Showing papers by "Alex K.-Y. Jen published in 2010"

Interface Engineering for Organic Electronics

Abstract: 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.

Efficient Polymer Solar Cells Based on the Copolymers of Benzodithiophene and Thienopyrroledione

Abstract: A low band gap polymer based on the copolymerization between benzodithiophene and thieno-pyrroledione units has been investigated in both conventional and inverted polymer bulk-heterojunction photovoltaic cells. High power conversion efficiencies of more than 4% in both device structures were demonstrated.

A Review on the Development of the Inverted Polymer Solar Cell Architecture

Abstract: The increase in energy production costs for fossil fuels has led to a search for an economically viable alternative energy source. One alternative energy source of particular interest is solar energy. A promising alternative to inorganic materials is organic semiconductor polymer solar cells due to their advantages of being cheaper, light weight, flexible and made into large areas by roll-to-roll processing. However, the conventional architecture that is typically used for fabricating solar cells requires high vacuum to deposit the top metal electrode which is not suitable for roll-to-roll processing. Recently an inverted device architecture has been investigated as a suitable architecture for developing the ideal roll-to-roll type processing of polymer-based solar cells. This review will go over the recent advances and approaches in the development of this type of inverted device architecture. We will highlight some of the work that we have done to integrate materials, device, interface, and processing o...

Metal grid/conducting polymer hybrid transparent electrode for inverted polymer solar cells

Abstract: A simple method was developed using metal grid/conducting polymer hybrid transparent electrode to replace indium tin oxide (ITO) for the fabrication of inverted structure polymer solar cells. The performance of the devices could be tuned easily by varying the width and separation of the metal grids. By combining the appropriate metal grid geometry with a thin conductive polymer layer, substrates with comparable transparency and sheet resistance to those of ITO could be achieved. Polymer solar cells fabricated using this hybrid electrode show efficiencies as high as ∼3.2%. This method provides a feasible way for fabricating low-cost, large-area organic solar cells.

Enhancement of aggregation-induced emission in dye-encapsulating polymeric micelles for bioimaging

Abstract: 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.

Effect of Chemical Modification of Fullerene-Based Self-Assembled Monolayers on the Performance of Inverted Polymer Solar Cells

Abstract: The interface of electron-selective ZnO in inverted polymer bulk-heterojunction (BHJ) solar cells was modified with a series of fullerene-based self-assembled monolayers (C60-SAM) containing different anchoring groups (catechol, carboxylic acid, and phosphonic acid), linkage location, and functionalization. The formation of the C60-SAM to the surface of ZnO was investigated by processing the SAM through either a solution immersion technique or a solution spin-coating method. It is found that the C60-SAMs with the carboxylic acid and catechol termination can be formed onto the surface of ZnO by simple solution spin-coating process, whereas all three anchoring groups can be formed by solution immersion technique. Heterojunction devices were fabricated under different processing conditions to form SAM leading to 2-fold, 75%, and 30% efficiency improvement with the carboxylic acid, catechol, and phosphonic acid C60-SAMs, respectively. The main contribution to the variation of efficiency from different SAMs is...

Electro-optic polymer infiltrated silicon photonic crystal slot waveguide modulator with 23 dB slow light enhancement

Abstract: A silicon/organic hybrid modulator integrating photonic crystal (PC) waveguide, 75 nm slot, and electro-optic (EO) polymer is experimentally demonstrated. Slow light in PC waveguide and strong field confinement in slot waveguide enable ultraefficient EO modulation with a record-low Vπ×L of 0.56 V mm and an in-device effective r33 of 132 pm/V. This result makes it the most efficient EO polymer modulator demonstrated to date. The modulated signal shows strong wavelength dependence and peak enhancement of 23 dB near the band edge of defect mode, which confirms the signature of the slow light effect.

Anode modification of inverted polymer solar cells using graphene oxide

Abstract: A simple method has been developed to modify the anode interface of inverted bulk-heterojunction (BHJ) polymer solar cells by spin-coating a thin layer of graphene oxide (GO) on top of the organic active layer. The device with GO exhibited a remarkable improvement in power conversion efficiency compared to devices without any interfacial layer, indicating that GO can effectively modify the BHJ/metal anode interface to facilitate efficient hole collection. The dependence of the device performance on the GO layer thickness was also investigated showing an optimum performance from a GO thickness of ∼2–3 nm.

Dielectric Surface-Controlled Low-Voltage Organic Transistors via n-Alkyl Phosphonic Acid Self-Assembled Monolayers on High-k Metal Oxide

Abstract: In this paper, we report on n-alkyl phosphonic acid (PA) self-assembled monolayer (SAM)/hafnium oxide (HfO(2)) hybrid dielectrics utilizing the advantages of SAMs for control over the dielectric/semiconductor interface with those of high-k metal oxides for low-voltage organic thin film transistors (OTFTs). By systematically varying the number of carbon atoms of the n-alkyl PA SAM from six to eighteen on HfO(2) with stable and low leakage current density, we observe how the structural nature of the SAM affects the thin-film crystal structure and morphology, and subsequent device performance of low-voltage pentacene based OTFTs. We find that two primary structural factors of the SAM play a critical role in optimizing the device electrical characteristics, namely, the order/disorder of the SAM and its physical thickness. High saturation-field-effect mobilities result at a balance between disordered SAMs to promote large pentacene grains and thick SAMs to aid in physically buffering the charge carriers in pentacene from the adverse effects of the underlying high-k oxide. Employing the appropriate n-alkyl PA SAM/HfO(2) hybrid dielectrics, pentacene-based OTFTs operate under -2.0 V with low hysteresis, on-off current ratios above 1 x 10(6), threshold voltages below -0.6 V, subthreshold slopes as low as 100 mV dec(-1), and field-effect mobilities as high as 1.8 cm(2) V(-1) s(-1).

Semiconducting polymer photodetectors with electron and hole blocking layers: high detectivity in the near-infrared.

Abstract: Sensing from the ultraviolet-visible to the infrared is critical for a variety of industrial and scientific applications Photodetectors with broad spectral response, from 300 nm to 1,100 nm, were fabricated using a narrow-band gap semiconducting polymer blended with a fullerene derivative By using both an electron-blocking layer and a hole-blocking layer, the polymer photodetectors, operating at room temperature, exhibited calculated detectivities greater than 1013 cm Hz1/2/W over entire spectral range with linear dynamic range approximately 130 dB The performance is comparable to or even better than Si photodetectors

Graphene oxide nanosheets based organic field effect transistor for nonvolatile memory applications

Abstract: Reversible switching characteristics of organic nonvolatile memory transistors (ONVMTs) using chemically synthesized graphene oxide (GO) nanosheets as a charge-trapping layer are reported. The transfer curves of GO based ONVMTs showed large gate bias dependent hysteresis with threshold voltage shifts over 20 V. After writing and erasing, stored data were well maintained showing more than two orders of ON/OFF ratio (ION/IOFF=∼102) for 104 s. These results suggest that GO nanosheets are one potential candidate as the charge-trapping layer in ONVMTs.

Synthesis, Characterization, and Photovoltaic Properties of Carbazole-Based Two-Dimensional Conjugated Polymers with Donor-π-Bridge-Acceptor Side Chains

Abstract: A series of carbazole-based narrow-band gap polymers with two-dimensional donor-π-bridge-acceptor (D-π-A) structures were synthesized and characterized for use in polymer bulk heterojunction solar cells. These D-π-A side-chain polymers were obtained through the Knoevenagel condensation between the aldehyde-containing precursor polymers and the corresponding acceptors. The resulting polymers have good solubility in common organic solvents and excellent thermal properties. The effects of the alkyl side chains and different dye contents on optical properties, electronic structures, charge-transporting ability, and device performance of these polymers were investigated. By blending these polymers as light-harvesting electron donors with (6,6)-phenyl-C71-butyric acid methyl ester (PC71BM) electron acceptors in bulk heterojunction solar cells, high power conversion efficiency (PCE), as high as 4.47%, could be achieved.

Highly efficient electro-optic polymers through improved poling using a thin TiO2-modified transparent electrode

Abstract: A sol-gel derived thin titanium dioxide (TiO2) layer was spin-coated onto indium-tin-oxide substrate to improve poling efficiency of recently developed electro-optic (E-O) polymers. The thin TiO2 layer significantly blocks excessive charge injection and reduces the leakage current during high field poling. Ultralarge E-O coefficients, up to 160–350 pm/V at 1310 nm, have been achieved. These results show higher poling efficiency (enhancement of 26%–40%) compared to the results of poled films without the TiO2 layer. This enhancement can be explained by field distribution flattening effect at high injection barrier with the insertion of TiO2 barrier layer.

40 GHz electro-optic modulation in hybrid silicon-organic slotted photonic crystal waveguides.

Abstract: In this Letter we demonstrate broadband electro-optic modulation with frequencies of up to 40GHz in slotted photonic crystal waveguides based on silicon-on-insulator substrates covered and infiltrated with a nonlinear optical polymer. Two-dimensional photonic crystal waveguides in silicon enable integrated optical devices with an extremely small geometric footprint on the scale of micrometers. The slotted waveguide design optimizes the overlap of the optical and electric fields in the second-order nonlinear optical medium and, hence, the interaction of the optical and electric waves.

Dually fluorescent sensing of pH and dissolved oxygen using a membrane made from polymerizable sensing monomers

Abstract: Using a thermal polymerization approach and polymerizable pH and oxygen sensing monomers with green and red emission spectra, respectively, new pH, oxygen, and their dual-sensing membranes were prepared using poly(2-hydroxyethyl methacrylate)-co-poly(acrylamide) as a matrix. The sensors were grafted on acrylate-modified quartz glass and characterized under different pH values, oxygen concentrations, ion strengths, temperatures and cell culture media. The pH and oxygen sensors were excited using the same excitation wavelength and exhibited well-separated emission spectra. The pH sensing films showed good response over the pH range 5.5–8.5, corresponding to pKa values in the biologically relevant range between 6.9 and 7.1. The oxygen sensing films exhibited linear Stern–Volmer quenching responses to dissolved oxygen. As the sensing membranes were prepared using thermally initiated polymerization of sensing moiety-containing monomers, no leaching of the sensors from the membranes to buffers or medium was observed. This advantageous characteristic accounts in part for the sensors’ biocompatibility without apparent toxicity to HeLa cells after 40 h incubation. The dual-sensing membrane was used to measure pH and dissolved oxygen simultaneously. The measured results correlated with the set-point values.

Synthesis, Nanostructure, Functionality, and Application of Polyfluorene-block-poly(N-isopropylacrylamide)s

Abstract: A series of amphiphilic rod−coil diblock copolymers with a polyfluorene (PF) as a hydrophobic and light-emitting rod and a poly(N-isopropylacrylamide) (PNIPAAm) as a hydrophilic coil were prepared. Their micellar nanostructures and fluorescence properties were stimulated using solvents, e.g., water and tetrahydrofuran (THF)/toluene (1:10 by volume), which were characterized using dynamic light scattering (DLS), transmission electron microscopy (TEM), atomic force microscopy (AFM), and fluorescence spectroscopy. A typical block copolymer P2 (Mn = 14 400, Mw/Mn = 1.80, the PF weight fraction is 9.4%) in water exhibited micelles with the PNIPAAm block as the corona, whereas the polymer showed inverse micelles in mixed organic solvents of THF/toluene with PF as the corona. Such different nanostructures resulted in their different fluorescence properties. The fluorescence spectrum of P2 did not indicate aggregations of the PF chains in the THF/toluene mixture. Blue emission with a high quantum yield (0.80) was...

Tuning the Kinetics and Energetics of Diels−Alder Cycloaddition Reactions to Improve Poling Efficiency and Thermal Stability of High-Temperature Cross-Linked Electro-Optic Polymers

Abstract: A comprehensive theoretical and experimental study of the bromo effect on Diels−Alder (DA) and retro-Diels−Alder (rDA) reactions between the anthracene-containing dienes and maleimide dienophile has been conducted to improve thermal stability and poling efficiency of electro-optic (EO) polymers. Calculations with density functional theory (DFT) reveal that the bromo substitution on anthracene-based dienes leads to significantly increased cycloaddition exothermicities (9−12 kcal/mol) but has a minor effect on their activation barriers (0.6−3 kcal/mol) when reacted with N-phenylmaleimide dienophile. These calculated values correlate very well with the experimental results obtained from a series of model compounds. The DA/rDA cross-linking protocols based on these compounds can be applied to several nonlinear optical (NLO) polymers and result in large EO coefficients (r33) (as high as 69 pm/V) and greatly improved thermal stability (up to 250 °C). This demonstrates that controlled DA/rDA reactions can be use...

Solution processed inverted tandem polymer solar cells with self-assembled monolayer modified interfacial layers

Abstract: Inverted tandem bulk-heterojunction solar cells with comparable efficiency to single layer devices have been demonstrated by utilizing two thin layers (∼50 nm) of poly-(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester as the active material and a fullerene self-assembled monolayer (C60-SAM) to modify the interfaces between the ZnO buffer layer and the active layer. Single and tandem solar cells without the SAM modification have much lower efficiencies than the ones with modification. The successful demonstrations of inverted tandem devices with SAM modification give promise of further device improvements if active materials with complementary absorption can be used.

Threshold voltage control in organic thin film transistors with dielectric layer modified by a genetically engineered polypeptide

Abstract: Precise control over the threshold voltage of pentacene-based organic thin film transistors was achieved by inserting a genetically engineered quartz-binding polypeptide at the semiconductor-dielectric interface. A 30 V range was accessed with the same peptide by adjusting the pH of the solution for peptide assembly while leaving other device properties unaffected. Mobility of 0.1–0.2 cm2 V−1 s−1 and on/off current ratio of >106 could be achieved for all devices regardless of the presence of the neutral peptide or the peptide assembled in acidic or basic conditions. This shift in threshold voltages is explained by the generation of charged species and dipoles due to variation in assembling conditions. Controlling device characteristics such as threshold voltage is essential for integration of transistors into electronic circuits.

Sub-Volt Silicon-Organic Electrooptic Modulator

Abstract: Lowering the operating voltage of electrooptic modulators is desirable for a variety of applications, most notably in analog photonics , and digital data communications . In particular for digital systems such as CPUs, it is desirable to develop modulators that are both temperature-insensitive and compatible with typically sub-2V CMOS electronics ; however, drive voltages in silicon-based MZIs currently exceed 6.5V . Here we show an MZI modulator based on an electrooptic polymer-clad silicon slot waveguide, with a halfwave voltage of only 0.69V, and a bandwidth of 500 MHz. We also show that there are also paths to significantly improve both the bandwidth and drive voltage . Our silicon-organic modulator has an intrinsic power consumption less than 0.66 pJ/bit, nearly an order of magnitude improvement over the previous lowest energy silicon MZI .

Solution-processed cross-linkable hole selective layer for polymer solar cells in the inverted structure

Abstract: Solution-processed cross-linkable tetraphenyldiamine-containing material (TPD-BVB) as a highly efficient hole selective transport layer was demonstrated. Polymer solar cells (PSCs) with an inverted structure fabricated with a thin cross-linked TPD-BVB film show comparable efficiency and superior long-term air stability when compared to devices fabricated with poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). Thus, solution-processed TPD-BVB is an attractive alternative to PEDOT:PSS as a hole extraction layer in inverted structure PSCs.

Using end groups to tune the linear and nonlinear optical properties of bis(dioxaborine)-terminated polymethine dyes.

Abstract: Six anionic pentamethine dyes with different 2,2-difluoro-4-aryl-1,3,2(2 H)-dioxaborin-6-yl termini were synthesized and isolated as tetra-n-octylammonium salts with a variety of aryl groups appended to increase conjugation beyond the dioxaborine termini. The increased conjugation was expected to decrease the energy of the lowest-lying excited state, and increase the transition dipole moment linking this state to the ground state, which would be anticipated to result in an increase in the real part of the third-order polarizability, Re(gamma). UV/Vis-NIR absorption spectroscopy indicates that the absorption maxima in DMSO vary from 691 to 761 nm, with the longest wavelength transitions observed for a derivative where the aryl group is 4-nitrophenyl. Closed-aperture Z-scan measurements at 1.3 microm in DMSO indicate that Re(gamma) varies from -2.9x10(-33) to -5.4x10(-33) esu in these systems. The largest magnitude of Re(gamma) was observed for a dye with E-4-styrylphenyl aryl groups. This result can be rationalized using a two-state expression which relates Re(gamma) to the energy and transition dipole moment of the transition from the ground state to the lowest-lying excited state. A nonamethine analogue of this compound was also synthesized and exhibits a slightly larger Re(gamma) with respect to a previously reported bis(dioxaborine)-terminated nonamethine. The extension of conjugation beyond the dioxaborine termini seems to result in an overall increase in Re(gamma). However, the effects are smaller than those found by increasing conjugation in the polymethine bridge due to reduced participation of terminal groups in the HOMO.

Interface engineering of organic electronics

Abstract: 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.

2,1,3-Benzothiadiazole (BTD)-moiety-containing red emitter conjugated amphiphilic poly(ethylene glycol)-block-poly(ε-caprolactone) copolymers for bioimaging

Abstract: 2,1,3-Benzothiadiazole (BTD)-containing red emitter was chemically conjugated onto amphiphilic poly(ethylene glycol)-block-poly(e-caprolactone) (PEG-b-PCL) copolymers to form two new fluorophore-conjugated block copolymers (P5 and P7). P5 is a cationic amino group-containing polymer, whereas P7 is a neutral polymer. The polymers formed micelles in aqueous solution with average diameters of 45 nm (P7) and 78 nm (P5), which were characterized using dynamic light scattering (DLS) and atomic force microscopy (AFM). Cell internalization of the micelles using mouse macrophage RAW 264.7 was investigated. The micelles formed from P5 were endocytosed into the cell's cytoplasm through a non-specific endocytosis process, which was affected by temperature and calcium ions. Micelles formed from P7 could not be endocytosed. The dramatic difference of cell uptake between P5 and P7 indicated the cationic amino groups had a strong influence on the cell internalization to enhance the endocytosis pathway. 3-(4,5-Dimethyl thiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) viability assay was used to evaluate the cytotoxicity of the P5 micelle and no significant toxicity was observed. This study is the first report regarding the synthesis of BTD-conjugated block copolymers and the application of the biomacromolecules for bioimaging.

Cooperative Near‐Field Surface Plasmon Enhanced Quantum Dot Nanoarrays

Abstract: 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.

Optimization of Active Layer and Anode Electrode for High-Performance Inverted Bulk-Heterojunction Solar Cells

Abstract: Inverted ZnO-NPs/C60-self-assembled monolayer (SAM)/poly(3-hexyl-thiophene):[6,6]-phenyl C61 butyric acid methyl ester solar cell devices were systemically optimized by varying the weight blend ratio of donor and acceptor from 1:0 to 1:1, the active layer thickness, the annealing temperature, the annealing time, and the top anode electrode. These inverted cells using C60-SAM modification show a transition to a more bulkheterojunction device at blend ratios of 1:0.3 to 1:0.4, thus leading to large increase in device efficiencies from 1.6% to 3.5%. Further increase in the ratio shows eventual saturation in device efficiency to 4.5%, thus indicating an optimum blend composition. A strong dependence of the annealing temperature and time on the fill factor of the device is observed, which is correlated to changes in the morphology of the active layer. The anode metal electrode work function was varied using Ca/Al, Al, Ag, Cu, Au, and Pd as the contacts. Devices incorporating a layer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) between the active layer and anode electrode exhibit similar Voc regardless of electrode work function, whereas devices without the PEDOT:PSS layer exhibited behavior more similar to the MIM model. Optimized devices show efficiencies of 4.5% using a blend ratio of 1:0.7, an active layer thickness of ~200 nm, and a thermal annealing condition of 160°C for 10 min using Ag as the top-metal-anode contact. Inverted polymer-based solar cells using cheaper metals like Cu showed similar device efficiency.

Rational Design Using Dewar’s Rules for Enhancing the First Hyperpolarizability of Nonlinear Optical Chromophores

Abstract: A rational material design based on Dewar’s predictions is introduced in this paper. A number of conjugation-bridge-modified phenylpolyene chromophores were proposed as candidates for nonlinear optical chromophores. Hyperpolarizabilities of these candidates were calculated using density functional theory with a two-state model and finite-field methods. Significant enhancement with up to 72% increase in the first hyperpolarizability was observed. Another design mechanism using the bond length alternation analysis was proposed and supported by the study. In addition to the strength of the acceptor and donor, and the positions modifying the electron delocalization pathway, the density of lower lying excited states is shown to play an important role in the molecular hyperpolarizability. Increasing the density of lower lying excited states can be an effective approach in the design of highly nonlinear chromophores.