Energy level alignment and morphology of interfaces between molecular and polymeric organic semiconductors

Ultraviolet photoelectron spectroscopy (UPS) was used to determine the energy level alignment at organic–organic conductor–semiconductor and semiconductor–semiconductor hetero-interfaces that are relevant for organic optoelectronic devices. Such interfaces were formed by in situ vacuum sublimation of small molecular materials [C₆₀ and pentacene (PEN)] and ex situ spin-coating of poly(3-hexylthiophene) (P3HT), all on the common substrate poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS). We found that the deposition sequence had a significant impact on the interface energetics. The hole injection barrier (HIB) of C₆₀ on PEDOT:PSS could be changed from 1.0 eV (moderate hole injection) to 1.7 eV (good electron injection) by introducing a layer of P3HT. The HIB of P3HT/PEDOT:PSS was increased by 0.35 eV due to an interfacial PEN layer. However, PEN deposited on PEDOT:PSS and P3HT/PEDOT:PSS exhibited the same value. These observations are explained by material-dependent dipoles at the interfaces towards PEDOT:PSS and substrate dependent inter-molecular conformation.     

Composite film of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and MoO3 as an efficient hole injection layer for polymer light-emitting diodes

We demonstrate improved performances in polymer light-emitting diodes (PLEDs) using a composite film of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and MoO₃ powder as a hole injection layer. The PLED with the composite film exhibits the current efficiency of 13.5 cd/A, driving voltage of 3.4 V, and half lifetime of 108.1 h, while those values of the PLED with a pristine PEDOT:PSS was 11.3 cd/A, 3.8 V, and 41.5 h, respectively. We also analyze the morphological, optical and electrical properties of the composite films by atomic force microscopy (AFM), UV–Vis-IR absorption, and ultraviolet photoemission spectroscopy (UPS). This work suggests that mixing MoO₃ into PEDOT:PSS is a simple and promising technique for use solution-based devices as an hole injection layer.     

Ultraviolet photodetectors based on low temperature processed ZnO/PEDOT:PSS Schottky barrier diodes

In this work, vertical Schottky barrier diodes (SBDs) were fabricated using a thin film of ZnO (50 nm) and PEDOT:PSS deposited by RF Sputtering and micro-drop casting, respectively. ITO and Au were used as ohmic contacts to ZnO and PEDOT:PSS films, respectively. The final structure consisted on Glass/ITO/ZnO/PEDOT:PSS/Au. The SBDs performance was characterized under dark and four different wavelengths conditions. From current–voltage characteristics, under dark and ambient conditions, a diode ideality factor of 1.4; a saturation current density of 1×10⁻⁹ A/cm²; a Schottky barrier height of 0.9 eV and a rectification ratio of 5 orders of magnitude at ±1 V were obtained. A carrier density of 5×10¹⁷ cm⁻³ for the ZnO film was estimated from capacitance–voltage measurements. For their characterization as photodiodes, the SBDs were illuminated with an ultra-bright UV (~380 nm) LED. A maximum UV responsivity of 0.013 A/W was obtained. The transient response of the SBDs was also analyzed with the UV LED connected to a pulsed signal of 0.5 Hz, demonstrating rise and fall times in the order of 200 ms. With a low temperature processing (<80 °C), visible-blind and UV photon-detection characteristics, the fabricated SBDs are candidates for flexible optoelectronics devices such as optical receivers for digital signal processing and measurement of light intensity.     

Fabrication and electrical characteristics of Perylene-3,4,9,10-tetracarboxylic dianhydride/p-GaAs diode structure

This study aims to experimentally investigate whether Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) organic layer at p-GaAs/Ag interface affects electrical transport across this interface or not. The electronic properties of metal–organic semiconductor–inorganic semiconductor structure between p type GaAs and PTCDA organic film have been investigated via current–voltage (I–V) and capacitance–voltage (C–V) methods. The Ag/PTCDA/p-GaAs contact exhibits a rectification behavior with the barrier height of 0.74 eV and ideality factor value of 3.42. Modification of the potential barrier of Ag/p-GaAs diode was achieved by using thin interlayer of the PTCDA organic material. This was attributed to the fact that the PTCDA organic interlayer increased the effective barrier height by influencing the space charge region of GaAs. The low and high frequency capacitance–voltage plots were used to determine the interface state density of the diode.     

Characterization of an Au/n-Si photovoltaic structure with an organic thin film

We demonstrate that a copper(II) organic complex can control the electrical characteristics of conventional Au/n-Si metal–semiconductor (MS) contacts. We investigated the electronic and photovoltaic properties of a Cu(II) complex/n-Si heterojunction diode. The ideality factor n and barrier height Φ_b of the diode were 2.22 and 0.736 eV, respectively. An ideality factor greater than unity indicates that the diode exhibits non-ideal current–voltage behavior. This behavior results from the effect of series resistance and the presence of an interfacial layer. The series resistance and barrier height determined using Norde’s method were 6.7 kΩ and 0.77 eV, respectively. The device showed photovoltaic behavior, with a maximum open-circuit voltage of 0.24 V and a short circuit current of 1.7 μA under light of 8 mW/cm².     

Electrical and photoelectrical characterization of an organic–inorganic heterojunction based on quinoline yellow dye

An organic–inorganic contact was fabricated by forming a thin film of quinoline yellow dye (QY) on a p-Si wafer and evaporating Al metal on the film. The current–voltage (I–V) and capacitance–voltage (C–V) measurements of Al/QY/p-Si heterostructure were applied in dark and room temperature to calculate the characteristic parameters of diode like ideality factor, barrier height and series resistance. Ideality factor and barrier height values were found as 1.23 and 0.87 eV from I–V data, respectively. The series resistance value of the device was determined as 1.8 kΩ by using modified Norde function. The C–V measurements were carried out at different frequencies and it was seen that capacitance value decreased with increasing frequency. Interface state density distribution was calculated by means of I–V measurement. In addition the optical absorption of thin QY film on glass was measured and optical band gap of the film was found as 2.73 eV. Furthermore, I–V measurements of Al/QY/p-Si/Al were taken under illumination between 40 and 100 mW/cm². It was observed that reverse bias current of the device increased with light intensity. Thus, the heterojunction had a strong response to the light and it can be suitable for electrical and optoelectronic applications like a photodiode.     

Energy level alignment in PCDTBT:PC70BM solar cells: Solution processed NiOx for improved hole collection and efficiency

Solution-based NiO_x outperforms PEDOT:PSS in device performance and stability when used as a hole-collection layer in bulk-heterojunction (BHJ) solar cells formed with poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole) (PCDTBT) and PC₇₀BM. The origin of the enhancement is clarified by studying the interfacial energy level alignment between PCDTBT or the 1:4 blended heterojunctions and PEDOT:PSS or NiO_x using ultraviolet and inverse photoemission spectroscopies. The 1.6 eV electronic gap of PEDOT:PSS and energy level alignment with the BHJ result in poor hole selectivity of PEDOT:PSS and allows electron recombination at the PEDOT:PSS/BHJ interface. Conversely, the large band gap (3.7 eV) of NiO_x and interfacial dipole (?0.6 eV) with the organic active layer leads to a hole-selective interface. This interfacial dipole yields enhanced electron blocking properties by increasing the barrier to electron injection. The presence of such a strong dipole is predicted to further promote hole collection from the organic layer into the oxide, resulting in increased fill factor and short circuit current. An overall decrease in recombination is manifested in an increase in open circuit voltage and power conversion efficiency of the device on NiO_x versus PEDOT:PSS interlayers.     

Determination of the laterally homogeneous barrier height of palladium Schottky barrier diodes on n-Ge (1 1 1)

We have studied the experimental linear relationship between barrier heights and ideality factors for palladium (Pd) on bulk-grown (1 1 1) Sb-doped n-type germanium (Ge) metal-semiconductor structures with a doping density of about 2.5×10¹⁵ cm^?3. The Pd Schottky contacts were fabricated by vacuum resistive evaporation. The electrical analysis of the contacts was investigated by means of current–voltage (I–V) and capacitance–voltage (C–V) measurements at a temperature of 296 K. The effective barrier heights from I–V characteristics varied from 0.492 to 0.550 eV, the ideality factor n varied from 1.140 to 1.950, and from reverse bias capacitance–voltage (C^?2–V) characteristics the barrier height varied from 0.427 to 0.509 eV. The lateral homogenous barrier height value of 0.558 eV for the contacts was obtained from the linear relationship between experimental barrier heights and ideality factors. Furthermore the experimental barrier height distribution obtained from I–V and (C^?2?V) characteristics were fitted by Gaussian distribution function, and their mean values were found to be 0.529 and 0.463 eV, respectively.     

The enhancement of electrical and optical properties of PEDOT:PSS using one-step dynamic etching for flexible application

The conductivity enhancement of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) by dynamic etching process was investigated to introduce the outstanding and simplest method for soft electronics. Four different samples which were pristine PEDOT:PSS, PEDOT:PSS doped with 5 wt.% DMSO, PEDOT:PSS with dipping process, and PEDOT:PSS with dynamic etching process were prepared to compare the properties such as conductivity, morphology, relative atomic percentage, and topography. All samples were characterized by four point probe, current atomic force microscopy (C-AFM), X-ray photoelectron spectroscopy (XPS), and UV–visible spectroscopy. The conductivity of the sample with dynamic etching process showed the highest value as 1299 S/cm among four samples. We proved that the dynamic etching process is superior to remove PSS phase from PEDOT:PSS film, to flow strong current through entire surface of PEDOT:PSS, and to show the smoothest surface (RMS 2.28 nm). XPS analysis was conducted for accurate chemical and structural surface environments of four samples and the relative atomic percentage of PEDOT in the sample with dynamic etching was the highest as 29.5%. The device performance of the sample with the dynamic etching process was outstanding as 10.31 mA/cm² of J_sc, 0.75 eV of V_oc, 0.46 of FF, and 3.53% of PCE. All properties and the device performance for PEDOT:PSS film by dynamic etching process were the most excellent among the samples.     

Electrical parameters of a DC sputtered Mo/n-type 6H-SiC Schottky barrier diode

A Mo/n-type 6H-SiC/Ni Schottky barrier diode (SBD) was fabricated by sputtering Mo metal on n-type 6H-SiC semiconductor. Before the formation of Mo/n-type 6H-SiC SBD, an ohmic contact was formed by thermal evaporation of Ni on n-type 6H-SiC and annealing at 950 °C for 10 min. It was seen that the structure had excellent rectification. The electrical parameters were extracted using its current–voltage (I–V) and capacitance–voltage (C–V) measurements carried out at room temperature. Very high (1.10 eV) barrier height and 1.635 ideality factor values were reported for Mo/n-type 6H-SiC using ln I–V plot. The barrier height and series resistance values of the diode were also calculated as 1.413 eV and 69 Ω from Norde׳s functions, respectively. Furthermore, 1.938 eV barrier height value of Mo/n-type 6H-SiC SBD calculated from C–V measurements was larger than the one obtained from I–V data.     

Controlling of electronic parameters of GaAs Schottky diode by poly(3,4-ethylenedioxithiophene)-block-poly(ethylene glycol) organic interlayer

The electronic properties of metal-organic semiconductor-inorganic semiconductor structure between GaAs and poly(3,4-ethylenedioxithiophene)-block-poly(ethylene glycol) organic film have been investigated via current-voltage and capacitance-voltage methods. The Au/PEDOT/n-GaAs contact exhibits a rectification behavior with the barrier height of 0.69 eV and ideality factor value of 3.94. The barrier height of the studied diode (0.67 eV) is lower than that of Ni/n-GaAs/In (0.85 eV) and Au/n-GaAs/In Schottky diodes. The decrease in barrier height of Au/n-GaAs/In Schottky diode is likely to be due to the variation in the space charge region in the GaAs. The obtained results indicate that control of the interfacial potential barrier for metal/n-GaAs diode was achieved using thin interlayer of the poly(3,4-ethylenedioxithiophene)-block-poly(ethylene glycol).     

Preparation of lateral spin-valve structure using doped conducting polymer poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)

To perform four-terminal nonlocal spin-valve measurements on organic spin-valves, we fabricated lateral spin-valve devices consisting of doped conducting polymer poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) [PEDOT:PSS] and ferromagnetic Ni₈₀Fe₂₀ narrow line (width: 530 nm) electrodes. Although the formula of the nonlocal magnetoresistance with the parameters of doped conducting polymers predicts sufficient nonlocal magnetoresistance, we could not observe any spin signal. The spin diffusion length in the doped PEDOT:PSS device does not appear to be as long as those predicted by both the Elliott–Yafet mechanism and the theory of spin relaxation in organic disordered solids.     

Electrical characterization of solid-state heterojunctions between PEDOT:PSS and an anionic polyelectrolyte

Stable organic heterojunctions are developed by deposition of the anionic polyelectrolyte poly(4-lithium styrenesulfonic acid) (LiPSSA) on the top of poly(3,4-ethylendioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) films. The electrical response of the heterojunctions to triangular voltage pulses in the range between −5 and +5 V is characterized by hysteresis phenomena, observed for hundreds of cycles with low distortions, at scan rates between 1 and 100 mV/s. The hysteresis is ascribed to the occurrence of redox transitions, evidenced by the presence of well-defined peaks in the current–voltage characteristics. The electrical behaviour of the PEDOT:PSS/LiPSSA devices is found to be mainly capacitive, and show humidity-sensitive functionality, demonstrated by the gradual and reversible increase of the area subtended by the J−V cycles as the relative humidity increases.     

Current–voltage and capacitance–voltage characteristics of Al Schottky contacts to strained Si-on-insulator in the wide temperature range

The electrical characteristics of Al/strained Si-on-insulator (sSOI) Schottky diode have been investigated using current–voltage (I–V) and capacitance–voltage (C–V) measurements in the wide temperature range of 200–400 K in steps of 25 K. It was found that the barrier height (0.57–0.80 eV) calculated from the I–V characteristics increased and the ideality factor (1.97–1.28) decreased with increasing temperature. The barrier heights determined from the C–V measurements were higher than those extracted from the I–V measurements, associated with the formation of an inhomogeneous Schottky barrier at the interface. The series resistance estimated from the forward I–V characteristics using Cheung and Norde methods decreased with increasing temperature, implying its strong temperature dependence. The observed variation in barrier height and ideality factor could be attributed to the inhomogeneities in Schottky barrier, explained by assuming Gaussian distribution of barrier heights. The temperature-dependent I–V characteristics showed a double Gaussian distribution with mean barrier heights of 0.83 and 1.19 eV and standard deviations of 0.10 and 0.16 eV at 200–275 and 300–400 K, respectively. From the modified Richardson plot, the modified Richardson constant were calculated to be 21.8 and 29.4 A cm⁻² K⁻² at 200–275 and 300–400 K, respectively, which were comparable to the theoretical value for p-type sSOI (31.6 A cm⁻² K⁻²).     

Effects of tetramethylene sulfone solvent additives on conductivity of PEDOT:PSS film and performance of polymer photovoltaic cells

A solvent additive in PEDOT:PSS solution is one of many methods to improve the conductivity of the poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films. We explore a new type of the solvent additive, namely tetramethylene sulfone (TMS), for the fabrication of the PEDOT:PSS conductive layer in the ITO/PEDOT:PSS/P3HT:PCBM/TiO_x/Al polymer photovoltaic cells, in comparison to a more common dimethyl sulfoxide (DMSO) solvent additive. At optimal conditions, the TMS additive at 10 wt.% has been found to enhance the conductivity of pristine PEDOT:PSS films from 0.04 S/cm up to approximately 189 S/cm, compared with the highest conductivity for the case of the DMSO additive at 15 wt.% of 117 S/cm. Possible mechanisms of this conductivity enhancement, relating to the polymer conformation and the film morphology, have been investigated by Raman spectroscopy, X-ray diffraction, atomic force microscopy, and transmission electron microscopy. The performance of the polymer photovoltaic cells fabricated with the solvent additives PEDOT:PSS films follows a similar trend to the conductivity of the films as a function of the additive concentration. The additives mainly lead to greater short circuit current density (J_sc) of the photovoltaic cells. The highest power conversion efficiency (PCE) of 2.24% of the device has been obtained with the 10 wt.% TMS additive of, compared to the PCE of 1.48% for the standard device without solvent additive.     

Optical properties and conductivity of PEDOT:PSS films treated by polyethylenimine solution for organic solar cells

We report on conductivity and optical property of three different types of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) films [pristine PH1000 film (PH1000-p), with 5 wt.% ethylene glycol additive (PH1000-EG) and with sulfuric acid post-treatment (PH1000-SA)] before and after polyethylenimine (PEI) treatment. The PEI is found to decrease the conductivity of all the PEDOT:PSS films. The processing solvent of 2-methoxyethanol is found to significantly enhance the conductivity of PH1000-p from 1.1 up to 744 S/cm while the processing solvent of isopropanol or water does not change the conductivity of PH1000-p much. As for the optical properties, the PEI treatment slightly changes the transmittance and reflectance of PH1000-p and PH1000-EG films, while the PEI leads to an substantial increase of the absorptance in the spectral region of 400–1100 nm of the PH1000-SA films. Though the optical property and conductivity of the three different types of PEDOT:PSS films vary with the PEI treatment, the treated PEDOT:PSS films exhibit similar low work function. We demonstrate solar cells with a simple device structure of glass/low-WF PEDOT:PSS/P3HT:ICBA/high-WF PEDOT:PSS cells that exhibit good performance with open-circuit voltage of 0.82 V and fill factor up to 0.62 under 100 mW/cm² white light illumination.     

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.     

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.     

Investigation of structural and optoelectronic properties of annealed nickel phthalocyanine thin films

Thin films of nickel phthalocyanine (NiPc) were prepared by thermal evaporation and the effects of annealing temperature on the structural and optical properties of the samples were studied using different analytical methods. Structural analysis showed that the grain size and crystallinity of NiPc films improved as annealing temperature increased from 25 to 150 °C. Also, maximum grain size (71.3 nm) was obtained at 150 °C annealing temperature. In addition, NiPc films annealed at 150 °C had a very smooth surface with an RMS roughness of 0.41 nm. Optical analysis indicated that band gap energy of films at different annealing temperatures varied in the range of 3.22–3.28 eV. Schottky diode solar cells with a structure of ITO/PEDOT:PSS/NiPc/Al were fabricated. Measurement of the dark current density–voltage (J–V) characteristics of diodes showed that the current density of films annealed at 150 °C for a given bias was greater than that of other films. Furthermore, the films revealed the highest rectification ratio (23.1) and lowest barrier height (0.84 eV) demonstrating, respectively, 23% and 11% increase compared with those of the deposited NiPc films. Meanwhile, photoconversion behavior of films annealed at 150 °C under illumination showed the highest short circuit current density (0.070 mA/cm²) and open circuit voltage of (0.55 V).     

Current transport and formation of energy structures in narrow Au/n-GaAs Schottky diodes

The current transport and formations of potential barrier height in narrow Au/n-GaAs Schottky diodes (SD) with a contact surface in length of 200 μm, width of 1 and 4 μm have been investigated.It was determined that features of current transport are in good agreements with the thermionic emission theory in the forward bias as like high-quality conventional (flat) SD. Features of current transport in the reverse bias also is well described by thermionic emission theory, but it has specific features unlike I–V characteristics flat SD.Forward bias of narrow SD current–voltage (I–U) characteristics are represented by straight lines in semi-logarithmic scale in a wide range, nearly nine order of current up to 0.7 V with near unit ideality factor. In the beginning of the reverse voltage, the current practically was extremely low, by increasing in voltage the current jump in steps approximately for 3–4 order in voltage of 3–4 V, then current increases linear for 3–5 order in semi-logarithmic scale by increasing in voltage up to nearly 7 V.Numerical values of parameters such as the saturation currents, the operating barrier height, ideality factor, dimensionless factor are obtained. The correlations between ideality factor and dimensionless factor were meaningful.The energy diagrams of narrow SD have been drawn in absence and presence of forward and reverse voltage. It is found that electronic processes in narrow SD are well described by energy model of real narrow metal–semiconductor contacts. The additional electric field arising in near contact area of the semiconductor because of creating contact potential difference between contact surface and to it adjoining free surfaces of the metal and semiconductor.