Pentacene Thin Films Research Articles

Effect of Iodine Doped Pentacene Thin Film on the Performance of Organic Light Emitting Diode

The study investigated the effect of iodine-doped pentacene film as a buffer layer in an organic light-emitting diode (OLED). In this study, an ITO (indium tin oxide)-based sample is used as a reference device for comparative purposes. In OLED devices, the buffer layers were deposited using the doping of iodine vapor with the pentacene materials under proper conditions. The thermal treatment of the doped pentacene film results in increasing the conductivity of the buffer layer. Surface morphology for the bilayer anode was carried out by FESEM (Field Emission Scanning Electron Microscope) analysis. In our work, maximum luminance of 2345 cd/m2 and current efficiency of 5.4 cd/A are obtained, along with more stability performance under annealing treatment in the device structure of FTO/iodine-doped pentacene (30 nm)/TPD [N, N′-Bis(3-methyl phenyl)-N, N′-diphenylbenzidine] (44 nm)/Alq3 [Tris(8-hydroxyquinoline)aluminum(III)] (52 nm)/LiF (lithium fluoride) (5 nm)/Al (aluminum) (110 nm).

Coherent photoexcitation of entangled triplet pair states.

The functional properties of organic semiconductors are defined by the interplay between optically bright and dark states. Organic devices require rapid conversion between these bright and dark manifolds for maximum efficiency, and one way to achieve this is through multiexciton generation (S1→1TT). The dark state 1TT is typically generated from bright S1 after optical excitation; however, the mechanistic details are hotly debated. Here we report a 1TT generation pathway in which it can be coherently photoexcited, without any involvement of bright S1. Using <10-fs transient absorption spectroscopy and pumping sub-resonantly, 1TT is directly generated from the ground state. Applying this method to a range of pentacene dimers and thin films of various aggregation types, we determine the critical material properties that enable this forbidden pathway. Through a strikingly simple technique, this result opens the door for new mechanistic insights into 1TT and other dark states in organic materials.

Design of Pentacene Thin-Film Transistor Based Hydrogen Gas Sensor with High-K Dielectric Materials for High Sensitivity

Electrical properties of an organic field-effect transistor were modelled in top gate top contact (TGTC) geometry and H2 gas sensors were designed for increased sensitivity based on the structure. Safety concerns related to hydrogen usage must be addressed; these hazardous characteristics include a wide flammable range (4%–75%) that results in a rapid burning velocity, a low minimum ignition energy (0.017 mJ), a high heat of combustion (143 kJ g−1), and the high diffusivity of hydrogen gas (0.61 cm2 s−1 in the air). These characteristics make it impossible to control hydrogen combustion after a specific time. All simulations were performed in the Silvaco TCAD ATLAS tool. We analysed the driving principle of gas sensors and introduced gas sensing properties in OFET using platinum metal at the gate electrode for H2 gas detection. IOFF, ION, and VTH are sensitivity parameters that alter when the metalwork function of the gate changes with respect to the gas present on it. The designed sensor was analysed for different dielectric materials. Results demonstrate that the increase in sensitivity for OFET-based H2 sensors is 73.4%, 80.7%, 90.5%, and 95.6% when the work function changes by 50, 100, 150, and 200 meV for Pt gate electrodes with an increase in dielectric value of insulating layer from SiO2 (3.9) to La2O3 (27). Results were compared with the In1-xGaxAs CGNWFET-based H2 sensor as the work function varies at 200 meV,the sensitivity enhancement with OFET-based H2 sensors is 8.09%.

Stress-driven recrystallization of pentacene films via diffusion-induced ingress of MOF nanocrystals into the grain boundaries

Metal-organic frameworks (MOFs) have been identified as versatile candidates for producing functional materials for various applications. However, the growth of MOF thin film becomes challenging due to non-availability of a proper solvent that restricts the use of the materials in electronic sensor fabrication. The receptor molecules in sensors are often used to functionalize the semiconducting channel. However, integrating such molecules degrade the crystallinity of channel materials, leading to poor sensor performance. In this work, we report the growth of a MOF (CPO-27-Ni) thin film and the recrystallization of semiconducting pentacene thin films due to diffusion of the crystallites into the grain boundaries. MOF films were successfully spin coated at various revolutions per minute (rpm) on pentacene surfaces. The growth of MOF films was studied using statistical analysis of rough surfaces by utilizing scaling theory to capture the evolution of surface morphologies. The x-ray reflectivity study unveiled the diffusion-induced ingress of the MOF through the grain boundaries of pentacene films that imparts compressive stress within the grains leading to subsequent rearrangement of pentacene molecules in the thin-film phase and recrystallizes the bulk crystallographic phase, which in a way will enhance the device performance.

Efficient Energy Transfer and Singlet Fission in Co‐Deposited Thin Films of Pentacene and Anthradithiophene

AbstractCo‐deposited molecular heterostructures with statistical intermixing of the constituents are attractive candidates to tune the optical and the transport properties, as well as the ability to promote photophysical processes like singlet fission. In order to comprehend and control the singlet fission mechanism in these systems, it is of utmost interest to study the underlying excited state dynamics. In this work, thin films of anthradithiophene blended with the efficient singlet fission material pentacene are investigated by means of time‐resolved and temperature‐dependent photoluminescence spectroscopy with a time resolution of a few picoseconds. The analysis of the photoluminescence dynamics points toward efficient funneling of excitons from anthradithiophene via isolated pentacene molecules to agglomerates of pentacene, where eventually singlet fission occurs. The efficient and largely temperature‐independent quenching of the luminescence in anthradithiophene is attributed to a favorable cascade‐like alignment of the energy levels, and it is hypothesized that Förster resonance energy transfer is the main driving mechanism for exciton transport to pentacene agglomerates. The system investigated here can serve as a blueprint for the design of other molecular heterostructures with spatially separated light harvesting and singlet fission regions.

Cluster-Based Approach Utilizing Optimally Tuned TD-DFT to Calculate Absorption Spectra of Organic Semiconductor Thin Films.

The photophysics of organic semiconductor (OSC) thin films or crystals has garnered significant attention in recent years since a comprehensive theoretical understanding of the various processes occurring upon photoexcitation is crucial for assessing the efficiency of OSC materials. To date, research in this area has relied on methods using Frenkel-Holstein Hamiltonians, calculations of the GW-Bethe-Salpeter equation with periodic boundaries, or cluster-based approaches using quantum chemical methods, with each of the three approaches having distinct advantages and disadvantages. In this work, we introduce an optimally tuned, range-separated time-dependent density functional theory approach to accurately reproduce the total and polarization-resolved absorption spectra of pentacene, tetracene, and perylene thin films, all representative OSC materials. Our approach achieves excellent agreement with experimental data (mostly ≤0.1 eV) when combined with the utilization of clusters comprising multiple monomers and a standard polarizable continuum model to simulate the thin-film environment. Our protocol therefore addresses a major drawback of cluster-based approaches and makes them attractive tools for OSC investigations. Its key advantages include its independence from external, system-specific fitting parameters and its straightforward application with well-known quantum chemical program codes. It demonstrates how chemical intuition can help to reduce computational cost and still arrive at chemically meaningful and almost quantitative results.

Interpretation of Hopping Transport Based on Pentacene Thin-Film Transistors

Interpretation of Hopping Transport Based on Pentacene Thin-Film Transistors

Low- and high-frequency vibrations synergistically enhance singlet exciton fission through robust vibronic resonances.

Singlet exciton fission (SEF) is initiated by ultrafast internal conversion of a singlet exciton into a correlated triplet pair [Formula: see text]. The "reaction coordinates" for ultrafast SEF even in archetypal systems such as pentacene thin film remain unclear. Couplings between fast electrons and slow nuclei are ubiquitous across a range of phenomena in chemistry. Accordingly, spectroscopic detection of vibrational coherences in the [Formula: see text] photoproduct motivated investigations into a possible role of vibronic coupling, akin to that reported in several photosynthetic proteins. However, acenes are very different from chlorophylls with 10× larger vibrational displacements upon photoexcitation and low-frequency vibrations modulating intermolecular orbital overlaps. Whether (and if so how) these unique features carry any mechanistic significance for SEF remains a poorly understood question. Accordingly, synthetic design of new molecules aiming to mimic this process across the solar spectrum has broadly relied on tuning electronic couplings. We address this gap and identify previously unrecognized synergistic interplay of vibrations, which in striking contrast to photosynthesis, vitally enhances SEF across a broad, nonselective and, therefore, unavoidable range of vibrational frequencies. We argue that attaching mechanistic significance to spectroscopically observed prominent quantum beats is misleading. Instead, we show that vibronic mixing leads to anisotropic quantum beats and propose readily implementable polarization-based two-dimensional electronic spectroscopy experiments which uniquely distinguish vibrations which drive vibronic mixing and promote SEF, against spectator vibrations simply accompanying ultrafast internal conversion. Our findings introduce crucial ingredients in synthetic design of SEF materials and spectroscopy experiments aiming to decipher mechanistic details from quantum beats.

Synaptic memristors based on flexible organic pentacene thin films by the thermal evaporation method for neuromorphic computing

As the development of neuromorphic computing, it is meaningful to explore the synaptic memristors based on organic materials owing to their advantages in low cost, good mechanical flexibility and strong biocompatibility. In this work, organic pentacene thin films have been deposited on different substrates by the thermal evaporation method. The prepared thin films on SiO2/Si substrates demonstrate the co-existence of digital and analog resistive switching (RS) behaviors as well as a series of synaptic plasticity. To characterize the flexibility of the organic thin films, lateral memristors have been fabricated on polyethylene terephthalate (PET) substrates and demonstrate comparable RS behaviors when the bending radius is decreased to 1.26 cm or after 1000 bending. Furthermore, vertical memristors with Pt/pentacene/indium tin oxide (ITO) structure have been constructed when the organic thin films are deposited on ITO/PET substrates, exhibiting bipolar RS behaviors with low SET voltage of 0.65 V. The vertical synaptic memristors can be used to simulate the “learning-forgetting” experience of human brain. More importantly, an artificial neural network (ANN) can be simulated based on the vertical synaptic memristors, demonstrating 93.8 % recognition accuracy for hand-written digit image. This study suggests potential applications of the organic pentacene thin films for neuromorphic computing.

Local mapping of surface potential in pentacene thin film under gate bias voltage obtained by scanning kelvin probe microscopy.

We report the local surface potential mapping of pentacene film prepared by physical vapor deposition with scanning kelvin probe microscopy where the sample is scanned under different gate voltages. Surface topography and the corresponding potential maps were obtained simultaneously. Spatial distribution of the surface potential at a low gate voltage is clearly correlated with topographic features. A lower electrostatic potential was measured at the grain boundaries (GBs), suggesting that GBs behave as hole traps. This observation is bolstered by conductive atomic force microscopy (C-AFM) data, which reveals a higher conductivity within the grains as opposed to the GBs. An increase in gate voltage minimizes the potential differences at the grain and GBs, suggesting a modification in trap occupancy. We expect that these experimental results, along with existing theories, will provide a better understanding of the microstructural-electrical properties of pentacene film. RESEARCH HIGHLIGHTS: Local surface potential mapping of pentacene film with scanning kelvin probe microscopy. Correlation between the surface potential map and topography at a low gate voltage. Decrease of the potential distribution inhomogeneity by the gate voltage increasement. Higher conductivity at inner grain than grain boundary in conductive atomic force microscopy.

Electronic States of Pentacene Thin Films at Interfaces with Ionic-Liquid Layers Probed by Photoelectron Yield Spectroscopy

Electronic States of Pentacene Thin Films at Interfaces with Ionic-Liquid Layers Probed by Photoelectron Yield Spectroscopy

Nanoscale Quantized Oscillations in Thin‐Film Growth Greatly Enhance Transconductance in Organic Transistors

AbstractA growth mode of pentacene thin films deposited by high vacuum sublimation where the morphology versus thickness h “rings” back and forth between rough 3D films with pyramid islands and smooth 2D films with ziqqurat islands is discovered. The roughness σ versus h exhibits seamless coherent oscillations whose amplitude and wavelength increase as integer multiples of 1.5 ML thickness. The quantized oscillations are reconducted to dynamic wetting/dewetting transitions involving the upper layers of pentacene film. Importantly, the transconductance of organic field effect transistors, either in solid state or electrolyte‐gated, exhibits antiphase oscillations with one‐decade swing. Charge mobilities in the wetting regime reach 0.1 cm2 V−1 s−1, in line with high‐end values reported for thin‐film pentacene transistors. Controlling this growth mode enables the limitations of charge transport imposed by the roughening transition to be overcome, a universal feature of high vacuum growth to date.

Early Stage Growth Process of Dinaphtho[2,3‐b:2',3'‐f]thieno[3,2‐b]thiophene (DNTT) Thin Film

The early stage growth of dinaphtho[2,3‐b:2',3'‐f]thieno[3,2‐b]thiophenes (DNTTs) thin films are investigated using grazing incidence X‐ray diffraction (GIXD) and surface morphology analysis using atomic force microscopy (AFM). The thin‐film growth conditions are controlled using a slow deposition method. The vertical orientation of DNTT is confirmed from the growth of the first layer using GIXD. The morphologies of the first‐layer grains are universal in the growth rate range of 0.155–0.017 ML min−1. In addition, the dependence of the nuclei density on the deposition flow rate indicates that two molecules (dimers) are required for nucleation. This result suggests that fewer molecules are sufficient for nucleation in the case of DNTT compared to pentacene thin film growth on SiO2.

Growth and Characterization of Centimeter-Scale Pentacene Crystals for Optoelectronic Devices

In this work, we present results on the growth of centimeter-scale pentacene crystals using the physical vapor transport method in a dual-temperature zone horizontal furnace. It was established that intensive crystal growth processes occurred in transition regions with sudden temperature changes, while crystal growth was practically not observed in regions with slightly varying temperatures. During crystal growth, co-precipitating golden needle-like crystals reaching lengths of more than 10 mm were obtained. Using the method of single-crystal X-ray diffraction at 85 and 293 K for dark-blue lamellar pentacene crystals, the crystal structure was refined in a triclinic system with sp.gr. P1¯. It was established that the golden needle crystals consisted of molecules of the pentacene derivative—5,14-pentacenedione, the crystal structure of which was solved for the first time in a rhombic system with sp.gr. P212121. The absorption and luminescence spectra of pentacene and 5,14-pentacenedione in toluene solutions were obtained and analyzed. The electrical properties of the prepared pentacene thin films and single crystals grown under physical vapor transport conditions were evaluated by fabricating and characterizing field-effect transistors (FETs). It was shown that the presence of impurities in the commercial pentacene material had a significant effect on the morphological quality of thin polycrystalline films and noticeably reduced the hole mobility.

The Effect of C60 and Pentacene Adsorbates on the Electrical Properties of CVD Graphene on SiO2

Graphene is an excellent 2D material for vertical organic transistors electrodes due to its weak electrostatic screening and field-tunable work function, in addition to its high conductivity, flexibility and optical transparency. Nevertheless, the interaction between graphene and other carbon-based materials, including small organic molecules, can affect the graphene electrical properties and therefore, the device performances. This work investigates the effects of thermally evaporated C60 (n-type) and Pentacene (p-type) thin films on the in-plane charge transport properties of large area CVD graphene under vacuum. This study was performed on a population of 300 graphene field effect transistors. The output characteristic of the transistors revealed that a C60 thin film adsorbate increased the graphene hole density by (1.65 ± 0.36) × 1012 cm-2, whereas a Pentacene thin film increased the graphene electron density by (0.55 ± 0.54) × 1012 cm-2. Hence, C60 induced a graphene Fermi energy downshift of about 100 meV, while Pentacene induced a Fermi energy upshift of about 120 meV. In both cases, the increase in charge carriers was accompanied by a reduced charge mobility, which resulted in a larger graphene sheet resistance of about 3 kΩ at the Dirac point. Interestingly, the contact resistance, which varied in the range 200 Ω-1 kΩ, was not significantly affected by the deposition of the organic molecules.

Strong light-matter coupling in pentacene thin films on plasmonic arrays.

Utilizing strong light-matter coupling is an elegant and powerful way to modify the energy landscapes of excited states of organic semiconductors. Consequently, the chemical and photophysical properties of these organic semiconductors can be influenced without the need of chemical modification but simply by implementing them in optical microcavities. This has so far mostly been shown in Fabry-Pérot cavities and with organic single crystals or diluted molecules in a host matrix. Here, we demonstrate strong, simultaneous coupling of the two Davydov transitions in polycrystalline pentacene thin films to surface lattice resonances supported by open cavities made of silver nanoparticle arrays. Such thin films are more easily fabricated and, together with the open architecture, more suitable for device applications.

Erratum: Structural and Optical Properties of TIPS Pentacene Thin Film Exposed to Gamma Radiation

Erratum: Structural and Optical Properties of TIPS Pentacene Thin Film Exposed to Gamma Radiation

Exciton Dynamics in MoS2-Pentacene and WSe2-Pentacene Heterojunctions.

We measured the exciton dynamics in van der Waals heterojunctions of transition metal dichalcogenides (TMDCs) and organic semiconductors (OSs). TMDCs and OSs are semiconducting materials with rich and highly diverse optical and electronic properties. Their heterostructures, exhibiting van der Waals bonding at their interfaces, can be utilized in the field of optoelectronics and photovoltaics. Two types of heterojunctions, MoS2-pentacene and WSe2-pentacene, were prepared by layer transfer of 20 nm pentacene thin films as well as MoS2 and WSe2 monolayer crystals onto Au surfaces. The samples were studied by means of transient absorption spectroscopy in the reflectance mode. We found that A-exciton decay by hole transfer from MoS2 to pentacene occurs with a characteristic time of 21 ± 3 ps. This is slow compared to previously reported hole transfer times of 6.7 ps in MoS2-pentacene junctions formed by vapor deposition of pentacene molecules onto MoS2 on SiO2. The B-exciton decay in WSe2 shows faster hole transfer rates for WSe2-pentacene heterojunctions, with a characteristic time of 7 ± 1 ps. The A-exciton in WSe2 also decays faster due to the presence of a pentacene overlayer; however, fitting the decay traces did not allow for the unambiguous assignment of the associated decay time. Our work provides important insights into excitonic dynamics in the growing field of TMDC-OS heterojunctions.

Effect of Static Magnetic Field on &lt;i&gt;Anchusa-Italica&lt;/i&gt;-Doped Pentacene

This work is devoted to the influence of magnetized water on dye extracted from Anchusa Italica plant and doped pentacene thin films. The findings resulted in optoelectronic behavior, showing that using magnetized water in the extraction process gives rise to distinct and superior characteristics as compared to using regular water. The Fourier-transform infrared method was used to analyze the structural properties of an Anchusa Italica-doped pentacene thin film. A comparative study on two samples was carried out: the first sample was affected by a static magnetic field and the other one was not. Optical properties including the absorption spectra absorption coefficient, optical energy gap, conventional and refractive factors were investigated by applying ultraviolet-visible spectroscopy ranging from 300 to 900 nm. The estimated band gap edge of the dye/doped pentacene affected with magnetization was reduced from 2.61 to 1.76 eV and converted into the recommended direct band gap to contribute to optical systems. The absorption spectra of the sample with magnetization effect appears to be more efficient than the one extracted using regular water. The power transmission coefficients (indirect to direct) were also affected because of the magnetic extraction procedure. The complex refractive index was used to study the magnetization effect on the resonance mode and transparent indicator. The absorption index was enhanced to 570 nm in the spectrum, whereas there was also a low attenuation coefficient. This is the first time that magnetized sol has been used in dye extraction processes.

Correction to “Thin Films and Bulk Phases Conucleate at the Interfaces of Pentacene Thin Films”

Correction to “Thin Films and Bulk Phases Conucleate at the Interfaces of Pentacene Thin Films”