P-type Pentacene Research Articles

Determination of the Electronic Structure, Charge-transfer, and Optical Properties of Neutral, Anionic, and Cationic Perfluoropentacene

Perfluoropentacene ( is an n-type organic semiconductor made by fluorination of p-type semiconductor Pentacene and can find applications in molecular thin film devices. In this work, a theoretical study of Perfluoropentacene was carried out based on density functional theory (DFT) and time dependent (TD-DFT) as implemented in Gaussian 09 package using B3LYP/6-311++G (d, p) and B3LYP/6-31+G(d) basis sets. The electronic, charge transfer, Linear and nonlinear optical properties of the molecule were calculated and reported for the neutral, anionic, and cationic forms of the molecule. The results show that the cationic state of the molecule has the strongest bond length at R(28,32) using the basis sets B3LYP/6-311++G (d,p) and the weakest bond length was found at R(4,6) in the ionic state with 6-31+G (d) basis set. The energy gap obtained for the neutral molecule using 6-31+G (d) and 6-311++G (d,p) basis sets are 2.00eV, 1.99eV respectively. The results show a strong agreement with a previously related work that reported the energy gap as 2.02eV thus indicating high stability of the molecule. Perfluoropentacene has the highest value of chemical hardness of 1.3929eV in its anionic state (Beta MO), so is considered to be harder and more stable than the neutral and cationic. The findings also revealed that with toluene as solvent, the strongest absorption was found at wavelength of 738.38, highest oscillator strength of 0.0599 and the lowest excitation energy of 1.6791eV. The calculated results of polarizability, first and second hyperpolarizability confirm that this molecule is a good non-linear optical material. On the whole, the molecule could be a good material for optoelectronic applications.

Ultraviolet Light-Densified Oxide-Organic Self-Assembled Dielectrics: Processing Thin-Film Transistors at Room Temperature.

Low-temperature, solution-processable, high-capacitance, and low-leakage gate dielectrics are of great interest for unconventional electronics. Here, we report a near room temperature ultraviolet densification (UVD) methodology for realizing high-performance organic-inorganic zirconia self-assembled nanodielectrics (UVD-ZrSANDs). These UVD-ZrSAND multilayers are grown from solution in ambient, densified by UV radiation, and characterized by X-ray reflectivity, atomic force microscopy, X-ray photoelectron spectroscopy, and capacitance measurements. The resulting UVD-ZrSAND films exhibit large capacitances of >700 nF/cm2 and low leakage current densities of <10-7 A/cm2, which rival or exceed those synthesized by traditional thermal methods. Both the p-type organic semiconductor pentacene and the n-type metal oxide semiconductor In2O3 were used to investigate UVD-ZrSANDs as the gate dielectric in thin-film transistors, affording mobilities of 0.58 and 26.21 cm2/(V s), respectively, at a low gate voltage of 2 V. These results represent a significant advance in fabricating ultra-thin high-performance dielectrics near room temperature and should facilitate their integration into diverse electronic technologies.

Signal amplification with patterned conducting polymer electrodes based organic thin film transistor circuit

Organic thin film transistors (OTFTs) fabricated with non-destructive patterning techniques are the building blocks in realizing flexible electronic interface for sensing applications. In this study, a single stage differential amplifier is demonstrated with flexible OTFTs. The OTFTs were fabricated with thermally evaporated Pentacene as the semiconducting layer. The electrodes of the OTFTs were realized using a conductive polymer composite, poyaniline:polystyrene sulphonic acid (PANi-PSS), patterned by a modified Parylene lift-off process. Electrical characteristics of bottom contact TFTs with polymeric PANi-PSS electrodes is superior to those with conventional metal electrodes due to a lower charge injection barrier and resultant lower contact resistance. The measurement of the transistor characteristics and the amplifier response reported has been carried out with a wafer probing test jig set up. The differential amplifier realized with p-type Pentacene transistors with mobility, 0.5 cm2/Vs, exhibited a voltage gain of 10 dB in a frequency bandwidth of 1 kHz.

Effective performance improvement based on dioctylbenzothienobenzothiophene/pentacene isotype organic heterojunction transistors

Organic thin film transistors (OTFTs) with isotype heterojunction semiconducting layers composed of p-type pentacene and dioctylbenzothienobenzothiophene (C8BTBT) have been fabricated. In our heterojunction OTFTs, continuous pentacene film is deposited on top of C8BTBT as a secondary semiconducting layer, which not only can play the role of interfacial layer for hole carriers injection from copper (Cu) source/drain (S/D) electrodes to C8BTBT but also provide another hole transport channel itself. The device performance is then effectively improved. According to the careful study of the C8BTBT/pentacene heterojunction from the film morphologies, it is found that the C8BTBT film facilitates the growth of the upper pentacene film which can further contribute to performance enhancement of the OTFTs. Moreover, diode characteristics with the C8BTBT/pentacene heterojunction show a negligible heterojunction effect that makes the off-state current of OTFTs easy to control. The resulting OTFT exhibits high performance with a mobility of 1.5 cm2/Vs and an on/off ratio of 105, even with low work function Cu S/D electrodes.

Three-Dimensional Topological Insulator Bi2Te3/Organic Thin Film Heterojunction Photodetector with Fast and Wideband Response from 450 to 3500 Nanometers.

In the pursuit of broadband photodetection materials from visible to mid-IR region, the fresh three-dimensional topological insulators (3D TIs) are theoretically predicted to be a promising candidate due to its Dirac-like stable surface state and high absorption rate. In this work, a self-powered inorganic/organic heterojunction photodetector based on n-type 3D TIs Bi2Te3 combined with p-type pentacene thin film was designed and fabricated. Surprisingly, it was found that the Bi2Te3/pentacene heterojunction photodetector exhibited a fast and wideband response from 450 to 3500 nm. The optimized responsivity of photodetector reached 14.89 A/W, along with the fast response time of 1.89 ms and the ultrahigh external quantum efficiency of 2840%. Moreover, at the mid-IR 3500 nm, our devices demonstrated a responsivity of 1.55 AW-1, which was several orders of magnitude higher than that of previous 3D TIs photodetector. These excellent properties indicate that the inorganic/organic heterojunction, that is, the combination of 3D TIs with organic materials, is an exciting structure for high performance photodetectors in the wideband detection region. On account of the fact that the device is constructed on mica substrate, this work also represents a potential scenario for flexible optoelectronic devices.

Effective performance improvement of organic thin film transistors by using tri-layer insulators

Organic thin film transistors (OTFTs) with silicon oxide (SiO2)/poly(4-vinylphenol) (PVP)/polymethylmethacrylate (PMMA) tri-layer structure (SPP) as dielectric layers have been fabricated. To verify the validity of such tri-layer structure, two different organic semiconductor materials such as p-type pentacene and n-type fluorinated copper phthalo–cyanine (F16CuPc) are both used for fabricating OTFTs. Comparing with the OTFTs even by using PMMA modification, the better interface quality existing between SPP dielectric and organic film leads a higher conductive efficiency for transport carriers in channel. And then the field effect carriers (hole in pentacene OTFTs and electron in F16CuPc OTFTs) mobilities are both increased obviously. Our results show the SPP dielectric structure can be widely used to improve performance of OTFTs.

A study of effects of electrode contacts on performance of organic-based light-emitting field-effect transistors

Herein is presented a comparative performance analysis of heterojunction organic-based light-emitting field-effect transistors (OLEFETs) with symmetric (Au only) and asymmetric (Au and LiF/Al) electrode contacts. The devices had a top source–drain contact with long-channel geometry and were produced by sequentially depositing p-type pentacene and n-type N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (P13) using a neutral cluster beam deposition apparatus. The spectroscopic, structural and morphological properties of the organic thin films were examined using photoluminescence (PL) spectroscopy, X-ray diffraction (XRD) method, laser scanning confocal and atomic force microscopy (LSCM, AFM). Based upon the growth of high-quality, well-packed crystalline thin films, the devices demonstrated ambipolar field-effect characteristics, stress-free operational stability, and light emission under ambient conditions. Various device parameters were derived from the fits of the observed characteristics. The hole mobilities were nearly equal irrespective of the electrode contacts, whereas the electron mobilities of the transistors with LiF/Al drain electrodes were higher due to the low injection barrier. For the OLEFETs with symmetric electrodes, electroluminescence (EL) occurred only in the vicinity of the hole-injecting electrode, whereas for the OLEFETs with asymmetric electrodes, the emission occurred in the vicinity of both hole- and electron-injecting electrodes. By tuning the carrier injection and transport through high- and low-work function metals, the hole-electron recombination sites could be controlled. The operating conduction and light emission mechanism are discussed with the aid of EL images obtained using a charge-coupled device (CCD) camera.

Solution-processed amorphous ZrO2 gate dielectric films synthesized by a non-hydrolytic sol-gel route.

Solution-processed zirconium oxide (ZrO2) dielectrics were formed via a non-hydrolytic sol–gel route at low-temperature, and are suitable for flexible thin film transistor (TFT) devices. Precursor solutions with equimolar zirconium halide and zirconium alkoxide were prepared, and amorphous ZrO2 films were obtained by spin-coating and annealing at 300 °C through the direct condensation reaction between them. The ZrO2 films exhibited a high dielectric constant near 10, and a low leakage current density of 5 × 10−8 A cm−2 at a field of 1 MV cm−1. High mobility p-type pentacene TFTs were fabricated using the ZrO2 dielectrics, with a saturation field-effect mobility of 3.7 cm2 V−1 s−1, a threshold voltage of −2.7 V, an on/off ratio of 1.1 × 106 and a subthreshold swing of 0.65 V dec−1.

Flexible Organic Tribotronic Transistor for Pressure and Magnetic Sensing.

Flexible electronics has attracted enormous interest in wearable electronics and human-machine interfacing. Here, a flexible organic tribotronic transistor (FOTT) without a top gate electrode has been demonstrated. The FOTT is fabricated on a flexible polyethylene terephthalate film using the p-type pentacene and poly(methyl methacrylate)/Cytop composites as the conductive channel and dielectric layer, respectively. The charge carriers can be modulated by the contact electrification between the dielectric layer and a mobile triboelectric layer. Based on the fabricated FOTT, pressure and magnetic sensors have been developed, respectively, that exhibit great sensitivity, fast response time, and excellent stability. The FOTT in this simple structure shows bright potentials of tribotronics in human-machine interaction, electronic skins, wearable electronics, intelligent sensing, and so on.

Ultrafast Exciton Dissociation and Long-Lived Charge Separation in a Photovoltaic Pentacene–MoS2 van der Waals Heterojunction

van der Waals heterojunctions between two-dimensional (2D) layered materials and nanomaterials of different dimensions present unique opportunities for gate-tunable optoelectronic devices. Mixed-dimensional p-n heterojunction diodes, such as p-type pentacene (0D) and n-type monolayer MoS2 (2D), are especially interesting for photovoltaic applications where the absorption cross-section and charge transfer processes can be tailored by rational selection from the vast library of organic molecules and 2D materials. Here, we study the kinetics of excited carriers in pentacene-MoS2 p-n type-II heterojunctions by transient absorption spectroscopy. These measurements show that the dissociation of MoS2 excitons occurs by hole transfer to pentacene on the time scale of 6.7 ps. In addition, the charge-separated state lives for 5.1 ns, up to an order of magnitude longer than the recombination lifetimes from previously reported 2D material heterojunctions. By studying the fractional amplitudes of the MoS2 decay processes, the hole transfer yield from MoS2 to pentacene is found to be ∼50%, with the remaining holes undergoing trapping due to surface defects. Overall, the ultrafast charge transfer and long-lived charge-separated state in pentacene-MoS2 p-n heterojunctions suggest significant promise for mixed-dimensional van der Waals heterostructures in photovoltaics, photodetectors, and related optoelectronic technologies.

Organic devices based on pentacene and perylene by the neutral cluster beam deposition method

In this study, on the basis of p-type pentacene and n-type N,N′-dioctyl-perylene-3,4,9,10-tetracarboxylic acid diimide (PTCDI-C8) organic field-effect transistors (OFETs) and two-input complementary NAND logic gates in the top-contact device configuration were produced and characterized. The organic active layers were deposited on hydroxyl-free polymethylmethacrylate (PMMA)-modified indium tin oxide (ITO) glass gate substrates by the neutral cluster beam deposition (NCBD) method. The morphological and structural properties of the organic semiconducting active layers on the PMMA substrates were examined using atomic force microscopy, X-ray diffraction and contact-angle goniometry. Based on the growth of high-quality, well-packed crystalline films on the PMMA dielectric-modified ITO gate substrates, the p- and n-type transistors exhibited hole and electron mobilities of 0.247 and 7.23×10−2cm2/Vs, respectively, in the air without encapsulation. The trap density and activation energy were also derived from the transport characteristics for the temperature dependence of the mobilities in the temperature range 20−300K for the first time. Because of the well balanced p- and n-type OFETs in the devices, the complementary metal-oxide semiconductor (CMOS) NAND logic circuits exhibited a high voltage gain and a large noise margin with slight hysteresis.

Effects of Doping and Electrode Contacts on Performance of Organic Light-Emitting Transistors Based on Pentacene and Tris(8-hydroxyquinoline)aluminum

Heterojunction-based organic light-emitting field-effect transistors (OLEFETs) with a top-contact, long-channel geometry were fabricated and comparatively characterized. The neutral cluster beam deposition (NCBD) method was used to successively deposit two layers of p-type pentacene and n-type tris(8-hydroxyquinoline)aluminum (Alq3). For doped OLEFETs, 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) was used as a highly fluorescent dye dopant to enhance the light-emission efficiency and change the emission color. OLEFETs revealed fine device characteristics based on deposition of highly crystalline active layers. The combination of the highly fluorescent DCM doping and asymmetric electrode configuration (Au and Li:Al or LiF/Al) exhibited efficient energy transfer and enhanced electroluminescence (EL) emission. The operating light-emission mechanisms were discussed based on EL photos acquired using a charge-coupled device (CCD) camera.

Photo-Patternable ZnO Thin Films Based on Cross-Linked Zinc Acrylate for Organic/Inorganic Hybrid Complementary Inverters.

Complementary inverters consisting of p-type organic and n-type metal oxide semiconductors have received considerable attention as key elements for realizing low-cost and large-area future electronics. Solution-processed ZnO thin-film transistors (TFTs) have great potential for use in hybrid complementary inverters as n-type load transistors because of the low cost of their fabrication process and natural abundance of active materials. The integration of a single ZnO TFT into an inverter requires the development of a simple patterning method as an alternative to conventional time-consuming and complicated photolithography techniques. In this study, we used a photocurable polymer precursor, zinc acrylate (or zinc diacrylate, ZDA), to conveniently fabricate photopatternable ZnO thin films for use as the active layers of n-type ZnO TFTs. UV-irradiated ZDA thin films became insoluble in developing solvent as the acrylate moiety photo-cross-linked; therefore, we were able to successfully photopattern solution-processed ZDA thin films using UV light. We studied the effects of addition of a tiny amount of indium dopant on the transistor characteristics of the photopatterned ZnO thin films and demonstrated low-voltage operation of the ZnO TFTs within ±3 V by utilizing Al2O3/TiO2 laminate thin films or ion-gels as gate dielectrics. By combining the ZnO TFTs with p-type pentacene TFTs, we successfully fabricated organic/inorganic hybrid complementary inverters using solution-processed and photopatterned ZnO TFTs.

Low-voltage organic transistors and inverters using HfOx dielectrics

Based on the p-type pentacene and n-type N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (PTCDI-C13), low-voltage organic field-effect transistors (OFETs) and inverters using hafnium (Hf)-based dielectrics were produced and characterized. All the pristine and cyclic olefin copolymer (COC)-passivated HfOx gate dielectrics were deposited by the solution-processed sol–gel chemistry, and organic thin films were deposited on the dielectrics by the neutral cluster beam deposition method. In comparison to the pristine HfOx-based OFETs, the COC-passivated transistors showed better device performance: higher hole and electron mobilities, reduced hysteresis, decreased trap densities, and particularly improved operational stability of n-type transistors. The inverters composed of the optimized p- and n-type OFETs with the asymmetric Au and LiF/Al electrodes using COC-passivated HfOx dielectrics exhibited high gains and good noise margins under ambient conditions.

Quasi-unipolar pentacene films embedded with fullerene for non-volatile organic transistor memories

Quasi-unipolar non-volatile organic transistor memory (NOTM) can combine the best characteristics of conventional unipolar and ambipolar NOTMs and, as a result, exhibit improved device performance. Unipolar NOTMs typically exhibit a large signal ratio between the programmed and erased current signals but also require a large voltage to program and erase the memory cells. Meanwhile, an ambipolar NOTM can be programmed and erased at lower voltages, but the resulting signal ratio is small. By embedding a discontinuous n-type fullerene layer within a p-type pentacene film, quasi-unipolar NOTMs are fabricated, of which the signal storage utilizes both electrons and holes while the electrical signal relies on only hole conduction. These devices exhibit superior memory performance relative to both pristine unipolar pentacene devices and ambipolar fullerene/pentacene bilayer devices. The quasi-unipolar NOTM exhibited a larger signal ratio between the programmed and erased states while also reducing the voltage required to program and erase a memory cell. This simple approach should be readily applicable for various combinations of advanced organic semiconductors that have been recently developed and thereby should make a significant impact on organic memory research.

Performance enhancement of pentacene and F16CuPc-based low-voltage devices using cross-linked blend gate dielectrics

Herein is reported the fabrication and systematic comparative analysis of low-voltage organic filed-effect transistors (OFETs) and inverters using bare ZrOx dielectrics and inorganic–organic hybrid CZB (cross-linked ZrOx/1,6-bis(trimethoxysily)hexane blend) dielectrics. Solution-processed sol–gel chemistry was employed to prepare the gate dielectrics. Two active layers of p-type pentacene and n-type copper hexadecafluorophthalocyanine (F16CuPc) were deposited on the dielectrics using the neutral cluster beam deposition method. Compared with bare ZrOx-based transistors and inverters, the CZB-based devices with low leakage current and high capacitance exhibited significantly higher hole and electron carrier mobilities of (0.12 → 1.03) and (1.3 × 10−3 → 4.9 × 10−3) cm2 (Vs)−1, respectively, and enhanced gains of (9.4 → 13.3), together with large output voltage swings and sharp inversions in the voltage transfer characteristics (VTCs). The CZB-based inverters also exhibited improved noise margins due to the higher gain and better symmetry of the VTCs compared with their bare ZrOx-based counterparts. The results indicate that on the basis of the enhanced electrical properties of CZB dielectrics and the growth of high-quality crystalline semiconducting films on CZB dielectric surfaces, such high-performance devices operating at low voltage levels are promising potential components for integrated circuits.

Versatile threshold voltage control of OTFTs via discontinuous pn-heterojunction formation

We demonstrate the versatility of the threshold voltage control for organic thin-film transistors (OTFTs) based on formation of discontinuous pn-heterojunction on the active channel layer. By depositing n-type dioctyl perylene tetracarboxylic diimide molecules discontinuously onto base p-type pentacene thin films (the formation of the discontinuous pn-heterojunction), a positive shift of the threshold voltage was attained which enabled realizing a depletion-mode transistor from an original enhancement-mode pristine pentacene transistor. Careful control of the threshold voltage based on this method led assembling a depletion-load inverter comprising a depletion-mode transistor and an enhancement-mode transistor connected in series that yielded tunable signal inversion voltage approaching 0V. In addition, the tunability could be applied to improve the program/erase signal ratio for non-volatile transistor memories by more than 4 orders of magnitude compared to reference memory devices made of pristine pentacene transistors.

Micro-scale twistable organic field effect transistors and complementary inverters fabricated by orthogonal photolithography on flexible polyimide substrate

We fabricated micro-scale organic field effect transistors (OFETs) and complementary inverters on a twistable polyimide (PI) substrate by applying orthogonal photolithography. By applying a highly fluorinated photoresist and development solvent, it becomes possible to create organic electronic devices with a micro-scale channel length without damaging the underlying polymer films. The 3μm-channel twistable pentacene OFET devices and complementary inverters created using p-type pentacene and n-type copper hexadecafluorophthalocyanine exhibited stable electrical characteristics from flat to twist configurations (angle of up to ∼50°). The realization of twistable micro-scale OFETs and inverter devices on a PI substrate may enable the production of functioning organic devices in practical, flexible configurations.

Discontinuous pn-Heterojunction for Organic Thin Film Transistors

Utilization of discontinuous pn-oragnic heterojunction is introduced as a versatile method to improve charge transport in organic thin film transistors (OTFTs). The method is demonstrated by depositing n-type dioctyl perylene tetracarboxylic diimide (PTCDI-C8) discontinuously onto base p-type pentacene OTFTs. A more pronounced impact of the discontinuous upper layer is obtained on the transistor performances when thinner base layers are employed; a >100-fold enhancement in hole mobility and a >20 V shift in threshold voltage are achieved after applying PTCDI-C8 discontinuously onto 2 nm thick pentacene thin films. Local surface potential measurements (Kelvin-probe force microscopy) and temperature-dependent transport measurements (77–300 K) reveal that the interfacial dipole formed at the pn-heterostructures effectively dopes the base pentacene films p-type and leads to a reduction in transport activation energy.

Micropatterned single-walled carbon nanotube electrodes for use in high-performance transistors and inverters.

We demonstrated the solution-processed single-walled carbon nanotube (SWNT) source-drain electrodes patterned using a plasma-enhanced detachment patterning method for high-performance organic transistors and inverters. The high-resolution SWNT electrode patterning began with the formation of highly uniform SWNT thin films on a hydrophobic silanized substrate. The SWNT source-drain patterns were then formed by modulating the interfacial energies of the prepatterned elastomeric mold and the SWNT thin film using oxygen plasma. The SWNT films were subsequently selectively delaminated using a rubber mold. The patterned SWNTs could be used as the source-drain electrodes for both n-type PTCDI-C8 and p-type pentacene field-effect transistors (FETs). The n- and p-type devices exhibited good and exactly matched electrical performances, with a field-effect mobility of around 0.15 cm(2) V(-1) s(-1) and an ON/OFF current ratio exceeding 10(6). The single electrode material was used for both the n and p channels, permitting the successful fabrication of a high-performance complementary inverter by connecting a p-type pentacene FET to an n-type PTCDI-C8 FET. This patterning technique was simple, inexpensive, and easily scaled for the preparation of large-area electrode micropatterns for flexible microelectronic device fabrication.