To capture the essence of the rapid progress in optical engineering exploited in high-performance polymer solar cells (PSCs), a comprehensive overview focusing on recent developments and achievements in PSC electrode engineering is provided in this review. To date, various kinds of electrode materials and geometries are exploited to enhance light-trapping in devices through distinct optical strategies. In addition to the widely used nanostructured electrodes that induce plasmonic-enhanced light absorption, planar ultra-thin metal films also have attracted significant attention due to their remarkably reflective transparent properties that beget efficient optical microcavities. These microcavities confine incident light with resonant frequencies between two reflective electrodes due to optically coherent interference, boosting the light absorption of thin-film PSCs while maintaining efficient charge dissociation and extraction. After reviewing the challenges in developing high-performance microcavity-enhanced PSCs (MCPSCs), we discuss strategies to improve MCPSC performance further to showcase the potential of harnessing microcavity resonance effects in thin-film PSCs.

A series of anionic self-doped conjugated polyelectrolytes (CPEs) by copolymerization of a 1,4-bis(4-sulfonatobutoxy)benzene moiety with different counter monomers of thiophene, bithiophene, and terthiophene is reported. The CPEs show high conductivity of ≈10⁻⁴ S cm⁻¹ due to being self-doped in a neutral state and exhibit excellent hole transporting property in the out-of-plane direction, compared with poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS). Moreover, the CPE incorporating a less electron-donating unit from terthiophene to thiophene exhibits a higher work function and therefore, PhNa-1T incorporating thiophene shows a relatively high work function of 5.21 eV than 4.97 eV of PEDOT:PSS. This can induce a higher internal field in the solar cell device, facilitating efficient charge collection to the electrode. As a result, polymer solar cell devices incorporating the CPEs as a hole transporting layer achieve enhanced photovoltaic performances from those of the conventional PEDOT:PSS-based devices. The solar cell efficiency reaches up to 9.89%, which is among the highest values demonstrated by PCE-10-based normal-type organic solar cells.

Hexaazatrinaphthylene (HATNA) derivatives have been successfully shown to function as efficient electron-transporting materials (ETMs) for perovskite solar cells (PVSCs). The cells demonstrate a superior power conversion efficiency (PCE) of 17.6 % with negligible hysteresis. This study provides one of the first nonfullerene small-molecule-based ETMs for high-performance p–i–n PVSCs.

Hexaazatrinaphthylene (HATNA) derivatives have been successfully shown to function as efficient electron-transporting materials (ETMs) for perovskite solar cells (PVSCs). The cells demonstrate a superior power conversion efficiency (PCE) of 17.6 % with negligible hysteresis. This study provides one of the first nonfullerene small-molecule-based ETMs for high-performance p–i–n PVSCs.

In this work, a high-performance ITO-free flexible polymer solar cell (PSC) is successfully described by integrating the plasmonic effect into the ITO-free microcavity architecture. By carefully controlling the sizes of embedded Ag nanoprisms and their doping positons in the stratified device, a significant enhancement in power conversion efficiency (PCE) is shown from 8.5% (reference microcavity architecture) to 9.4% on flexible substrates. The well-manipulated plasmonic resonances introduced by the embedded Ag nanoprisms with different LSPR peaks allow the complementary light-harvesting with microcavity resonance in the regions of 400–500 nm and 600–700 nm, resulting in the substantially increased photocurrent. This result not only signifies that the spectral matching between the LSPR peaks of Ag nanoprisms and the relatively low absorption response of photoactive layer in the microcavity architecture is an effective strategy to enhance light-harvesting across its absorption region, but also demonstrates the promise of tailoring two different resonance bands in a synergistic manner at desired wavelength region to enhance the efficiency of PSCs.

Four new molecular donors are reported using a D1-A-D2-A-D1 structure, where D1 is an oligiothiophene, A is a benzothiadiazole, and D2 is indacenodithieno[3,2-b]thiophene. The resulting materials provide efficiencies as high as 6.5% in organic solar cells, without the use of solvent additives or thermal/solvent annealing. A strong correlation between the end group (D1-A) dipole moment and the fill factor (FF), mobility, and loss in the open-circuit voltage (V_OC) is observed. Indacenodithieno[3,2-b]thiophene-fluorobenzothiadiazole-terthiophene (IDTT-FBT-3T) possesses the largest end group dipole moment, and in turn, has the highest mobility, FF, and power conversion efficiency in devices. It also has a similarly high V_OC (0.95 V) to the other materials (0.93–0.99 V), despite possessing a much higher highest occupied molecular orbital (HOMO) energy level.

Low-voltage self-assembled monolayer field-effect transistors (SAMFETs) that operate under an applied bias of less than −3 V and a high hole mobility of 10⁻² cm² V⁻¹ s⁻¹ are reported. A self-assembled monolayer (SAM) with a quaterthiophene semiconducting core and a phosphonic acid binding group is used to fabricate SAMFETs on both high-voltage (AlO_x/300 nm SiO₂) and low-voltage (HfO₂) dielectric platforms. High performance is achieved through enhanced SAM packing density via a heated assembly process and through improved electrical contact between SAM semiconductor and metal electrodes. Enhanced electrical contact is obtained by utilizing a functional methylthio head group combined with thermal annealing post gold source/drain electrode deposition to facilitate the interaction between SAM and electrode.

In this study, we investigate the influence of molecular geometry of the donor polymers and the perylene diimide dimers (di-PDIs) on the bulk heterojunction (BHJ) morphology in the nonfullerene polymer solar cells (PSCs). The results reveal that the pseudo 2D conjugated poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b′]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)] (PTB7-Th) has better miscibility with both bay-linked di-PDI (B-di-PDI) and hydrazine-linked di-PDI (H-di-PDI) compared to its 1D analog, poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7), to facilitate more efficient exciton dissociation in the BHJ films. However, the face-on oriented π–π stacking of PTB7-Th is severely disrupted by the B-di-PDI due to its more flexible structure. On the contrary, the face-on oriented π–π stacking is only slightly disrupted by the H-di-PDI, which has a more rigid structure to provide suitable percolation pathways for charge transport. As a result, a very high power conversion efficiency (PCE) of 6.41% is achieved in the PTB7-Th:H-di-PDI derived device. This study shows that it is critical to pair suitable polymer donor and di-PDI-based acceptor to obtain proper BHJ morphology for achieving high PCE in the nonfullerene PSCs.

Highly efficient tandem and semitransparent (ST) polymer solar cells utilizing the same donor polymer blended with [6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) as active layers are demonstrated. A high power conversion efficiency (PCE) of 8.5% and a record high open-circuit voltage of 1.71 V are achieved for a tandem cell based on a medium bandgap polymer poly(indacenodithiophene-co-phananthrene-quinoxaline) (PIDT-phanQ). In addition, this approach can also be applied to a low bandgap polymer poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(5-fluoro-2,1,3-benzothia-diazole)] (PCPDTFBT), and PCEs up to 7.9% are achieved. Due to the very thin total active layer thickness, a highly efficient ST tandem cell based on PIDT-phanQ exhibits a high PCE of 7.4%, which is the highest value reported to date for a ST solar cell. The ST device also possesses a desirable average visible transmittance (≈40%) and an excellent color rendering index (≈100), permitting its use in power-generating window applications.

A synergistic approach combining new material design and interfacial engineering of devices is adopted to produce high efficiency inverted solar cells. Two new polymers, based on an indacenodithieno[3,2-b]thiophene-difluorobenzothiadiazole (PIDTT-DFBT) donor–acceptor (D–A) polymer, are produced by incorporating either an alkyl thiophene (PIDTT-DFBT-T) or alkyl thieno[3,2-b]thiophene (PIDTT-DFBT-TT) π-bridge as spacer. Although the PIDTT-DFBT-TT polymer exhibits decreased absorption at longer wavelengths and increased absorption at higher energy wavelengths, it shows higher power conversion efficiencies in devices. In contrast, the thiophene bridged PIDTT-DFBT-T shows a similar change in its absorption spectrum, but its low molecular weight leads to reduced hole mobilities and performance in photovoltaic cells. Inverted solar cells based on PIDTT-DFBT-TT are explored by modifying the electron-transporting ZnO layer with a fullerene self-assembled monolayer and the MoO₃ hole-transporting layer with graphene oxide. This leads to power conversion efficiencies as high as 7.3% in inverted cells. PIDTT-DFBT-TT's characteristic strong short wavelength absorption and high efficiency suggests it is a good candidate as a wide band gap material for tandem solar cells.

Recent reports have shown that self-assembled monolayers (SAMs) can induce doping effects in graphene transistors. However, a lack of understanding persists surrounding the quantitative relationship between SAM molecular design and its effects on graphene. In order to facilitate the fabrication of next-generation graphene-based devices it is important to reliably and predictably control the properties of graphene without negatively impacting its intrinsic high performance. In this study, SAMs with varying dipole magnitudes/directions are utilized and these values are directly correlated to changes in performance seen in graphene transistors. It is found that, by knowing the z-component of the SAM dipole, one can reliably predict the shift in graphene charge neutrality point after taking into account the influence of the metal electrodes (which also play a role in doping graphene). This relationship is verified through density functional theory and comprehensive device studies utilizing atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and electrical characterization of graphene transistors. It is shown that properties of graphene transistors can be predictably controlled with SAMs when considering the total doping environment. Additionally, it is found that methylthio-terminated SAMs strongly interact with graphene allowing for a cleaner graphene transfer and enhanced charge mobility.

A multi-ring, ladder-type low band-gap polymer (PIDTCPDT-DFBT) is developed to show enhanced light harvesting, charge transport, and photovoltaic performance. It possesses excellent planarity and enhanced effective conjugation length compared to the previously reported fused-ring polymers. In order to understand the effect of extended fused-ring on the electronic and optical properties of this polymer, a partially fused polymer PIDTT-T-DFBT is also synthesized for comparison. The fully rigidified polymer provides lower reorganizational energy, resulting in one order higher hole mobility than the reference polymer. The device made from PIDTCPDT-DFBT also shows a quite promising power conversion efficiency of 6.46%. Its short-circuit current (14.59 mA cm⁻²) is also among the highest reported for ladder-type polymers. These results show that extending conjugation length in fused-ring ladder polymers is an effective way to reduce band-gap and improve charge transport for efficient photovoltaic devices.

The versatility of a fluoro-containing low band-gap polymer, poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b’]dithiophene)-alt-4,7-(5-fluoro-2,1,3-benzothia-diazole)] (PCPDTFBT) in organic photovoltaics (OPVs) applications is demonstrated. High boiling point 1,3,5-trichlorobenzene (TCB) is used as a solvent to manipulate PCPDTFBT:[6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) active layer morphology to obtain high-performance single-junction devices. It promotes the crystallization of PCPDTFBT polymer, thus improving the charge-transport properties of the active layer. By combining the morphological manipulation with interfacial optimization and device engineering, the single-junction device exhibits both good air stability and high power-conversion efficiency (PCE, of 6.6%). This represents one of the highest PCE values for cyclopenta[2,1-b;3,4-b’]dithiophene (CPDT)-based OPVs. This polymer is also utilized for constructing semitransparent solar cells and double-junction tandem solar cells to demonstrate high PCEs of 5.0% and 8.2%, respectively.

Although high power conversion efficiencies (PCE) have already been demonstrated in conventional structure polymer solar cells (PSCs), the development of high performance inverted structure polymer solar cells is still lagging behind despite their demonstrated superior stability and feasibility for roll-to-roll processing. To address this challenge, a detailed study of solution-processed, inverted-structure PSCs based on the blends of a low bandgap polymer, poly(indacenodithiophene-co-phananthrene-quinoxaline) (PIDT-PhanQ) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) as the bulk heterojunction (BHJ) layer is carried out. Comprehensive characterization and optical modeling of the resulting devices is performed to understand the effect of device geometry on photovoltaic performance. Excellent device performance can be achieved by optimizing the optical field distribution and spatial profiles of excitons generation within the active layer in different device configurations. In the inverted structure, because the peak of the excitons generation is located farther away from the electron-collecting electrode, a higher blending ratio of fullerene is required to provide higher electron mobility in the BHJ for achieving good device performance.

A series of light-harvesting conjugated polymers were designed and synthesized for polymer solar cells. These newly designed polymers comprise an unusual two-dimensional conjugated structure with an electron-rich thiophene–triphenylamine backbone and stable planar indacenodithiophene π-bridges terminated with tunable electron acceptors. It was found that the electron-withdrawing strength of the acceptor could be used to manipulate the energy level of the lowest unoccupied molecular orbital and bandgap (as much as 0.3 eV), generating derivatives with complementary absorbance in the visible spectrum. This approach provides great flexibility in fine tuning the electronic and optical properties of the resultant polymers and facilitates the investigation of how these chemical modifications alter the subsequent photovoltaic properties of these materials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

In this study, we demonstrate in-situ n-doping and crosslinking of semiconducting polymers as efficient electron-transporting materials for inverted configuration polymer solar cells. The semiconducting polymers were crosslinked with bis(perfluorophenyl) azide (bis-PFPA) to form a robust solvent-resistant film, thereby preventing solvent-induced erosion during subsequent solution-based device processing. In addition, chemical n-doping of semiconducting polymers with (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl)dimethylamine (N-DMBI) substantially improved the power conversion efficiency of solar cells from 0.69% to 3.42%. These results open the way for progress on generally applicable polymeric interface materials, providing not only high device performance but also an effective fabrication method for solution-processed multilayer solar cell devices.

An efficient process is developed by spin-coating a single-component, self-assembled monolayer (SAM) to simultaneously modify the bottom-contact electrode and dielectric surfaces of organic thin-film transistors (OTFTs). This effi cient interface modifi cation is achieved using n-alkyl phosphonic acid based SAMs to prime silver bottom-contacts and hafnium oxide (HfO₂) dielectrics in low-voltage OTFTs. Surface characterization using near edge X-ray absorption fi ne structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), and spectroscopic ellipsometry suggest this process yields structurally well-defi ned phosphonate SAMs on both metal and oxide surfaces. Rational selection of the alkyl length of the SAM leads to greatly enhanced performance for both n-channel (C₆₀) and p-channel (pentacene) based OTFTs. Specifi cally, SAMs of n-octylphos-phonic acid (OPA) provide both low-contact resistance at the bottom-contact electrodes and excellent interfacial properties for compact semiconductor grain growth with high carrier mobilities. OTFTs based on OPA modifi ed silver electrode/HfO₂ dielectric bottom-contact structures can be operated using < 3V with low contact resistance (down to 700 Ohm-cm), low subthreshold swing (as low as 75 mV dec⁻¹), high on/off current ratios of 107, and charge carrier mobilities as high as 4.6 and 0.8 cm² V⁻¹ s⁻¹, for C60 and pentacene, respectively. These results demonstrate that this is a simple and efficient process for improving the performance of bottom-contact OTFTs.

An efficient process is developed by spin-coating a single-component, self-assembled monolayer (SAM) to simultaneously modify the bottom-contact electrode and dielectric surfaces of organic thin-film transistors (OTFTs). This effi cient interface modifi cation is achieved using n-alkyl phosphonic acid based SAMs to prime silver bottom-contacts and hafnium oxide (HfO₂) dielectrics in low-voltage OTFTs. Surface characterization using near edge X-ray absorption fi ne structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), and spectroscopic ellipsometry suggest this process yields structurally well-defi ned phosphonate SAMs on both metal and oxide surfaces. Rational selection of the alkyl length of the SAM leads to greatly enhanced performance for both n-channel (C₆₀) and p-channel (pentacene) based OTFTs. Specifi cally, SAMs of n-octylphos-phonic acid (OPA) provide both low-contact resistance at the bottom-contact electrodes and excellent interfacial properties for compact semiconductor grain growth with high carrier mobilities. OTFTs based on OPA modifi ed silver electrode/HfO₂ dielectric bottom-contact structures can be operated using < 3V with low contact resistance (down to 700 Ohm-cm), low subthreshold swing (as low as 75 mV dec⁻¹), high on/off current ratios of 107, and charge carrier mobilities as high as 4.6 and 0.8 cm² V⁻¹ s⁻¹, for C60 and pentacene, respectively. These results demonstrate that this is a simple and efficient process for improving the performance of bottom-contact OTFTs.

Three amphiphilic block copolymers are employed to form polymeric micelles and function as nanocarriers to disperse hydrophobic aggregation-induced emission (AIE) dyes, 1,1,2,3,4,5-hexaphenylsilole (HPS) and/or bis(4-(N-(1-naphthyl) phenylamino)-phenyl)fumaronitrile (NPAFN), into aqueous solution for biological studies. Compared to their virtually non-emissive properties in organic solutions, the fluorescence intensity of these AIE dyes has increased significantly due to the spatial confinement that restricts intramolecular rotation of these dyes and their better compatibility in the hydrophobic core of polymeric micelles. The effect of the chemical structure of micelle cores on the photophysical properties of AIE dyes are investigated, and the fluorescence resonance energy transfer (FRET) from the green-emitting donor (HPS) to the red-emitting acceptor (NPAFN) is explored by co-encapsulating this FRET pair in the same micelle core. The highest fluorescence quantum yield (∼62%) could be achieved by encapsulating HPS aggregates in the micelles. Efficient energy transfer (>99%) and high amplification of emission (as high as 8 times) from the NPAFN acceptor could also be achieved by spatially confining the HPS/NPAFN FRET pair in the hydrophobic core of polymeric micelles. These micelles could be successfully internalized into the RAW 264.7 cells to demonstrate high-quality fluorescent images and cell viability due to improved quantum yield and reduced cytotoxicity.

The field of organic electronics has been developed vastly in the past two decades due to its promise for low cost, lightweight, mechanical flexibility, versatility of chemical design and synthesis, and ease of processing. The performance and lifetime of these devices, such as organic light-emitting diodes (OLEDs), photovoltaics (OPVs), and field-effect transistors (OFETs), are critically dependent on the properties of both active materials and their interfaces. Interfacial properties can be controlled ranging from simple wettability or adhesion between different materials to direct modifications of the electronic structure of the materials. In this Feature Article, the strategies of utilizing surfactant-modified cathodes, hole-transporting buffer layers, and self-assembled monolayer (SAM)-modified anodes are highlighted. In addition to enabling the production of high-efficiency OLEDs, control of interfaces in both conventional and inverted polymer solar cells is shown to enhance their efficiency and stability; and the tailoring of source–drain electrode–semiconductor interfaces, dielectric–semiconductor interfaces, and ultrathin dielectrics is shown to allow for high-performance OFETs.

Fluorescence from quantum dots (QDs) sandwiched between colloidal gold nanoparticles and lithographically created metal nanoarrays is studied using engineered peptides as binding agents. For optimized structures, a 15-fold increase is observed in the brightness of the QDs due to plasmon-enhanced fluorescence. This enhanced brightness is achieved by systematically tuning the vertical distance of the QD from the gold nanoparticles using solid-specific peptide linkers and by optimizing the localized surface plasmon resonance by varying the geometric arrangement of the patterned gold nanoarray. The size and pitch of the patterned array affect the observed enhancement, and sandwiching the QDs between the patterned features and colloidal gold nanoparticles yields even larger enhancements due to the increase in local electromagnetic hot spots induced by the increased surface roughness. The use of bifunctional biomolecular linkers to control the formation of hot spots in sandwich structures provides new ways to fabricate hybrid nanomaterials of architecturally induced functionality for biotechnology and photonics.

Fluorescence from quantum dots (QDs) sandwiched between colloidal gold nanoparticles and lithographically created metal nanoarrays is studied using engineered peptides as binding agents. For optimized structures, a 15-fold increase is observed in the brightness of the QDs due to plasmon-enhanced fluorescence. This enhanced brightness is achieved by systematically tuning the vertical distance of the QD from the gold nanoparticles using solid-specific peptide linkers and by optimizing the localized surface plasmon resonance by varying the geometric arrangement of the patterned gold nanoarray. The size and pitch of the patterned array affect the observed enhancement, and sandwiching the QDs between the patterned features and colloidal gold nanoparticles yields even larger enhancements due to the increase in local electromagnetic hot spots induced by the increased surface roughness. The use of bifunctional biomolecular linkers to control the formation of hot spots in sandwich structures provides new ways to fabricate hybrid nanomaterials of architecturally induced functionality for biotechnology and photonics.

A hydrophobic two-photon absorbing (2PA) red emitter (R) was successfully incorporated into micelles formed from two block copolymers, poly(ε-caprolactone)-block-poly(ethylene glycol)s, for imaging and toxicity studies. In micelles, the chromophore R exhibits a 2PA cross-section of 400 GM (1 GM = 1 × 10⁻⁵⁰ cm⁴ s photon⁻¹ molecule⁻¹) at 820 nm, which is among the highest values reported for red 2PA emitters. The micelles with a cationic amino moiety-containing poly(ethylene glycol) corona showed an enhancement of cell internalization and delivered the dye into the cytoplasmic regions of the mouse macrophage RAW 264.7 cells. In comparison, the dye in micelles with neutral poly(ethylene glycol) as corona could not be delivered into the cells. Cytotoxicity of the micelle-R constructs was studied using a 3-(4,5-dimethyl thiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. More than 90% of the cells were viable after they were stained with the dye-containing micelles at different concentrations (dye concentrations of 2–6 μM and polymer concentrations of 0.05–0.15 mg/mL) for 16 h. This is the first reported application of a hydrophobic 2,1,3-benzothiadiazole-containing 2PA red emitter delivered into the cytoplasm of cells for bioimaging and toxicity assessment. © 2009 Wiley Periodicals, Inc. J Biomed Mater Res, 2010

We report the design and synthesis of three alcohol-soluble neutral conjugated polymers, poly[9,9-bis(2-(2-(2-diethanolaminoethoxy) ethoxy)ethyl)fluorene] (PF-OH), poly[9,9-bis(2-(2-(2-diethanol-aminoethoxy)ethoxy)ethyl)fluorene-alt-4,4′-phenylether] (PFPE-OH) and poly[9,9-bis(2-(2-(2-diethanolaminoethoxy) ethoxy)ethyl)fluorene-alt-benzothiadizole] (PFBT-OH) with different conjugation length and electron affinity as highly efficient electron injecting and transporting materials for polymer light-emitting diodes (PLEDs). The unique solubility of these polymers in polar solvents renders them as good candidates for multilayer solution processed PLEDs. Both the fluorescent and phosphorescent PLEDs based on these polymers as electron injecting/transporting layer (ETL) were fabricated. It is interesting to find that electron-deficient polymer (PFBT-OH) shows very poor electron-injecting ability compared to polymers with electron-rich main chain (PF-OH and PFPE-OH). This phenomenon is quite different from that obtained from conventional electron-injecting materials. Moreover, when these polymers were used in the phosphorescent PLEDs, the performance of the devices is highly dependent on the processing conditions of these polymers. The devices with ETL processed from water/methanol mixed solvent showed much better device performance than the devices processed with methanol as solvent. It was found that the erosion of the phosphorescent emission layer could be greatly suppressed by using water/methanol mixed solvent for processing the polymer ETL. The electronic properties of the ETL could also be influenced by the processing conditions. This offers a new avenue to improve the performance of phosphorescent PLEDs through manipulating the processing conditions of these conjugated polymer ETLs.

For plastic (opto)electronic devices such as light-emitting diodes (LEDs), photovoltaic (PV) cells and field-effect transistors (FETs), the processes of charge (hole/electron) injection, charge transport, charge recombination (exciton formation), charge separation (exciton diffusion and dissociation) and charge collection are critical to enhance their performance. Most of these processes are relevant to nanoscale and interfacial phenomena. In this review, we highlight the state-of-the-art developments of interface-tailored and nanoengineered polymeric materials to optimize the performance of (opto)electronic devices. These include (1) interfacial engineering of anode and cathode for polymer LEDs; (2) nanoengineered (C₆₀ and inorganic semiconductor nanoparticles) π-conjugated polymeric materials for PV cells; and (3) polymer and monolayer dielectrics/interfaces for FETs and light-emitting and nano-FETs. Copyright © 2009 Society of Chemical Industry

This Focus Review describes molecular glasses as a new class of materials for nonlinear optical (NLO) applications, especially for electro-optic (E-O) devices. Examples of E-O molecular glasses are reviewed with a focus on the molecular design of NLO chromophores and solid-state engineering of molecular glasses. Molecular glasses based on dendrimers of multiple chromophores, molecular glass blends of chromophores, and molecular glasses based on reversible self-assembly of chromophores are introduced as promising architectures to prepare morphologically stable molecular glasses with large E-O activities and improved material properties for device applications. Future directions to fully exploit the potential of molecular glasses for NLO materials are presented.

In order to fulfill the promise of organic electronic devices, performance-limiting factors, such as the energetic discontinuity of the material interfaces, must be overcome. Here, improved performance of polymer light-emitting diodes (PLEDs) is demonstrated using self-assembled monolayers (SAMs) of triarylamine-based hole-transporting molecules with phosphonic acid-binding groups to modify the surface of the indium tin oxide (ITO) anode. The modified ITO surfaces are used in multilayer PLEDs, in which a green-emitting polymer, poly[2,7-(9,9-dihexylfluorene)-co-4,7-(2,1,3-benzothiadiazole)] (PFBT5), is sandwiched between a thermally crosslinked hole-transporting layer (HTL) and an electron-transporting layer (ETL). All tetraphenyl-diamine (TPD)-based SAMs show significantly improved hole-injection between ITO and the HTL compared to oxygen plasma-treated ITO and simple aromatic SAMs on ITO. The device performance is consistent with the hole-transporting properties of triarylamine groups (measured by electrochemical measurements) and improved surface energy matching with the HTL. The turn-on voltage of the devices using SAM-modified anodes can be lowered by up to 3 V compared to bare ITO, yielding up to 18-fold increases in current density and up to 17-fold increases in brightness at 10 V. Variations in hole-injection and turn-on voltage between the different TPD-based molecules are attributed to the position of alkyl-spacers within the molecules.