Analysis of a Flexible Photoconductor, Manufactured with Organic Semiconductor Films.

This work presents the evaluation of the electrical behavior of a flexible photoconductor with a planar heterojunction architecture made up of organic semiconductor films deposited by high vacuum evaporation. The heterojunction was characterized in its morphology and mechanical properties by scanning electron microscopy and atomic force microscopy. The electrical characterization was carried out through the approximations of ohmic and SCLC (Space-Charge Limited Current) behaviors using experimental J-V (current density-voltage) curves at different voltages and under different light conditions. The optimization of the photoconductor was carried out through annealing and accelerated lighting processes. With these treatments, the Knoop Hardness of the flexible photoconductor has reached a value of 8 with a tensile strength of 5.7 MPa. The ohmic and SCLC approximations demonstrate that the unannealed device has an ohmic behavior, whereas the annealed device has an SCLC behavior, and after the optimization process, an ohmic behavior and a maximum current density of 0.34 mA/mm2 were obtained under blue light. The approximations of the device's electron mobility (µn) and free carrier density (n0) were performed under different light conditions, and the electrical activation energy and electrical gap were obtained for the flexible organic device, resulting in appropriate properties for these applications.

Influence of the Coordinated Ligand on the Optical and Electrical Properties in Titanium Phthalocyanine-Based Active Films for Photovoltaics.

Tetravalent titanyl phthalocyanine (TiOPc) and titanium phthalocyanine dichloride (TiCl2Pc) films were deposited via the high-vacuum thermal evaporation technique and subsequently structurally and morphologically characterized, to be later evaluated in terms of their optoelectronic behavior. The IR and UV-vis spectroscopy of the films displayed α- and ß-phase signals in TiOPc and TiCl2Pc. Additionally, the UV-vis spectra displayed the B and Q bands in the near-UV region of 270-390 nm and in the visible region between 600 and 880 nm, respectively. The films presented the onset gap (~1.30 eV) and the optical gap (~2.85 eV). Photoluminescence emission bands at 400-600 nm and 800-950 nm are present for the films. One-layer ITO/TiCl2Pc or TiOPc/Ag and two-layer ITO/PEDOT:PSS/TiCl2Pc or TiOPc/Ag planar heterojunction devices with poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) deposited by the spin-coating technique were constructed. In these devices, an electrical activation energy between 0.18 and 0.21 eV and a refractive index between 1.14 and 1.44 were obtained. The devices presented a change in the J-V curves for the illuminated and darkness conditions, as much as 1.5 × 102 A/cm2, related to the device architecture and phthalocyanine ligand. The latter indicates that the films should be used for optoelectronic applications.

Fabrication and Characterization of Hybrid Hole Transporting Layers of Organotin (IV) Semiconductors within Molybdenum Oxide/Poly(3,4-ethylenedyoxithiophene) Polystyrene Sulfonate Matrices.

The hybrid film of molybdenum oxide (MoO3) and poly(3,4-ethylenedyoxithiophene) polystyrene sulfonate (PEDOT:PSS) is a promising candidate for use as hole transport layer (HTL) in low-cost devices. A fast, controllable and economic process was used to fabricate high-performance HTLs by adding organotin (IV) semiconductors to the MoO3/PEDOT:PSS films. These hybrid films were fabricated by spin-coating and the MoO3/PEDOT:PSS-organotin (IV) complex films were characterized by infrared spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM). Some mechanical and optical properties of the hybrid films were obtained and, to electrically characterize the hybrid films, hetero-junction glass/ITO/MoO3/PEDOT:PSS-organotin (IV) complex/Ag devices were prepared. Regarding the mechanical properties, the films have high plastic deformation, with a maximum stress of around 40 MPa and a Knoop hardness of 0.14. With respect to optical behavior, the films showed high transparency, with optical gap values between 2.8 and 3.5 eV and an onset gap of around 2.4 eV, typical of semiconductors. Additionally, the films in their respective devices show ambipolar and ohmic behavior with small differences depending on the substituent in organotin (IV) semiconductors. The MoO3/PEDOT:PSS matrix defines the mechanical behavior of the films and the tin complexes contribute their optoelectronic properties.

Efficient Film Fabrication and Characterization of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) (PEDOT:PSS)-Metalloporphine Nanocomposite and Its Application as Semiconductor Material.

The use of composite films with semiconductor behavior is an alternative to enhance the efficiency of optoelectronic devices. Composite films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and metalloporphines (MPs; M = Co, Cu, Pd) have been prepared by spin-coating. The PEDOT:PSS-MP films were treated with isopropanol (IPA) vapor to modify the polymer structure from benzoid to quinoid. The quinoid structure promotes improvements in the optical and electrical behavior of films. The composite films' morphology and structure were characterized using infrared and Raman spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM). Composite films were analyzed for their optical behavior by ultraviolet-visible spectroscopy: at λ < 450 nm, the films become transparent, indicating the capacity to be used as transparent electrodes in optoelectronic devices. At λ ≥ 450 nm, the absorbance in the films increased significantly. The CoP showed an 8 times larger current density compared to the CuP. A light induced change in the J-V curves was observed, and it is larger for the CoP. The conductivity values yielded between 1.23 × 102 and 1.92 × 103 Scm-1 and were higher in forward bias.

Innovative Implementation of an Alternative Tetrathiafulvene Derivative for Flexible Indium Phthalocyanine Chloride-Based Solar Cells.

Herein, we present the photovoltaic properties of an indium phthalocyanine chloride (InClPc)-based flexible planar heterojunction device, introducing the tetrathiafulvene derivative 4,4'-Dimethyl-5,5'-diphenyltetrathiafulvalene (DMDP-TTF) as the electron donor layer. UV-vis spectroscopy is widely used to characterize the electronic behavior of the InClPc/DMDP-TTF active layer. The interactions between the DMDP-TTF and phthalocyanine are predominantly intermolecular and the result of the aggregation of InClPc. Tauc bands were obtained at 1.41 and 2.8 eV; these energy peaks can result in a charge transfer ascribed to the transition from the DMDP-TTF to π-orbitals that are associated with the phthalocyanine ring or even with the same indium metal center. Conductive carbon (CC) was used for the cathode. Finally, an indium tin oxide (ITO)/InClPc/DMDP-TTF/CC device was fabricated by high-vacuum thermal evaporation onto a flexible substrate and the photovoltaic properties were evaluated. A diode type I-V curve behavior was observed with a photovoltaic response under illumination. A generated photocurrent of 2.25 × 10-2 A/cm2 was measured. A conductivity reduction with the incident photon energy from 1.61 × 10-7 S/cm to 1.43 × 10-7 S/cm is observed. The diode resistance presents two different behaviors with the applied voltage. A VTFL of 5.39 V, trap concentration of 7.74 × 1016 cm-3, and carrier mobility values of ~10-6 cm2/V s were calculated, showing improved characteristics via the innovative implementation of an alternative TTF-derivative, indicating that the DMDP-TTF has a strong interaction at the junction where free available states are increased, thus inducing higher mobilities due to the large number of π-orbitals, which indicates the feasibility of its use in solar cells technology.

Design of Promising Heptacoordinated Organotin (IV) Complexes-PEDOT: PSS-Based Composite for New-Generation Optoelectronic Devices Applications.

The synthesis of four mononuclear heptacoordinated organotin (IV) complexes of mixed ligands derived from tridentated Schiff bases and pyrazinecarboxylic acid is reported. This organotin (IV) complexes were prepared by using a multicomponent reaction, the reaction proceeds in moderate to good yields (64% to 82%). The complexes were characterized by UV-vis spectroscopy, IR spectroscopy, mass spectrometry, 1H, 13C, and 119Sn nuclear magnetic resonance (NMR) and elemental analysis. The spectroscopic analysis revealed that the tin atom is seven-coordinate in solution and that the carboxyl group acts as monodentate ligand. To determine the effect of the substituent on the optoelectronic properties of the organotin (IV) complexes, thin films were deposited, and the optical bandgap was obtained. A bandgap between 1.88 and 1.98 eV for the pellets and between 1.23 and 1.40 eV for the thin films was obtained. Later, different types of optoelectronic devices with architecture "contacts up/base down" were manufactured and analyzed to compare their electrical behavior. The design was intended to generate a composite based on the synthetized heptacoordinated organotin (IV) complexes embedded on the poly(3,4-ethylenedyoxithiophene)-poly(styrene sulfonate) (PEDOT:PSS). A Schottky curve at low voltages (<1.5 mV) and a current density variation of as much as ~3 × 10-5 A/cm2 at ~1.1 mV was observed. A generated photocurrent was of approximately 10-7 A and a photoconductivity between 4 × 10-9 and 7 × 10-9 S/cm for all the manufactured structures. The structural modifications on organotin (IV) complexes were focused on the electronic nature of the substituents and their ability to contribute to the electronic delocalization via the π system. The presence of the methyl group, a modest electron donor, or the non-substitution on the aromatic ring, has a reduced effect on the electronic properties of the molecule. However, a strong effect in the electronic properties of the material can be inferred from the presence of electron-withdrawing substituents like chlorine, able to reduce the gap energies.

Innovative Incorporation of Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) as Hole Carrier Transport Layer and as Anode for Organic Solar Cells Performance Improvement.

In this work, we present a comparative study of benzoid poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) as electrode and as hole carrier transport layer (HTL) in the manufacture of organic photovoltaic devices using Fischer metal-carbene complexes. The performance of the different devices was evaluated for solar cell applications. Scanning electronic microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the thin films that integrated the devices. A more ordered and crystallized active film microstructure is observed when using benzoid PEDOT:PSS as nucleation layer. The optical gap for both direct and indirect electronic transitions was evaluated from ultraviolet-visible spectroscopy data (UV-vis), as well as the absorption coefficient (α), and the values are in the range of 2.10-2.93 eV. Photovoltaic devices with conventional architecture, using two different chromium carbenes as active layers, were manufactured, and their electrical behavior was studied. The devices were irradiated with different wavelengths between the infrared and ultraviolet regions of the electromagnetic spectrum. Using the PEDOT:PSS film as hole carrier transport layer (HTL) decreases the slope on the ohmic and space charge limited current (SCLC) regions and eliminates the trap-charge limited current (T-CLC) mechanism. Furthermore, a saturation current of ~1.95 × 10-10 A and higher current values ~1.75 × 10-2 A at 4 V, ~4 orders in magnitude larger were observed. The PEDOT:PSS films as HTL in the devices reduced the injection barrier, thus showing a better performance than as anodes in this type of organic solar cells.

Comparative Study of Conduction Mechanisms in Disodium Phthalocyanine-Based Organic Diodes for Flexible Electronics.

In the current work, flexible diodes with flat heterojunction and dispersed heterojunction architecture were manufactured with to study the behavior of thin films of disodium phthalocyanine (Na2Pc). The thin film devices, using the electronic acceptor tetracyano-π-quinodimethane (TCNQ), were fabricated by high-vacuum thermal evaporation with annealing post-treatment in order to optimize their behavior. Theoretical calculations based on density functional theory (DFT) with dispersion force analysis were carried out in order to simulate molecular interactions and to establish the nature of the weak interactions between the Na2Pc and TCNQ fragments. In the optimized structure of the coupled Na2Pc-TCNQ, the electronic relationship between phthalocyanine and TCNQ was observed to be through hydrogen bonds with bond lengths of 2.94 and 3.13 Å. Dispersed heterojunction device current density values were considerably larger than those of the flat heterojunction device. Barrier heights of 1.024 and 0.909 eV and charge mobilities of 10-10 and 10-9 m2/Vs for the flat heterojunction device and the dispersed heterojunction device, respectively, were observed. A small effect was observed on the electrical properties by thermal annealing on the flat heterojunction device. The threshold voltage decreased from 1.203 to 1.147 V and φb decreased by 0.001 eV.

New Approaches in Flexible Organic Field-Effect Transistors (FETs) Using InClPc.

Organic semiconductor materials have been the center of attention because they are scalable, low-cost for device fabrication, and they have good optical properties and mechanical flexibility, which encourages their research. Organic field-effect transistors (OFETs) have potential applications, specifically in flexible and low-cost electronics such as portable and wearable technologies. In this work we report the fabrication of an InClPc base flexible bottom-gate/top-contact OFET sandwich, configured by the high-evaporation vacuum technique. The gate substrate consisted of a bilayer poly(ethylene terephthalate) (PET) and indium-tin oxide (ITO) with nylon 11/Al2O3. The device was characterized by different techniques to determine chemical stability, absorbance, transmittance, bandgap, optical properties, and electrical characteristics in order to determine its structure and operational properties. IR spectroscopy verified that the thin films that integrated the device did not suffer degradation during the deposition process, and there were no impurities that affected the charge mobility in the OFET. Also, the InClPc semiconductor IR fingerprint was present on the deposited device. Surface analysis showed evidence of a nonhomogeneous film and also a cluster deposition process of the InClPc. Using the Tauc model, the device calculated indirect bandgap transitions of approximately 1.67 eV. The device's field effect mobility had a value of 36.2 cm2 V-1 s-1, which was superior to mobility values obtained for commonly manufactured OFETs and increased its potential to be used in flexible organic electronics. Also, a subthreshold swing of 80.64 mV/dec was achieved and was adequate for this kind of organic-based semiconductor device. Therefore, semiconductor functionality is maintained at different gate voltages and is transferred accurately to the film, which makes these flexible OFETs a good candidate for electronic applications.

New Development of Membrane Base Optoelectronic Devices.

It is known that one factor that affects the operation of optoelectronic devices is the effective protection of the semiconductor materials against environmental conditions. The permeation of atmospheric oxygen and water molecules into the device structure induces degradation of the electrodes and the semiconductor. As a result, in this communication we report the fabrication of semiconductor membranes consisting of Magnesium Phthalocyanine-allene (MgPc-allene) particles dispersed in Nylon 11 films. These membranes combine polymer properties with organic semiconductors properties and also provide a barrier effect for the atmospheric gas molecules. They were prepared by high vacuum evaporation and followed by thermal relaxation technique. For the characterization of the obtained membranes, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) were used to determine the chemical and microstructural properties. UV-ViS, null ellipsometry, and visible photoluminescence (PL) at room temperature were used to characterize the optoelectronic properties. These results were compared with those obtained for the organic semiconductors: MgPc-allene thin films. Additionally, semiconductor membranes devices have been prepared, and a study of the device electronic transport properties was conducted by measuring electrical current density-voltage (J-V) characteristics by four point probes with different wavelengths. The resistance properties against different environmental molecules are enhanced, maintaining their semiconductor functionality that makes them candidates for optoelectronic applications.