Decamethylcobaltocene as an efficient n-dopant in organic electronic materials and devices

n-Doping of copper phthalocyanine (CuPc), which has an electron affinity (EA) of 3.52 eV, by decamethylcobaltocene (DMC) is demonstrated. DMC has a remarkably low solid-state ionization energy (IE) of 3.3 eV, as measured by ultra-violet photoemission spectroscopy (UPS). Further UPS measurements show a large 1.4 eV upward shift of the Fermi-level within the single particle gap of CuPc between the p- and n-doped films. n-Doping is also confirmed by current–voltage (I–V) measurements, which show a 10⁶-fold increase in current density due to improved electron injection and enhanced conductivity of the bulk film. An organic p–i–n CuPc homojunction is also fabricated using F₄-TCNQ and DMC as p- and n-dopants, respectively. Current–voltage characteristics demonstrate excellent rectification with a turn on voltage of approximately 1.3 eV, which is consistent with the built-in voltage measured by UPS and capacitance–voltage (C–V) measurements.     

Doping efficiency and energy-level scheme in C60F48-doped zinc–tetraphenylporphyrin films

High resolution synchrotron-based core level spectroscopy was used to examine the energy level alignment at the interface of zinc–tetraphenylporphyrin films doped by the surface acceptor C₆₀F₄₈. Two distinct fluorofullerene charge states were identified, corresponding to ionized and neutral molecules, and their relative concentration as a function of coverage was used to evaluate the probability of occupation of the acceptor lowest unoccupied molecular orbital (LUMO). From an initial acceptor energy of ?0.25 eV, the C₆₀F₄₈ LUMO shifts upwards with coverage due to a doping-induced interfacial dipole potential, and stabilization of the LUMO at an energy 0.45 eV above the Fermi energy was obtained. While the energy difference upon saturation is consistent with the results obtained for other donor–acceptor systems that have been interpreted as Fermi level pinning, the present work shows that the energy offset is a direct consequence of the interplay between Fermi–Dirac statistics in combination with the interfacial dipole potential.     

Effects of Sb,Zn doping on structural,electrical and optical properties of SnO2 thin films

Highly transparent, low resistive pure and Sb, Zn doped nanostructured SnO₂ thin films have been successfully prepared on glass substrates at 400° C by spray pyrolysis method. Structural, electrical and optical properties of pure and Sb, Zn doped SnO₂ thin films are studied in detail. Powder X-ray diffraction confirms the phase purity, increase in crystallinity, size of the grains (90–45 nm), polycrystalline nature and tetragonal rutile structure of thin films. The scanning electron microscopy reveals the continuous change in surface morphology of thin films and size of the grains decrease due to Sb, Zn doping in to SnO₂. The optical transmission spectra of SnO₂ films as a function of wavelength confirm that the optical transmission increases with Sb, Zn doping remarkably. The optical band gap of undoped film is found to be 4.27 eV and decreases with Sb, Zn doping to 4.19 eV, 4.07 eV respectively. The results of electrical measurements indicate that the sheet resistance of the deposited films improves with Sb, Zn doping. The Hall measurements confirm that the films are degenerate n-type semiconductors.     

Phase transition and surface morphology effects on optical,electrical and lithiation/delithiation behavior of nanostructured Ce-doped V2O5 thin films

Cerium doped V₂O₅ thin films were prepared by the sol−gel process. X-ray diffraction analysis revealed the phase transition from α-V₂O₅ orthorhombic to β-V₂O₅ tetragonal structure by annealing at 400 °C. The SEM and AFM images revealed that annealing temperature changed the surface morphology of the V₂O₅ films from fiber like wrinkle network to elongated sheets. Also, the particle shape was significantly influenced by Ce doping and a nanorod-like morphology was formed at 1.5 mol% Ce−doped V₂O₅. Power spectral density analysis indicated that surface roughness and fractal dimension of β−V₂O₅ increase by Ce doping. Optical measurement showed that the band gap narrowing (from 2.68 to 2.28 eV) occurred when the annealing temperature and dopant concentration increased. The variation of activation energy of the films was explained based on the small polaron hopping mechanism. The α−V₂O₅ film showed enhanced lithium−ion storage capacity compared to pristine β−V₂O₅ film and 1 mol% Ce−doped α−V₂O₅ thin film revealed the best ion storage capacity (Q_a=207.19 mC/cm², I_max=4.13 mA/cm² at scan rate of ν=20 mV/s).     

Effect of fullerene doping on the electrical properties of P3HT/PCBM layers

Poly (3-hexylthiophene-2, 5-diyl) (P3HT) and its blend with Phenyl-C₆₁-Butyric acid-Methyl-Ester (PCBM) and fullerene (C₆₀) thin films were prepared and their electrical properties for memory applications were studied. Due to doping, a sharp decrease in the resistance for a P3HT:PCBM:C₆₀ device was observed at around 70 °C which makes it useful for thermal switching applications. Addition of C₆₀ to P3HT:PCBM blend gave a high value for R_RESET/R_SET in thermal switching. For bias switching, threshold voltage reduces to 1.4 V from 25 V with the addition of C₆₀ to P3HT layer.     

Effect of Bi doping on structural,morphological, optical and ethanol vapor response properties of SnO2 nanoparticles

The gas sensing behavior of thick films of Bi doped SnO₂ has been investigated towards ethanol vapor. The screen printing technique was used to prepare the thick films. The films were sintered at 650 °C for 2 h. The structural, surface morphological, optical and gas sensing properties of undoped and Bi doped SnO₂ thick films have been studied. X-ray diffraction and Raman spectroscopy confirmed that the films consisted exclusively of tetragonal tin oxide, without any impurity phases. FE-SEM studies revealed the formation of highly porous microstructure with grain size in few tens of nanometers. From the optical studies, the band gap was found to be decreased with bismuth doping (3.96 eV for undoped, 3.83 eV, 3.71 eV and 3.6 eV for 1 mol%, 2 mol% and 3 mol% Bi, respectively). The 3 mol % Bi doped SnO₂ thick films exhibited the highest sensitivity to 100 ppm of ethanol vapor at 300 °C. The effect of microstructure on sensitivity, response time and recovery time of the sensor was studied and discussed.     

Simplified phosphorescent organic light-emitting diodes with a WO3-doped wide bandgap organic charge transport layer

The effects of p-type doping of wide bandgap ambipolar 4,4′-N,N′-dicarbazolebiphenyl (CBP) with WO₃ were investigated through detailed electrical device characterization. It was found that, to achieve effective doping for improved hole injection and transport, the doping level should be greater than 20 mol% and the doped layer should be at least 10 nm thick. A large downward shift of the Fermi level in WO₃-doped CBP causes band bending and depletion at the doped/undoped CBP interface, resulting in an additional energy barrier which hampers hole transport. Simplified green phosphorescent organic light-emitting diodes (PhOLEDs) with CBP as the hole transport and host material were fabricated. With a WO₃-doped hole transport layer, the PhOLEDs attained brightness of 11,163 cd/m² at 20 mA/cm², and exhibited an improved reliability under constant-current stressing as compared to undoped PhOLEDs.     

Structural,morphological, electrical and optical studies of Cr doped SnO2 thin films deposited by the spray pyrolysis technique

Tin oxide (SnO₂) and chromium (Cr) doped tin oxide (Cr:SnO₂) thin films were deposited on the preheated glass substrates at 673 K by spray pyrolysis. Concentration of Cr was varied in the solution by adding chromium (III) chloride hexahydrate from 0 to 3 at%. The effect of Cr doping on the structural, electrical and optical properties of tin oxide films is reported. X-ray diffraction pattern confirms the tetragonal crystal structure for undoped and Cr doped tin oxide films. Scanning electron microscopic photographs show the modification of surface morphology of tin oxide film due to varying concentration of Cr. X-ray photoelectron spectra of Cr:SnO₂ (3 at%) thin film revealed the presence of carbon, tin, oxygen, and chromium. Carrier concentration and mobility of the SnO₂ films decrease with increasing concentration of Cr and 0.5 at% Cr doped tin oxide film acquires a mobility of 70 cm²/V s. Average optical transmittance in the 550–850 nm range varies from 38% to 47% with varying Cr concentration in the solution.     

Growth of Zn doped Cu(In, Ga)Se2 thin films by RF sputtering for solar cell applications

Cu(In, Ga)Se₂ (CIGS) surface was modified with Zn doping using a magnetron sputtering method. CuInGa:Zn precursor films targeting a CuIn_0.7Ga_0.3Se₂ stoichiometry with increasing Zn content from 0 to 0.8 at% were prepared onto Mo-coated glass substrates via co-sputtering of Cu–Ga alloy, In and Zn targets. The CuInGa:Zn precursors were then selenized with solid Se pellets. The structures and morphologies of grown Zn doped CIGS films were found to depend on the Zn content. At zinc doping level ranging between 0.2 and 0.6 at%, the Zn doping improved the crystallinity and surface morphology of CIGS films. Compared with the performance of the non-doped CIGS cell, the fabricated CIGS solar cell displayed a relative efficiency enhancement of 9–22% and the maximum enhancement was obtained at a Zn content of 0.4 at%.     

Effect of trap states on the electrical doping of organic semiconductors

We demonstrate that direct charge transfer (CT) from trap states of host molecules to the p-dopant molecules raises the doping effect of organic semiconductors (OS). Electrons of the trap states in 4,4′-N,N′-dicarbazolyl-biphenyl (CBP) (E_HOMO = 6.1 eV) are directly transferred to the p-dopant, 2,2′-(perfluoronaphthalene-2,6-diylidene) dimalononitrile (F6-TCNNQ) (ELUMO = 5.4 eV). This doping process enhances the conductivity of doped OS by different ways from the ordinary doping mechanism of generating free hole carriers and filling trap states of doped OS. Trap density and trap energy are analysed by impedance spectroscopy and it is shown that the direct charge transfer from deep trap states of host to dopants enhances the hole mobility of doped OS and the I–V characteristics of hole only devices.     

Highly ordered C60 films on epitaxial Fe/MgO(0 0 1) surfaces for organic spintronics

Hybrid interfaces between ferromagnetic surfaces and carbon-based molecules play an important role in organic spintronics. The fabrication of devices with well defined interfaces remains challenging, however, hampering microscopic understanding of their operation mechanisms. We have studied the crystallinity and molecular ordering of C₆₀ films on epitaxial Fe/MgO(0 0 1) surfaces, using X-ray diffraction and scanning tunneling microscopy (STM). Both techniques confirm that fcc molecular C₆₀ films with a (1 1 1)-texture can be fabricated on epitaxial bcc-Fe(0 0 1) surfaces at elevated growth temperatures (100–130 °C). STM measurements show that C₆₀ monolayers deposited at 130 °C are highly ordered, exhibiting quasi-hexagonal arrangements on the Fe(0 0 1) surface oriented along the [1 0 0] and [0 1 0] directions. The mismatch between the surface lattice of the monolayer and the bulk fcc C₆₀ lattice prevents epitaxial overgrowth of multilayers.     

Effect of Al dopant concentration on structural,optical and photoconducting properties in nanostructured zinc oxide thin films

Thin films of undoped and doped ZnO, with different Al concentrations (1–5 wt%) were deposited onto glass substrates, by the sol–gel spin coating method. Grazing incidence X-ray diffraction (GIXRD) studies confirmed the nature of films as poly-crystalline, with typical hexagonal wurtzite structure. The films showed variation in crystallite size and change in relative intensities, upon different Al doping concentrations. The surface morphology of the films examined using FE-SEM, showed the grain size becoming smaller upon Al doping. The influence of Al with different concentrations, onto ZnO on the optical absorption and transmittance was studied using UV–Vis–NIR spectrophotometer in the wavelength range 300–2500 nm. The UV absorption shifted towards shorter wavelength upon Al doping. The average transmittance in the visible region increased for Al doped films up to 1–2 wt% and decreased for other concentration. The dark and photo conductivity measurements of the films indicated increase in the current values upon doping up to 1–2 wt% of Al and decreased for further concentrations. The rise and decay time measured from the photoresponse study, indicate larger values of rise time for the doped films compared to undoped ZnO. However, the film with 1–2 wt% doping of Al showed better response within the doping concentration. The thermal activation energy obtained from temperature-dependant conductivity showed decrease in the value upon Al doping up to 2 wt% and increased beyond this concentration in the temperature range 300–400 K.     

A comparative study of electrical and optical properties of InN and In0.48Ga0.52N

We present results of our studies concerning electrical and optical properties of In_0.48Ga_0.52N and InN. Hall measurement were carried out at temperatures between T=77 and 300 K. Photoluminescence (PL) spectrum in InN and In_0.48Ga_0.52N. InN has a single peak at 0.77 eV at 300 K. However, the PL in In_0.48Ga_0.52N has two peaks; a prominent peak at 1.16 eV and a smaller peak at 1.55 eV. These two peaks are attributed to Indium segregation corresponding to a high Indium concentration of 48% and a low concentration of 36%. High electric field measurements indicate that drift velocity that tends to saturate at around V_d=1.0×10⁷ cm/s at 77 K in InN at an electric field of F=12 kV/cm. However, in In_0.48Ga_0.52N the I–V curve is almost linear up to an electric field of F=45 kV/cm, where the drift velocity is V_d=1.39×10⁶ cm/s. At applied electric fields above this value a S-type negative differential resistance (NDR) is observed leading to an instability in the current and to the irreversible destruction of the sample.     

Dinuclear cyclometalated platinum (II) complexes: Synthesis,photophysics, and monomolecular electroluminescence

Two novel dinuclear platinum (II) complexes of (C₁₂Rppy)₂Pt₂(dipic) (R = H and F) were synthesized and characterized, where C₁₂Rppy is a 2-phenylpyridine derivative modified with dodecyloxy groups and dipic is a bi-picolinic acid derivative linked by biphenyl unit. Their physical, surface morphologies and optoelectronic properties, as well as molecular orbitals calculation were investigated. Intense excimer emission for both dinuclear platinum (II) complexes were observed in their neat films rather than in their dichloromethane solution under photo-excitation. In contrary, these dinuclear platinum (II) complexes exhibited a stronger monomolecular emission instead of excimer emission in their doped single-emissive-layer polymer light-emitting devices (PLEDs) under electric field owing to the effect of two alkyloxy groups in the ligand of 2-phenylpyridine. Better electroluminescent emission with a maximum current efficiency of 1.3 cd/A and a maximum luminance of 1407 cd/cm² was observed in the (C₁₂Hppy)₂Pt₂(dipic)-doped devices. To our best knowledge, the performance of (C₁₂Rppy)₂Pt₂(dipic) (R = H and F) is among the top values for the solution-processed dinuclear platinum (II) complex-based PLEDs reported so far.     

High-performance n-type organic field-effect transistors fabricated by ink-jet printing using a C60 derivative

We report on the performance of ink-jet-printed n-type organic thin-film transistors (OTFTs) based on a C₆₀ derivative, namely, C₆₀-fused N-methyl-2-(3-hexylthiophen-2-yl)pyrrolidine (C₆₀TH-Hx). The new devices exhibit excellent n-channel performance, with a highest mobility of 2.8 × 10^?2 cm² V^?1 s^?1, an I_On/I_Off ratio of about 1 × 10⁶, and a threshold voltage of 7 V. The C₆₀TH-Hx films show large crystalline domains that result from the influence of an evaporation-induced flow, thus leading to high electron mobility in the ink-jet-printed devices.     

Annealing effects on physical properties of doped CdTe thin films for photovoltaic applications

Polycrystalline Cadmium Telluride (CdTe) thin films were prepared on glass substrates by thermal evaporation at the chamber ambient temperature and then annealed for an hour in vacuum ~1×10⁻⁵ mbar at 400 °C. These annealed thin films were doped with copper (Cu) via ion exchange by immersing these films in Cu (NO₃)₂ solution (1 g/1000 ml) for 20 min. Further these films were again annealed at different temperatures for better diffusion of dopant species. The physical properties of an as doped sample and samples annealed at different temperatures after doping were determined by using energy dispersive x-ray analysis (EDX), x-ray diffraction (XRD), Raman spectroscopy, transmission spectra analysis, photoconductivity response and hot probe for conductivity type. The optical band gap of these thermally evaporated Cu doped CdTe thin films was determined from the transmission spectra and was found to be in the range 1.42–1.75 eV. The direct energy band gap was found annealing temperatures dependent. The absorption coefficient was >10⁴ cm⁻¹ for incident photons having energy greater than the band gap energy. Optical density was observed also dependent on postdoping annealing temperature. All samples were found having p-type conductivity. These films are strong potential candidates for photovoltaic applications like solar cells.     

Effect of fluorine doping on the structural,optical and electrical properties of spray deposited cadmium stannate thin films

Cadmium stannate (Cd₂SnO₄) thin films were coated on Corning 1737 glass substrates at 540 °C by spray pyrolysis technique, from the aqueous solution of cadmium acetate and tin (II) chloride precursors. Fluorine doped Cd₂SnO₄ (F: Cd₂SnO₄) thin films were prepared by adding ammonium fluoride in the range of 0–5 wt% of the total weight of cadmium acetate and tin (II) chloride in the spray solution. Thickness of the prepared films is about 300 nm. X-ray diffraction analysis of the Cd₂SnO₄ and 3 wt% F: Cd₂SnO₄ films shows the signature for the growth along (222) direction. Scanning electron micrographs showed that fluorine doping effectively modifies the surface morphology of Cd₂SnO₄ films. Average optical transmittance in the visible region (500–850 nm) for Cd₂SnO₄ is ~79% and it is increased to ~83% for 1 wt% doping concentration of the NH₄F in the solution. Fluorescence spectra of F: Cd₂SnO₄ (1 wt% and 3 wt%) exhibit peak at 601 nm. F: Cd₂SnO₄ film (1 wt%) shows mobility of ~42 cm²/V s, carrier concentration of ~9.5×10¹⁹ cm^?3 and resistivity of ~1.5×10^?3 Ω cm.     

Structural characterization of Zn1−xCdxO (0≤x≤0.20) microrods grown by spray pyrolysis

Zn_1−xCd_xO (x= 0.00, 0.05, 0.10, 0.15 and 0.20) thin films were obtained by spray pyrolysis and characterized by XRD, SEM, EDAX and optical measurements. The Zn_1−xCd_xO microrods are in the wurtzite crystallographic phase with (0 0 2) preferred orientation. A narrowing of the fundamental band gap from 3.30 to 3.10 eV was observed with the increasing nominal Cd content up to 20 at% due to the direct modulation of the band gap caused by Cd substitution. The undoped ZnO film showed two emission bands in the spectra: one sharp UV luminescence at ∼382 nm and one broad visible emission ranging from 430 to 600 nm. The sharp peak at ∼382 nm is split into two at 376 and 400 nm upon Cd doping at levels of 5 and 10 at%. However this splitting is not observed in the doped ZnO samples containing 15 at% Cd and more. It should also be mentioned that the broad peak at the range of 430–600 nm has almost disappeared in the films containing 5, 10 and 15 at% Cd.     

Evaluation of different oxidation methods for silicon for scanning capacitance microscopy

Different oxides, namely, native, thermal, and wet-chemical (H₂SO₄+H₂O₂ based) oxides on Si are evaluated in the context of scanning capacitance microscopy (SCM). The samples investigated consisted of uniformly doped Si substrates and p-type epitaxial doping-staircase structures with concentrations ranging from 5×10¹⁴ to 2×10¹⁹ cm⁻³. The bias for which the SCM signal (dC/dV) is maximised for the lowest doped region was used for comparing the different oxidation methods. It is shown that for a better evaluation of the surface oxide properties, it is essential to obtain dC/dV curves for a sufficiently large doping range. Best results in terms of low values of flat-band voltages (1 V), uniformity, and consistency across a large doping range were obtained for the wet-chemical oxide. For the native oxide case, the difference in the dC/dV peak bias values obtained at regions doped to 5×10¹⁴ to 10¹⁷ cm⁻³ was anomalously large and suggests appreciable distortion of the dC/dV curves. For the same oxidation procedure the full-width at half-maximum of the dC/dV curve obtained on the cleaved surface is typically 2 times larger than that on the planar (1 0 0) surface. It is most likely that interface states are responsible for the observed distortion.     

Effect of doping concentration on the properties of bismuth doped tin sulfide thin films prepared by spray pyrolysis

Bismuth doped tin sulfide (SnS:Bi) thin films were deposited onto glass substrates by the spray pyrolysis technique at the substrate temperature of 350 °C. The effect of doping concentration [Bi/Sn] on their structural, optical and electrical properties was investigated as a function of bismuth doping between 0 and 8 at%. The XRD results showed that the films were polycrystalline SnS with orthorhombic structure and the crystallites in the films were oriented along (111) direction. Atomic force microscopy revealed that the particle size and surface roughness of the films increased due to Bi-doping. Optical analysis exhibited the band gap value of 1.40 eV for SnS:Bi (6 at%) which was lower than the band gap value for 0 at% of Bi (1.60 eV). The film has low resistivity of 4.788×10⁻¹ Ω-cm and higher carrier concentration of 3.625×10¹⁸ cm⁻³ was obtained at a doping ratio of 6 at%.