Electro-optical characterization and analysis of CuPc-based solar cells with high photovoltage

Organic solar cells using the CuPc and PTCBI semiconductor layers were studied. A high open circuit voltage of 1.15 V was obtained in a device with ITO/PEDOT:PSS/CuPc (15 nm)/PTCBI (7 nm)/Al structure. Results were interpreted in terms of a modified CuPc-Al Schottky diode for the thin PTCBI case and a CuPc-PTCBI heterojunction for the thick PTCBI case. Also, the formation of a thin aluminum oxide layer under the aluminum electrode was postulated. This layer has a beneficial aspect wherein shunting losses are reduced and a high photovoltage is enabled. However, it adds greatly to the series resistance to a point where the short circuit current density is reduced. CuPc Schottky diodes with an ITO/PEDOT:PSS/CuPc/Al structure yielded a high V _oc of 900 mV for a CuPc layer of thickness 140 nm. The V _oc increased with increase in CuPc layer thickness.     

Use of graphene for forming Al-based p-type reflectors for near ultraviolet InGaN/AlGaN-based light-emitting diode

We demonstrated the improved performance of near UV (365 nm) InGaN/AlGaN-based LEDs using highly reflective Al-based p-type reflectors with graphene sheets as a diffusion barrier. The use of graphene sheets did not degrade the reflectance of ITO/Al contacts, viz. ∼81% at 365 nm. The ITO/graphene/Al contacts annealed at 300 °C exhibited better ohmic behavior with a specific contact resistance of 1.5 × 10⁻³ Ωcm² than the ITO/Al contact (with 9.5 × 10⁻³ Ωcm²). Near UV LEDs fabricated with the ITO/graphene/Al contact annealed at 300 °C showed a 7.2% higher light output (at 0.1 W) than LEDs with the ITO/Al reflector annealed at 300 °C. The SIMS results exhibited that, unlike the ITO/graphene/Al, the ITO/Al contacts undergo a significant indiffusion of Al atoms toward the GaN after annealing. Furthermore, both Ga and Mg atoms were also more extensively outdiffused in the ITO/Al contacts after annealing. On the basis of the SIMS and electrical results, the possible explanations for the annealing-induced degradation of the ITO/Al contacts are described and discussed.     

Improvement of the efficiency of phthalocyanine organic Schottky solar cells with ITO electrode treatment

The devices investigated in this work consisted of an indium tin oxide (ITO)-coated glass substrate, phthalocyanine (Pc) layer and an aluminum electrode. The Schottky cell exhibits optimal performance with one ohmic and one barrier contact. The work function of the ITO film is typically around 4.5–4.8 eV, while the HOMO level of phthalocyanine films is typically around 5.2 eV. It is known that surface treatment of ITO can change its work function. We investigated various ITO surface treatments for improving the performance of phthalocyanine-based Schottky solar cells. We found that cells of ITO treated with HCl and UV ozone exhibited the best performance. Four different phthalocyanines (Pcs), namely nickel phthalocyanine (NiPc), copper phthalocyanine (CuPc), iron phthalocyanine (FePc) and cobalt phthalocyanine (CoPc) were investigated. A power conversion efficiency as high as 10% was achieved for the CuPc cell with monochromatic excitation at 632.8 nm, with a light intensity of 2.7 W/cm². PACS 72.40.+w; 73.61.Ph     

Effects of annealing temperature on GO–Cu2O composite films grown by electrochemical deposition for PEC photoelectrode

In this work, graphene oxide–cuprous oxide (GO–Cu₂O) composite films were grown on fluorine-doped tin oxide substrates by electrochemical deposition. We investigated the effects of the annealing temperature on the morphological, structural, optical and photoelectrochemical (PEC) properties of GO–Cu₂O composite films. As a result, our work shows that while GO–Cu₂O composite films exhibit the highest XRD (111) peak intensity at 300 °C sample, the highest photocurrent density value obtained was −4.75 mA/cm² at 200 °C sample (using 0.17 V versus a reversible hydrogen electrode (RHE)). In addition, a reduction reaction at 300 °C sample was observed using XPS analysis from the shift in the O1s peak in addition to a weaker O1s peak intensity.     

Preserving long-term emission stability of carbon nanotube field emitter using aluminum layer

Carbon nanotube (CNT) field emitter was fabricated, and then its emission stability was evaluated with three different anode structures; indium tin oxide (ITO)/glass, ZnS:Cu,Al(green phosphor)/ITO/glass, and Al/ZnS:Cu,Al/ITO/glass. It was found that the electron emission from CNTs to the phosphor layer degrades much faster than the emission to ITO layer does. The current decay time from 100 μA/cm² to 50 μA/cm² for ITO/glass and ZnS:Cu,Al/ITO/glass were 250 h and 20 h, respectively. Such rapid decay in emission current with the phosphor-coated anode was found to be attributed to the formation of Zn particles on CNTs during the field emission. However, the deposition of aluminum layer on the phosphor, in other words, using the anode structure of Al/ZnS:Cu,Al/ITO/glass recovered the stability that is comparable to that with an ITO/glass. The aluminum layer was found to efficiently prevent phosphor elements from being degassed, preserving the long-term emission stability of carbon nanotubes.     

Sonochemical synthesis and application of rhodium–graphene nanocomposite

Abstract  

Highly water dispersible rhodium–graphene nanocomposite have been successfully synthesized by the simple reduction of Rh³⁺ salt on poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) (PEO/PPO/PEO) triblock copolymer or pluronic-stabilized graphene oxide (GO) nanosheets with borohydride. Rhodium nanoparticles, having average size of 1–3 nm, are homogeneously distributed through out the graphene sheets. Some porous structures of graphene sheets have also been observed after the reduction of pluronic-stabilized GO in the presence of metal ions. The material is very effective for hydrogenation of arenes, especially for benzene as the substrate material at the room temperature and 5 atm pressure of hydrogen.     

ITO: Zr bi-layers deposited by reactive O2 and Ar plasma with high work function for silicon heterojunction solar cells

We report the influence of reactive oxygen (O₂) and argon (Ar) plasma based ITO:Zr bi-layers for silicon heterojunction (SHJ) solar cells. The purpose of reactive O₂ sputtered ITO:Zr was to improve the Hall mobility and work function while the Ar based ITO:Zr films play an important role to maintain good electrical characteristics. The thickness of reactive O₂ based ITO:Zr films was fixed at 15 nm while Ar based films was varied from 65 to 125 nm, respectively. ITO:Zr bi-layers with the thickness of 15/105 nm deposited by O₂ and Ar plasma, respectively, showed lowest resistivity of 2.358 × 10⁻⁴ Ω cm and high Hall mobility of 39.3 cm²/V · s. All ITO:Zr bi-layers showed an average transmittance of above 80% in the visible wavelength (380–800 nm) region. Work function of ITO:Zr bi-layers was calculated from the X-ray photoelectron spectroscopic (XPS) data. The ITO:Zr work function was enhanced from 5.3 eV to 5.16 eV with the variation of ITO:Zr bi-layers from 15/65 to 15/125 nm, respectively. Front barrier height in SHJ solar cells can be modified by using TCO films with high work function. The SHJ solar cells were fabricated by employing the ITO:Zr bi-layer as front anti-reflection coating. The SHJ solar cells fabricated on ITO:Zr bi-layer with the thickness of 15/105 nm showed the best photo-voltage parameters as; V_oc = 739 mV, J_sc = 39.12 mA/cm², FF = 75.97%, η = 21.96%.     

Structural and electronic implications for carrier injection into organic semiconductors

We report on the structural and electronic interface formation between ITO (indium-tin-oxide) and prototypical organic small molecular semiconductors, i.e., CuPc (copper phthalocyanine) and α-NPD (N,N′-di(naphtalen-1-yl)-N,N′-diphenyl-benzidine). In particular, the effects of in situ oxygen plasma pretreatment of the ITO surface on interface properties are examined in detail: Organic layer-thickness dependent Kelvin probe measurements revealed a good alignment of the ITO work function and the highest occupied electronic level of the organic material in all samples. In contrast, the electrical properties of hole-only and bipolar organic diodes depend strongly on the treatment of ITO prior to organic deposition. This dependence is more pronounced for diodes made of polycrystalline CuPc than for those of amorphous α-NPD layers. X-ray diffraction and atomic force microscopic (AFM) investigations of CuPc nucleation and growth evidenced a more pronounced texture of the polycrystalline film structure on the ITO substrate that was oxygen plasma treated prior to organic layer deposition. These findings suggest that the anisotropic electrical properties of CuPc crystallites, and their orientation with respect to the substrate, strongly affect the charge carrier injection and transport properties at the anode interface.     

Fabrication of cosputtered Zn–In–Sn–O films and their applications to organic light-emitting diodes

Zn–In–Sn–O (ZITO) films have been grown by rf magnetron cosputtering system from ceramic oxide targets of ZnO and ITO onto glass substrate. X-ray diffraction analysis shows that the microstructure is amorphous below the substrate temperature of 250 ^°C. The films exhibit sheet resistance as low as 16.7 Ω/□ and optical transparency comparable to grater than that of Sn-doped indium oxide (ITO) films. The work function ranged 5.05–5.19 eV, which is a higher work function compared to ITO (4.7 eV). The fabricated ZITO films are used in fabrication of organic light-emitting diodes (OLEDs). The ZITO anode with the zinc content of 12.5 at.% [Zn/(Zn+In+Sn)] fabricated at 250 ^°C-based OLED shows lower turn-on voltage and higher current density compared to that of ITO-based control device.     

The effect of carbon contamination and argon ion sputtering on the work function of chlorinated indium tin oxide

The work function of indium tin oxide (ITO) was increased by treating ITO with dichlorobenzene with UV light. Carbon contamination of the Cl-ITO was measured using X-ray Photoelectron Spectroscopy (XPS) and argon ion sputtering was used to remove the carbon from the surface. It was found that the carbon contamination from residual dichlorobenzene significantly lowered the work function of the ITO and after argon ion sputtering the work function increased to 5.8 eV. It was found that chlorination of ITO occurs after more than 6 min of UV exposure. Further sputtering of ITO resulted in the removal of the functionalized chlorine, the introduction of argon ion contaminants on the ITO decreases its work function.     

Observation of ferromagnetism and anomalous Hall effect in laser-deposited chromium-doped indium tin oxide films

We report on the structural, magnetic, and magnetotransport characteristics of Cr-doped indium tin oxide (ITO) films grown on SiO₂/Si substrates by pulsed laser deposition. Structural analysis clearly indicates that homogeneous films of bixbyite structure are grown without any detectable formation of secondary phases up to 20 mol% Cr doping. The carrier concentration is found to decrease with Cr ion addition, displaying a change in the conduction type from n-type to p-type around 15 mol% Cr doping. Room temperature ferromagnetism is observed, with saturation magnetization of ∼0.7 emu/cm³, remnant magnetization of ∼0.2 emu/cm³ and coercive field of ∼30 Oe for 5 mol% Cr-doped ITO. Magnetotransport measurements reveal the unique feature of diluted magnetic semiconductors, in particular, an anomalous Hall effect governed by electron doping, which indicates the intrinsic nature of ferromagnetism in Cr-doped ITO. These results suggest that Cr-doped ITO could be promising for semiconductor spin electronics devices.     

A hybrid photodiode with planar heterojunction structure consisting of ZnO nanoparticles and CuPc thin film

A photodiode with planar heterojunction was fabricated using copper (II) phthalocyanine (CuPc) organic semiconductor and zinc oxide (ZnO) inorganic nanoparticles (NPs, ～5 nm). The current–voltage (I–V) characteristics of ITO/ZnO NPs/CuPc/Ag device in dark and under illumination with a solar simulator were investigated in detail. The measurement results showed that the device exhibited good rectifying behavior in dark and under illumination. A rectification ratio (RR) of 15.44 at 1.95 V was achieved for the device under 100 mW/cm² illumination power. Also, the RR of the device as a function of light intensity was observed. The photoresponsive mechanism of the photodiode was illuminated in term of its energy band diagram.     

Scanning transmission X‐ray microscopy probe for in situ mechanism study of graphene‐oxide‐based resistive random access memory

Here, an in situ probe for scanning transmission X‐ray microscopy (STXM) has been developed and applied to the study of the bipolar resistive switching (BRS) mechanism in an Al/graphene oxide (GO)/Al resistive random access memory (RRAM) device. To perform in situ STXM studies at the C K‐ and O K‐edges, both the RRAM junctions and the I₀ junction were fabricated on a single Si₃N₄ membrane to obtain local XANES spectra at these absorption edges with more delicate I₀ normalization. Using this probe combined with the synchrotron‐based STXM technique, it was possible to observe unique chemical changes involved in the BRS process of the Al/GO/Al RRAM device. Reversible oxidation and reduction of GO induced by the externally applied bias voltages were observed at the O K‐edge XANES feature located at 538.2 eV, which strongly supported the oxygen ion drift model that was recently proposed from ex situ transmission electron microscope studies.     

Effect on the reduction of the barrier height in rear-emitter silicon heterojunction solar cells using Ar plasma-treated ITO film

In this study, we investigated the effect of plasma treatment on an indium tin oxide (ITO) film under an ambient Ar atmosphere. The sheet resistance of the plasma-treated ITO film at 250 W (37.6 Ω/sq) was higher than that of the as-deposited ITO film (34 Ω/sq). Plasma treatment was found to decrease the ITO grain size to 21.81 nm, in comparison with the as-deposited ITO (25.49 nm), which resulted in a decrease in the Hall mobility. The work function of the Ar-plasma-treated ITO (WF_ITO=4.17 eV) was lower than that of the as-deposited ITO film (WF_ITO = 5.13 eV). This lower work function was attributed to vacancies that formed in the indium and oxygen vacancies in the bonding structure. Rear-emitter silicon heterojunction (SHJ) solar cells fabricated using the plasma-treated ITO film exhibited an open circuit voltage (V_OC) of 734 mV, compared to SHJ cells fabricated using the as-deposited ITO film, which showed a V_OC of 704 mV. The increase in V_OC could be explained by the decrease in the work function, which is related to the reduction in the barrier height between the ITO and a-Si:H (n) of the rear-emitter SHJ solar cells. Furthermore, the performance of the plasma-treated ITO film was verified, with the front surface field layers, using an AFORS-HET simulation. The current density (J_SC) and V_OC increased to 39.44 mA/cm² and 736.8 mV, respectively, while maintaining a WF_ITO of 3.8 eV. Meanwhile, the efficiency was 22.9% at V_OC = 721.5 mV and J_SC = 38.55 mA/cm² for WF_ITO = 4.4 eV. However, an overall enhancement of 23.75% in the cell efficiency was achieved owing to the low work function value of the ITO film. Ar plasma treatment can be used in transparent conducting oxide applications to improve cell efficiency by controlling the barrier height.     

Improvement of water softening efficiency in capacitive deionization by ultra purification process of reduced graphene oxide

Capacitive deionization (CDI) is the next generation of water desalination and softening technology by using relatively low capacitive current of electrochemical double layer. Among various carbon-based materials used for making electrode, reduced graphene oxide (rGO) has been intensively studied due to its excellent electrical conductivity and high surface area. Although Hummer method for making graphene oxide (GO) and rGO is a simple process, it remains some impurities in inherent GO and rGO which affect negatively to the CDI performance. In this work, we successfully prepared ultra purified GO and rGO by modifying Hummer method in order to remove entirely excess elements degrading the CDI performance. The electrosorption capacity of ultra purified rGO is considerably better than that of previous rGO, and maximum removal achieves 3.54 mg g⁻¹ at applied voltage of 2.0 V. Thus, this result could be comparable to other researches in CDI process.     

Electronic properties of the polycrystalline tin dioxide interface with conjugated organic layers

The results on the electronic structure of the unoccupied electronic states of the polycrystalline SnO₂ in the energy range from 5 eV to 25 eV above the Fermi level are presented. The modification of the electronic structure and of the surface potential upon deposition of the ultrathin films of copper phthalocyanine (CuPc) and of perylene tetracarboxylic acid dianhydride (PTCDA) film onto the SnO₂ surface were studied using the very low energy electron diffraction (VLEED) method and the total current spectroscopy (TCS) measurement scheme. A substantial attenuation of the TCS signal coming from the SnO₂ surface was observed upon formation of a 1.5–2 nm thick organic deposit layer while no new spectral features from the deposit were distinguishable. It was observed that the electronic structure typical for the organic films was formed within the organic deposit thickness range from 2 nm to 7 nm. The interfacial charge transfer was characterized by the formation of the polarization layer up to 5 nm thick in the organic films. The PTCDA deposition on SnO₂ was accompanied by the negative charge transfer onto the organic layer and to the 0.65 eV increase the surface work function. At the CuPc/SnO₂ interface, the negative charge was transferred to the SnO₂ surface and the overall surface work function decreased by 0.15 eV.     

Nonvolatile unipolar resistive switching in ultrathin films of graphene and carbon nanotubes

We report unipolar resistive switching in ultrathin films of chemically produced graphene (reduced graphene oxide) and multiwalled carbon nanotubes. The two-terminal devices with yield >99% are made at room temperature by forming continuous films of graphene of thickness ∼20 nm on indium tin oxide coated glass electrode, followed by metal (Au or Al) deposition on the film. These memory devices are nonvolatile, rewritable with ON/OFF ratios up to ∼ 10⁵ and switching times up to 10 μs. The devices made of MWNT films are rewritable with ON/OFF ratios up to ∼400. The resistive switching mechanism is proposed to be nanogap formation and filamentary conduction paths.     

Surface-enhanced Raman effect in ultra-thin CuPc films employing periodic silver nanostructures

In order to investigate the interaction of organic molecules with metals by means of Raman spectroscopy, special substrates were designed which combine interference and surface-enhancement mechanisms. Triangular shaped silver nanostructures with an angle bisector and a height of about 80 nm were prepared by nanosphere lithography on silicon substrates with a 100-nm oxide layer. Utilizing these substrates the dependence of the Raman signal intensity on the thickness of copper phthalocyanine (CuPc) was studied in the range from few percentages of a monolayer coverage up to 80 nm using an in situ setup. At an excitation in resonance with the plasmons of the nanostructures (2.6 eV) an increase of the signal was observed during film growth. Contrary to that, excitation at 1.92 eV in resonance with the CuPc absorption band leads to a strongly enhanced Raman signal for submonolayer coverage which hardly changes with the CuPc film thickness in the ultra-low coverage regime.     

Switching and memory effects in composite films of semiconducting polymers with particles of graphene and graphene oxide

The effects of switching were investigated in composite films based on multifunctional polymers. i.e., derivatives of carbazole (PVK) and fluorene (PFD), as well as based on particles of graphene (Gr) and graphene oxide (GO). The concentration of Gr and GO particles in the PVK(PFD) matrix was varied in the range of 2–3 wt %, which corresponded to the percolation threshold in these systems. The atomic composition of the composite films PVK: GO was examined using X-ray photoelectron spectroscopy. It was found that the effect of switching in structures of the form Al/PVK(PFD): GO(Gr)/ITO/PET manifests itself in a sharp change of the electrical resistance of the composite film from a low-conducting state to a relatively high-conducting state when applying a bias to Al-ITO electrodes of ∼0.1–0.3 V (E ∼ 3–5 × 10⁴ V/cm), which is below the threshold switching voltages for similar composites. The mechanism of resistance switching, which is associated with the processes of capture and accumulation of charge carriers by Gr (GO) particles introduced into the matrices of the high-molecular-weight (PVK) and relatively low-molecular-weight (PFD) polymers, was discussed.

     

Reduced graphene oxide field-effect transistor with indium tin oxide extended gate for proton sensing

In this study, the reduced graphene oxide field-effect transistor (rGO FET) with indium tin oxide (ITO) extended gate electrode was demonstrated as a transducer for proton sensing application. In this structure, the proton sensing area of the ITO extended gate electrode is isolated from the active area of the rGO FET. The proton sensing properties based on the rGO FET transducer were analyzed. The rGO FET device with encapsulation by a tetratetracontane (TTC) layer showed good stability in electrolytic solutions. The device showed an ambipolar behavior with shifts in Dirac point as the pH of the electrolyte is varied. The pH sensitivity based on the Dirac point shift as a sensing parameter was about 43–50 mV/pH for a wide range of pH values from 2 to 12. The ITO extended gate rGO FET may be considered a potential transducer for sensing of H⁺ in electrolytes. Its sensing area can be modified further for various ions sensing applications.