielding mobility values. Upon doping, mobility increased and then slightly decreased while carrier concentration increased by two orders of magnitude, which in tandem leads to conductivity increasing from 4 × 10^?10 S/cm when undoped to 2 × 10^?7 S/cm at 30 mol% F3TCNQ-Adl. The hole density was calculated based on mobility values extracted from OFET data and conductivity values extracted from bulk I–V data for the MTDATA: x mol% F3TCNQ-Sdl films. These films were then shown to function as the hole injection/hole transport layer in a phosphorescent blue OLED.     

Electrical and optical characteristics of phosphorescent organic light-emitting device with thin-codoped layer insertion

In this paper, we demonstrated the changes of electrical and optical characteristics of a phosphorescent organic light-emitting device (OLED) with tris(phenylpyridine)iridium Ir(ppy)₃ thin layer (4 nm) slightly codoped (1%) inside the emitting layer (EML) close to the cathode side. Such a thin layer helped for electron injection and transport from the electron transporting layer into the EML, which reduced the driving voltage (0.40 V at 100 mA/cm²). Electroluminescence (EL) spectral shift at different driving voltage was observed in our blue OLED with [(4,6-di-fluoropheny)-pyridinato-N,C^2′]picolinate (FIrpic) emitter, which came from the recombination zone shift. With the incorporation of thin-codoped Ir(ppy)₃, such EL spectral shift was almost undetectable (color coordinate shift (0.000, 0.001) from 100 to 10,000 cd/m²), due to the compensation of Ir(ppy)₃ emission at low driving voltage. Such a methodology can be applied to a white OLED which stabilized the EL spectrum and the color coordinates ((0.012, 0.002) from 100 to 10,000 cd/m²).     

A low drive voltage,transparent, metal-free n–i–p electrophosphorescent light emitting diode

We demonstrate a transparent, inverted, electrophosphorescent n–i–p organic light emitting diode (OLED) exhibiting a luminance of 500 cd/m² at 3.1 V, and with a luminous power efficiency of 23 lm/W when light emitted from both top and bottom surfaces is summed. We find that 10% more light is emitted from the top surface; hence a power efficiency of 12 lm/W is obtained for a device viewed through the top, transparent contact. This device, with applications to head-up and displays employing n-type Si driver circuitry, has significantly higher power efficiency and lower drive voltage than undoped fluorescent inverted OLEDs. Efficient injection of both electrons and holes is made possible by controlled n- and p-doping of the transport layers with high doping levels. The light emitting region is protected from ITO sputtering damage by a 210 nm thick p-doped hole transport layer. The transparency of the device at the peak OLED emission wavelength of 510 nm is (80 ± 5)%.     

Optoelectronic characteristics of MEH-PPV polymer LEDs with thin,doped composition-graded a-SiC:H carrier injection layers

The optoelectronic characteristics of poly(2-methoxy-5-(2′ethyl-hexoxy)-1,4-phenylene-vinylene) (MEH-PPV) polymer LEDs (PLEDs) have been improved by employing thin doped composition-graded (CG) hydrogenated amorphous silicon–carbide (a-SiC:H) films as carrier injection layers and O₂-plasma treatment on indium–tin-oxide (ITO) transparent electrode, as compared with previously reported ones having doped constant-optical-gap a-SiC:H carrier injection layers. For PLEDs with an n-type a-SiC:H electron injection layer (EIL) only, the electroluminescence (EL) threshold voltage and brightness were improved from 7.3 V, 3162 cd/m² to 6.3 V, 5829 cd/m² (at a current density J = 0.6 A/cm²), respectively, by using the CG technique. The enhancement of EL performance of the CG technique was due to the increased electron injection efficiency resulting from a smoother barrier and reduced recombination of charge carriers at the EIL and MEH-PPV interface. Also, surface modification of the ITO transparent electrode by O₂-plasma treatment was used to further improve the EL threshold voltage and brightness of this PLED to 5.1 V, 6250 cd/m² (at J = 0.6 A/cm²). Furthermore, by employing the CG n[p]-a-SiC:H film as EIL [hole injection layer (HIL)] and O₂-plasma treatment on the ITO electrode, the brightness of PLEDs could be enhanced to 9350 cd/m² (at a J = 0.3 A/cm²), as compared with the 6450 cd/m² obtained from a previously reported PLED with a constant-optical-gap n-a-SiCGe:H EIL and p-a-Si:H HIL.     

Organic/metal hybrid cathode for transparent organic light-emitting diodes

We report a highly transparent organic/metal hybrid cathode of a Cs-doped electron transport layer (Cs-ETL)/Ag for transparent organic light-emitting diode (TOLED) applications. Particular attention is paid to the surface morphology on the Ag film and its influence on the optical transparency and electrical conductivity. With the use of Cs-ETL, a smooth and continuous surface morphology of Ag film was achieved, leading to a high transmittance of ～75% in TOLED with a low sheet resistance of 4.5 Ω/Sq in cathode film. We successfully applied our Cs-ETL/Ag transparent cathode to fabricate highly transparent OLEDs. Our approach suggests a new electrode structure for transparent OLED applications.     

Effect of thickness on the structural,optical and electrical properties of RF magnetron sputtered GZO thin films

Gallium-doped zinc oxide (GZO) thin films with very high conductivity and transparency were successfully deposited by RF magnetron sputtering at a substrate temperature of 400 °C. The dependence of the film properties over the thickness was investigated. X-ray diffraction (XRD) results revealed the polycrystalline nature of the films with hexagonal wurtzite structure having preferential orientation along [001] direction normal to the substrate. The lowest resistivity obtained from electrical studies was 5.4×10⁻⁴ Ω cm. The optical properties were studied using a UV–vis spectrophotometer and the average transmittance in the visible region (400–700 nm) was found to be 92%, relative to the transmittance of a soda–lime glass reference for a GZO film of thickness 495 nm and also the transparency of the films decreases in the near IR region of the spectra. The mobility of the films showed a linear dependence with crystallite size. GZO film of thickness 495 nm with the highest figure of merit indicates that the GZO film is suitable as an ideal transparent conducting oxide (TCO) material for solar cell applications.     

Low and small resistance hole-injection barrier for NPB realized by wide-gap p-type degenerate semiconductor,LaCuOSe:Mg

LaCuOSe:Mg is a wide-gap p-type semiconductor with a high conductivity and a large work function. Potential of LaCuOSe:Mg as a transparent hole-injection electrode of organic light-emitting diodes (OLEDs) was examined by employing N,N′-diphenyl-N,N′-bis (1,1′-biphenyl)-4,4′-diamine (NPB) for a hole transport layer. Photoemission spectroscopy revealed that an oxygen plasma treated surface of LaCuOSe:Mg formed a hole-injection barrier as low as 0.3 eV, which is approximately a half of a conventional ITO/NPB interface. Hole-only devices composed of a LaCuOSe:Mg/NPB/Al structure showed a low threshold voltage ∼0.2 V and high-density current drivability of 250 mA cm⁻² at 2 V, which is larger by two orders of magnitude than that of ITO/NPB/Al devices. These results demonstrate that LaCuOSe:Mg has great potential as an efficient transparent anode for OLEDs and other organic electronic devices.     

Thin film encapsulation for organic light emitting diodes using a multi-barrier composed of MgO prepared by atomic layer deposition and hybrid materials

We demonstrated an organic/inorganic multi-barrier and encapsulation for flexible OLED devices. The multi-barrier consisted of a silica nanoparticle-embedded hybrid nanocomposite, in short, S-H nanocomposite, and MgO, which were used as organic and inorganic materials, respectively. The S-H nanocomposite was spin-coated followed by UV curing. The thickness of the S-H nanocomposite was 200 nm, and 40 nm of MgO was deposited by atomic layer deposition (ALD) using Mg(CpEt)₂ and H₂O at 70 °C. The results of a Ca test showed that the 4.5 dyads of the MgO/S-H nanocomposite had a low water vapor transmission rate (WVTR) of 4.33 × 10^?6 g/m²/day and an optical transmittance of 84%. The normalized luminance degradation of the thin film encapsulated OLED was also identical to that of glass-lid encapsulation after 1000 h of the real operation time. We proposed low temperature ALD as a deposition method to create relatively thin film for OLED passivation without degradation, such as creation of dark spots. The results confirmed that it may be feasible for our multi-barrier to passivate flexible OLEDs devices.