Roll‐to‐Roll fabrication of large area functional organic materials

With the prospect of extremely fast manufacture of very low cost devices, organic electronics prepared by thin film processing techniques that are compatible with roll‐to‐roll (R2R) methods are presently receiving an increasing interest. Several technologies using organic thin films are at the point, where transfer from the laboratory to a more production‐oriented environment is within reach. In this review, we aim at giving an overview of some of the R2R‐compatible techniques that can be used in such a transfer, as well the current status of R2R application within some of the existing research fields such as organic photovoltaics, organic thin film transistors, light‐emitting diodes, polymer electrolyte membrane fuel cells, and electrochromic devices. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

A new high‐performance blue to transmissive electrochromic material and use of silver nanowire network electrodes as substrates

Synthesis of a novel, high‐performance blue to transmissive switching electrochromic material is described. The polymer (P1) was prepared by both electrochemical ( P1E ) and chemical ( P1C ) means from the corresponding monomer. The electrochemically synthesized polymer ( P1E ) revealed 64% optical contrast change (on ITO) in the visible region and very fast switching times of 0.32 s (coloration) and 0.90 s (bleaching). On the other hand, the chemically synthesized, solution processable polymer ( P1C ) also showed a high optical contrast value (49%, on ITO) with very fast switching times of 0.86 s for coloration and 0.57 s for bleaching. These high optical contrast values coupled with fast switching times place these materials along with high‐performance blue to transmissive electrochromic polymers. Significantly, these improved characteristics were achieved by side chain engineering of a known, inferior blue to transmissive polymer, PBEBT. Towards fabrication of flexible electrochromic devices, the performance of P1C was also tested on silver nanowire network electrodes. Even though the full potential of the material could not be demonstrated, a good optical contrast of 24% was achieved using these electrodes. Under the same potential range allowed by silver nanowire network electrodes, P1C on ITO showed an optical contrast of 30%. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1680–1686     

Low‐temperature side‐chain cleavage and decarboxylation of polythiophene esters by acid catalysis

Solubility switching of polymers is very useful in thin layer processing of conjugated polymers, as it allows for multilayer processing and increases the stability of the polymer. Acid catalyzed thermocleavage of ester groups from thiophene polymers carrying primary, secondary, and tertiary substituents have been examined by TGA‐MS using different sulphonic acids. A substantial lowering of the cleavage temperature is observed, and the ester cleavage can even be performed in situ on roll‐to‐roll‐coated films on polyethylene terephthalate (PET). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Organic light‐emitting device dark spot growth behavior analysis by diffusion reaction theory

Dark spot growth rate tracing experiments performed on an organic light‐emitting device show that moisture entering into the device is relatively properly fitted by Fick's diffusion equation in the substrate/indium tin oxide (ITO)/hole transport layer (HTL)/silver (Ag) structure. It is believed that the moisture is dissolved into the polymer layer, which results in a decrease in the diffusion coefficient in the device with the substrate/ITO/HTL/electroluminescent (EL) polymer/Ag structure. The diffusion and chemical reaction occurring in the cathode layer further decreases the diffusion coefficient in the device with the substrate/ITO/HTL/EL polymer/calcium/Ag structure. Useful parameters, such as diffusion and solubility constants, describing possible mechanisms happening during dark spot growth on organic light‐emitting diode devices are extracted. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1697–1703, 2001     

Nonvolatile write‐once read‐many‐times memory behaviors of polyimides containing tetraphenyl fluorene core and the pendant triphenylamine or carbazole moieties

To better understand the structure–property relationships, two novel aromatic diamines containing tetraphenyl fluorene (TPF) moiety through triphenylamine (TPA) unit and carbazole (Cz) unit modification are designed and synthesized, respectively. Four thermally stable and excellent solubility polyimides are prepared and characterized. The excellent film‐formation ability and thin film stability are investigated by X‐ray diffraction (XRD) and atom force microscopy (AFM) measurements, respectively. The memory devices are fabricated, PIs films with low water uptakes sandwiched between indium‐tin oxide (ITO) ground electrode and Al top electrode, and exhibit nonvolatile write‐once read‐many‐times (WORM) memory behaviors with low threshold voltages, due to increasing the retention time through regulating the energy level. The current conduction mechanisms of all devices are linearly fitted by theoretical conduction model. Molecular simulations are used to demonstrate switching mechanism and the memory effects. The experimental results provide a sight for the design‐adjustable switching voltage of memory devices. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1630–1644     

Manufacture and demonstration of organic photovoltaic‐powered electrochromic displays using roll coating methods and printable electrolytes

Electrochromic devices (ECDs) were prepared on flexible substrates using spray coating and slot‐die coating methods. The electrochromic materials were the conjugated electroactive polymers, poly((2,2‐bis(2‐ethylhexyloxymethyl)‐propylene‐1,3‐dioxy)‐3,4‐thiophene‐2,5‐diyl) as a vibrantly colored active material (ECP‐Magenta) and poly(N‐octadecyl‐(propylene‐1,3‐dioxy)‐3,4‐pyrrole‐2,5‐diyl) as a minimally colored, charge balancing material (MCCP). Two electrolyte systems were compared to allow development of fully printable and laminated devices on flexible substrates. Devices of various sizes, up to 7 × 8 cm², are demonstrated with pixelated devices containing pixel sizes of 4 × 4 mm² or 13 × 13 mm². The transmission contrast exhibited by the devices, when switched between the fully bleached and fully colored state, was 58% at a visible wavelength of 550 nm, and the devices exhibited switching times of <10 s. Additionally, we demonstrate the utilization of printed organic photovoltaic devices (with or without the use of a lithium‐polymer battery) to power the devices between the colored and bleached state, illustrating a self‐powered ECD. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

A new near‐infrared switchable electrochromic polymer and its device application

A new near‐infrared switchable electrochromic polymer containing carbazole pendant (poly‐SNSC), synthesized by electrochemical polymerization of 2,5‐bis‐dithienyl‐1H‐pyrrole (SNS) main chain, has been prepared. The electrochemical and optical properties of SNSC monomer and its polymer have been investigated. Because of having two different electro‐donor moieties; that is, carbazole and SNS, SNSC gave two separate electrochemical oxidation and also light brown color of the film in the neutral state turn into gray on oxidation. An electrochromic device, contructed in the sandwich configuration [indium tin oxide (ITO)‐coated glass/anodically coloring polymer (poly‐SNSC)//gel electrolyte//cathodically coloring polymer (PEDOT)/ITO‐coated glass] and exhibited a high coloration efficiency (1216 cm² C^–1), a very short response time (about 0.3 s), low driving voltage, and a high redox stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Conjugated Polymers Via Direct Arylation Polymerization in Continuous Flow: Minimizing the Cost and Batch‐to‐Batch Variations for High‐Throughput Energy Conversion

Continuous flow methods are utilized in conjunction with direct arylation polymerization (DArP) for the scaled synthesis of the roll‐to‐roll compatible polymer, poly[(2,5‐bis(2‐hexyldecyloxy)phenylene)‐alt‐(4,7‐di(thiophen‐2‐yl)‐benzo[c][1,2,5]thiadiazole)] (PPDTBT). PPDTBT is based on simple, inexpensive, and scalable monomers using thienyl‐flanked benzothiadiazole as the acceptor, which is the first β‐unprotected substrate to be used in continuous flow via DArP, enabling critical evaluation of the suitability of this emerging synthetic method for minimizing defects and for the scaled synthesis of high‐performance materials. To demonstrate the usefulness of the method, DArP‐prepared PPDTBT via continuous flow synthesis is employed for the preparation of indium tin oxide (ITO)‐free and flexible roll‐coated solar cells to achieve a power conversion efficiency of 3.5% for 1 cm² devices, which is comparable to the performance of PPDTBT polymerized through Stille cross coupling. These efforts demonstrate the distinct advantages of the continuous flow protocol with DArP avoiding use of toxic tin chemicals, reducing the associated costs of polymer upscaling, and minimizing batch‐to‐batch variations for high‐quality material.     

Electrochromic material containing unsymmetrical substituted N,N,N′,N′‐tetraaryl‐1,4‐phenylenediamine: Synthesis and their optical,electrochemical, and electrochromic properties

A novel dibromo compound containing unsymmetrical substituted bi‐triarylamine was synthesized. A conjugated polymer was prepared via the Suzuki coupling from the newly prepared dibromo compound and 9,9‐dioctylfluorene‐2,7‐bis(trimethyleneboronate). The glass transition temperature (T_g) of the conjugated polymer was 140 °C, 10% weight‐loss temperatures (T_d10) in nitrogen was 458 °C, and char yield at 800 °C in nitrogen higher than 64%. Cyclic voltammogram of the polymer film cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited two reversible oxidation redox couples at 0.70 and 1.10 V versus Ag/Ag⁺ in acetonitrile solution. The polymer films revealed excellent stability of electrochromic characteristics, with a color change from yellow green of the neutral form to the dark green and blue of oxidized forms at applied potentials ranging from 0 to 1.3 V. The color switching time and bleaching time were 4.25 and 7.22 s for 860 nm and 5.51 s and 6.48 s for 560 nm. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1469–1476, 2010     

Iridium complex grafted to 3,6‐carbazole‐alt‐tetraphenylsilane copolymers for blue electrophosphorescence

We designed a 3,6‐dibromo‐9‐hexyl‐9H‐carbazole derivative with the blue emissive iridium complex bis[2‐(4,6‐difluorophenyl)pyridyl‐N,C^2′](picolinato)iridium(III) (FIrpic) linked at the alkyl terminal. Based on this monomer, novel 3,6‐carbazole‐alt‐tetraphenylsilane copolymers grafted with FIrpic were synthesized by palladium‐catalyzed Suzuki coupling reaction, and the content of FIrpic in the polymers could be controlled by feed ratio of the monomers. The polymer films mainly show blue emission from FIrpic, and the emission intensity from the polymer backbones is much weaker compared with the doped analogues, which demonstrates an efficient energy transfer from polymeric host to covalently bonded guest. The phase separation in the polymers was suppressed, which can be identified by atomic force microscopy and designed electroluminescent (EL) devices. EL devices based on the polymers exhibited blue phosphorescence from FIrpic. The luminous efficiency of preliminary devices reached 2.3 cd/A, and the efficiency roll‐off at high current densities was suppressed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1859–1865, 2010     

Novel high‐performance polymer memory devices containing (OMe)2tetraphenyl‐p‐phenylenediamine moieties

The functional polyimide (OMe)₂TPPA‐6FPI ( PI ) and the polyamide (OMe)₂TPPA‐6FPA ( PA ) consisting of electron‐donating N,N′‐bis(4‐aminophenyl)‐N,N′‐di(4‐methoxylphenyl)1,4‐phenylenediamine [(OMe)₂TPPA‐diamine] for memory application were prepared in this study. These polyimide and polyamide memory devices were fabricated with the sandwich configuration of indium tin oxide (ITO)/polymer/Al, and could be switched from the initial low‐conductivity (OFF) state to the high‐conductivity (ON) state with high ON/OFF current ratios of 10⁷ and 10⁹, respectively. PI exhibited dynamic random access memory (DRAM) performance, whereas PA showed static random access memory (SRAM) behavior. To get more insight into the memory behaviors of these two different types of polymer memory devices, molecular simulation on the basic unit was carried out. Furthermore, the differences of highest occupied molecular orbital (HOMO) energy level, lowest unoccupied molecular orbital (LUMO) charge density isosurfaces, dipole moment, and linkage conformation between PI and PA were found to affect the volatile memory behavior. Both polymer memory devices revealed excellent stability with long operation time of 10⁴ s at continuous applied voltage of ‐2 V. The effect of polymer thickness on the volatile memory behavior of PA was also investigated in this study. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis,characterization, and electroluminescence of novel copolyfluorenes and their applications in white light emission

New copolyfluorenes (PC8OF0–PC8OF50) comprised of 9,9‐dioctylfluorene and jacketed units 2,5‐bis[(5‐octyloxy‐phenyl)‐1,3,4‐ oxadiazole]‐1‐(3,5‐dibromophenyl)‐benzene (35C8) were synthesized by palladium‐catalyzed Suzuki coupling reaction. They were characterized by molecular weight determination, ¹H NMR, elemental analysis, DSC, TGA, absorption and emission spectroscopy, and cyclic voltammetry (CV). These copolymers were readily soluble in common organic solvents and exhibited high glass transition temperature and thermal stability.The copolymer films showed absorption peaks from 381 nm to 351 nm, and PL peaks from 432 nm to 421 nm with a blue shift originated from 35C8 units. Both the HOMO energy levels and LUMO levels changed little as the content of 35C8 units increased (?5.59 eV to ?5.48 eV and ?2.60 eV to ?2.49 eV). Electroluminescent devices: ITO/PEDOT:PSS[poly(ethylenedioxythiophene):polystyrenesulfonate]/polymer/Ca (25 nm)/Ag(80 nm) (a), ITO/PEDOT:PSS/polymer/TPBI [1,3,5‐ tris(N‐phenylbenzimidazol‐2‐yl)benzene](15 nm)/Mg:Ag(10:1, wt)/Ag (b), and ITO/ PEDOT:PSS/PVK[Poly(N‐vinylcarbazole)]/polymer/TPBI(15 nm)/Ca(25 nm)/Ag(80 nm) (c) were fabricated to investigate the influence of jacketed contents and device architectures on emission characteristics. The maximum brightness and current efficiency of the PC8OF25 device (5097.8 cd/m² and 0.484 cd/A) surpassed those of the PC8OF0 device (3122.8 cd/m² and 0.416 cd/A). The EL emissions of PC8OF0 – PC8OF50 were pure blue and low‐energy excimer emission bands were successfully suppressed, indicating that these copolymers could be good candidates for blue light‐emitting materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4555–4565, 2009     

Synthesis and properties of high‐performance functional polyimides containing rigid nonplanar conjugated tetraphenylethylene moieties

A simple diamine (TetraPEDA) containing rigid nonplanar conjugated tetraphenylethylene (TetraPE) moieties was designed and synthesized through Wittig–Horner and Suzuki coupling reactions. Four kinds of high‐performance functional polyimides (PI) were thus prepared by the polymerization of TetraPEDA and four dianhydrides, respectively. Because of the introduction of the aromatic rigid nonplanar TetraPE structure, the PI exhibited special fluorescent characteristics, as the maximum fluorescence emission of the four PI was observed at 425–505 nm in NMP solution and at 470–491 nm in film state. Also these organo‐soluble PI showed outstanding properties, such as low dielectric constant (even without fluorinated substituent), light color, high glass transition temperatures (382–443 °C) and thermal stability in air (T_d5% up to 565 °C), and excellent mechanical properties. The polymer memory devices with the configuration of indium tin oxide/PI/aluminum (ITO/PI/Al) exhibited distinct volatile memory characteristics of static random access memory, with an ON/OFF current ratio of 1 × 10⁴ to 1 × 10⁵. These functional PI showed attractive potential applications in the field of high performance flexible polymer photoconducting devices or fluorescent polymer memory devices. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and electro‐optical properties of light‐emitting polymers containing oxadiazole derivatives for light‐emitting diodes applications

Two PPV‐based bipolar polymers containing 1,3,4‐oxadiazole pendant groups were synthesized via the Gilch polymerization reaction for use in light‐emitting diodes (LEDs). The resulting polymers were characterized using ¹H and ¹³C NMR, elemental analysis, DSC, and TGA. These polymers were found to be soluble in common organic solvents and are easily spin‐coated onto glass substrates, producing high optical quality thin films without defects. The electro‐optical properties of ITO/PEDOT/polymer/Al devices based on these polymers were investigated using UV‐visible, PL, and EL spectroscopy. The turn‐on voltages of the OC₁Oxa‐PPV and OC₁₀Oxa‐PPV devices were found to be 8.0 V. The maximum brightness and luminescence efficiency of the OC₁Oxa‐PPV device were found to be 544 cd/m² at 19 V and 0.15 cd/A, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1098–1110, 2008     

White electroluminescent single‐polymer achieved by incorporating three polyfluorene blue arms into a star‐shaped orange core

A series of star‐like dopant/host single‐polymer systems with a D‐A type star‐shaped orange core and three blue polyfluorene arms were designed and synthesized. Through tuning the doping concentration of the orange core and thermal annealing treatment of white polymer light‐emitting diodes based on them, highly efficient white electroluminescence has been achieved. A typical single‐layer device (ITO/PEDOT:PSS/polymer/Ca/Al) realized pure white emission with a luminous efficiency of 16.62 cd A^?1, an external quantum efficiency of 6.28% and CIE coordinates of (0.33, 0.36) for S‐WP‐002TPB3 containing 0.02 mol % orange core. The high efficiency of the devices could be mainly attributed to the suppressed concentration quenching of the dopant units, more efficient energy transfer from polymer host to orange dopant and thermal annealing‐induced α‐phase polyfluorene (PF) self‐dopant in amorphous PF host. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A new soluble conducting polymer and its electrochromic devices

A new polythiophene derivative was synthesized by both chemical and electrochemical oxidative polymerization of 1‐(1‐phenylethyl)‐2,5‐di(2‐thienyl)‐1H‐pyrrole (PETPy). Of which the chemical method produces a polymer that is completely soluble in organic solvents. The structures of both the monomer and the soluble polymer were elucidated by nuclear magnetic resonance (¹H and ¹³C NMR) and Fourier transform infrared (FTIR) spectroscopy. The average molecular weight has been determined by gel permeation chromatography to be M_n = 3.29 × 10³ for the chemically synthesized polymer. Polymer of PETPy was synthesized via potentiostatic electrochemical polymerization in acetonitrile (AN)/NaClO₄/LiClO₄ (0.1 M) solvent–electrolyte couple. Characterizations of the resulting polymer were performed by cyclic voltammetry, FTIR, scanning electron microscopy, and UV–vis spectroscopy. Four‐probe technique was used to measure the conductivities of the samples. Moreover, the spectroelectrochemical and electrochromic properties of the polymer films were investigated. In addition, dual‐type polymer electrochromic devices based on P(PETPy) with poly(3,4‐ethylenedioxythiophene) were constructed. Spectroelectrochemistry, electrochromic switching, and open circuit stability of the devices were studied. They were found to have good switching times, reasonable contrasts, and optical memories. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2215–2225, 2006     

Hole‐buffer polymer composed of alternating p‐terphenyl and tetraethylene glycol ether moieties: Synthesis and application in polymer light‐emitting diodes

Carrier balance is essential to obtain efficient emission in polymer light‐emitting diodes (PLEDs). A new polymer 3P5O composed of alternating p‐terphenyl and tetraethylene glycol ether segments is designed and synthesized by the Suzuki coupling reaction and successfully employed as hole‐buffer layer to improve carrier balance. Multilayer PLEDs [ITO/PEDOT:PSS/ 3P5O /SY/LiF/Al], with Super Yellow (SY) as the emitting layer and 3P5O as the hole‐buffer layer, reveal maximum luminance (17,050 cd/m²) and maximum current efficiency (6.6 cd/A) superior to that without the hole‐buffer layer (10,017 cd/m², 3.0 cd/A). Moreover, it also shows better performance than that using conventional BCP as hole‐blocking layer [ITO/PEDOT:PSS/SY/BCP/LiF/Al (80 nm): 13,639 cd/m², 4.1 cd/A]. The performance enhancement has been attributed to hole‐buffering characteristics of 3P5O that results in improved carrier recombination ratio and wider carrier recombination region. Current results indicate that the 3P5O is a promising hole‐buffer polymer to enhance the performance of optoelectronic devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 785–794     

Impact of Top Electrodes (Cu,Ag, and Al) on Resistive Switching behaviour of Cu-rich Cu2ZnSnS4 (CZTS) Ideal Kesterite

Cu₂ZnSnS₄ (CZTS) active material-based resistive random-access memory (RRAM) devices are investigated to understand the impact of three different Cu, Ag, and Al top electrodes. The dual resistance switching (RS) behaviour of spin coated CZTS on ITO/Glass is investigated up to 10² cycles. The stability of all the devices (Cu/CZTS/ITO, Ag/CZTS/ITO, and Al/CZTS/ITO) is investigated up to 10³ sec in low- (LRS) and high- (HRS) resistance states at 0.2 V read voltage. The endurance up to 10² cycles with 30 msec switching width shows stable write and erase current. Weibull cumulative distribution plots suggest that Ag top electrode is relatively more stable for set and reset state with 33.61 and 25.02 shape factors, respectively. The charge carrier transportation is explained by double logarithmic plots, Schottky emission plots, and band diagrams, substantiating that at lower applied electric field intrinsic copper ions dominate in Cu/CZTS/ITO, whereas, at higher electric filed, top electrodes (Cu and Ag) dominate over intrinsic copper ions. Intrinsic Cu⁺ in CZTS plays a decisive role in resistive switching with Al electrode. Further, the impedance spectroscopy measurements suggest that Cu⁺ and Ag⁺ diffusion is the main source for the resistive switching with Cu and Ag electrodes.     

Intramolecular energy transferable (2,2‐diphenylvinyl)phenyl substituted poly(p‐phenylenevinylene) derivative with efficient photoluminescence and electroluminescence

A poly(p‐phenylenevinylene) (PPV) derivative containing a bulky (2,2‐diphenylvinyl)phenyl group in the side chain, EHDVP‐PPV, was synthesized by Gilch route. The reduced tolane‐bisbenzyl (TBB) defects, as well as the structure of the polymer, was confirmed by various spectroscopic methods. The intramolecular energy transfer from the (2,2‐diphenylvinyl)phenyl side group to the PPV backbone was studied by UV‐vis and photoluminescence (PL) of the obtained polymer and model compound. The polymer film showed maximum absorption and emission peaks at 454 and 546 nm, respectively, and high PL efficiency of 57%. A yellow electroluminescence (λ_max = 548 nm) was obtained with intensities of 6479 cd/m² when the light‐emitting diodes of ITO/PEDOT/EHDVP‐PPV/LiF/Al were fabricated. The maximum power efficiency of the devices was 0.729 lm/W with a turn‐on voltage of 3.6 V. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5636–5646, 2004     

Multipurpose conjugated block copolymers based on novel triphenylylamine derivatives and squaric acid for electrochromic and resistive memory devices

Here, we synthesized two kinds of novel conjugated block copolymers P1 and P2 by reacting squaric acid and three kinds of homemade diamine monomers. The polymers P1 and P2 can be dissolved in many normal organic solvents and form films by solution-cast method with high mechanical properties. In addition, when the 10% weight loss is selected as a reference point, the polymers P1 and P2 showed the thermal decomposition temperatures at around 309 and 312 °C, respectively. The polymer films exhibit high coloration efficiencies (CE) (262–282 cm² C⁻¹) and good cyclic stabilities. In addition, the ITO/polymer/Al sandwich memory devices exhibited non-volatile resistive switching behaviors with low write, erase voltages (more than −0.6 V and less than 3.1 V, respectively), good ON/OFF ratio (843 and 1435) and reliable cycling endurance (more than 30,000 cycles). These properties illustrate that the polymers could be considered as potential electrode materials for both electrochromic and resistive memory devices.