Growth Rate and Cross-Linking Kinetics of Poly(divinyl benzene) Thin Films Formed via Initiated Chemical Vapor Deposition.

Initiated chemical vapor deposition (iCVD) allows for the formation of highly cross-linked, polymer thin films on a variety of substrates. Here, we study the impact of substrate stage temperature and filament temperature on the deposition and cross-linking characteristics of iCVD from divinyl benzene. Maintaining a constant monomer surface concentration reveals that deposition rates upward of 15 nm/min can be achieved at substrate stage temperatures of 50 °C. The degree of cross-linking is limited by the rate of initiation of the pendant vinyl bonds. At a filament temperature of 200 °C, the pendant vinyl bond conversion is highly sensitive to the surface concentration of initiator radicals. A significant decrease of the pendant vinyl bond conversion is observed with increasing stage temperatures. At higher filament temperatures, the pendant vinyl bond conversion appears to plateau at approximately 50%. However, faster deposition rates yield lower conversion. This trade-off is mitigated by increasing the filament temperature to increase initiator radical production. A higher flux of initiator radicals toward the surface at a constant deposition rate increases the rate of initiation of pendant vinyl bonds and therefore their overall conversion. At a deposition rate of ∼7 nm/min, an increase in the filament temperature from 200 to 240 °C results in an 18% increase in the pendant vinyl bond conversion.

Ultrathin and Conformal Initiated Chemical-Vapor-Deposited Layers of Systematically Varied Surface Energy for Controlling the Directed Self-Assembly of Block CoPolymers.

Directed self-assembly (DSA) of block copolymer (BCP) thin films is a promising approach to enable next-generation patterning at increasingly smaller length scales. DSA utilizes interfacial wetting layers to force the BCP domains to self-assemble with the desired orientation with respect to the substrate. Here, we demonstrate that initiated chemical-vapor-deposited (iCVD) polydivinylbenzene (pDVB) ultrathin films can direct the self-assembly of poly(styrene- block-methylmethacrylate). We found that the methyl radicals formed at increased filament temperatures during the iCVD process result in the backbone methylation of pDVB. By tuning the degree of backbone methylation, we systematically changed the wetting properties of the iCVD pDVB from a slight poly(methylmethacrylate) preference to complete poly(styrene) preference. Additionally, we utilize the conformal nature of the iCVD to form a wetting layer over a topographical line and space pattern, which is subsequently used to produce self-assembled BCP films with both perpendicular orientation and long-range alignment.

Scalable and durable polymeric icephobic and hydrate-phobic coatings.

Ice formation and accumulation on surfaces can result in severe problems for solar photovoltaic installations, offshore oil platforms, wind turbines and aircrafts. In addition, blockage of pipelines by formation and accumulation of clathrate hydrates of natural gases has safety and economical concerns in oil and gas operations, particularly at high pressures and low temperatures such as those found in subsea or arctic environments. Practical adoption of icephobic/hydrate-phobic surfaces requires mechanical robustness and stability under harsh environments. Here, we develop durable and mechanically robust bilayer poly-divinylbenzene (pDVB)/poly-perfluorodecylacrylate (pPFDA) coatings using initiated chemical vapor deposition (iCVD) to reduce the adhesion strength of ice/hydrates to underlying substrates (silicon and steel). Utilizing a highly-cross-linked polymer (pDVB) underneath a very thin veneer of fluorine-rich polymer (pPFDA) we have designed inherently rough bilayer polymer films that can be deposited on rough steel substrates resulting in surfaces which exhibit a receding water contact angle (WCA) higher than 150° and WCA hysteresis as low as 4°. Optical profilometer measurements were performed on the films and root mean square (RMS) roughness values of Rq = 178.0 ± 17.5 nm and Rq = 312.7 ± 23.5 nm were obtained on silicon and steel substrates, respectively. When steel surfaces are coated with these smooth hard iCVD bilayer polymer films, the strength of ice adhesion is reduced from 1010 ± 95 kPa to 180 ± 85 kPa. The adhesion strength of the cyclopentane (CyC5) hydrate is also reduced from 220 ± 45 kPa on rough steel substrates to 34 ± 12 kPa on the polymer-coated steel substrates. The durability of these bilayer polymer coated icephobic and hydrate-phobic substrates is confirmed by sand erosion tests and examination of multiple ice/hydrate adhesion/de-adhesion cycles.

Phase transition-induced band edge engineering of BiVO4 to split pure water under visible light.

Through phase transition-induced band edge engineering by dual doping with In and Mo, a new greenish BiVO4 (Bi1-XInXV1-XMoXO4) is developed that has a larger band gap energy than the usual yellow scheelite monoclinic BiVO4 as well as a higher (more negative) conduction band than H(+)/H2 potential [0 VRHE (reversible hydrogen electrode) at pH 7]. Hence, it can extract H2 from pure water by visible light-driven overall water splitting without using any sacrificial reagents. The density functional theory calculation indicates that In(3+)/Mo(6+) dual doping triggers partial phase transformation from pure monoclinic BiVO4 to a mixture of monoclinic BiVO4 and tetragonal BiVO4, which sequentially leads to unit cell volume growth, compressive lattice strain increase, conduction band edge uplift, and band gap widening.

Chemical Vapor Deposition of Thin, Conductive, and Fouling-Resistant Polymeric Films.

Fouling has been a persistent issue within applications ranging from membrane separation to biomedical implantation. Research to date focuses on fouling-resistant coatings, where electrical conductivity is unnecessary. In this study, we report the synthesis of multifunctional thin films with both fouling resistance and electrical conductivity for their potential applications in the electrolysis-based self-cleaning of separation membranes and in the field of bioelectronics. This unique combination of properties results in multifunctional coatings that are a zwitterionic derivative of intrinsically conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) synthesized via oxidative chemical vapor deposition (oCVD). Their fouling resistance is shown to be comparable to that of known dielectric fouling-resistant surfaces, such as a poly(4-vinylpyridine)-co-divinylbenzene (p4VP-DVB)-derived zwitterionic coating, an amphiphilic poly(1H,1H,2H,2H-perfluorodecyl acrylate-co-2-hydroxyethyl methacrylate) (pPFDA-HEMA) coating, and a glass surface, and are far superior to the fouling resistance of gold or polydimethylsiloxane (PDMS) surfaces. The fouling resistances of seven surfaces are quantitatively characterized by molecular force probe (MFP) analysis. In addition, four-point probe electrical measurements, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), variable-angle spectroscopic ellipsometry (VASE), profilometry, water contact angle (WCA) measurements, surface ζ-potential measurements, and atomic force microscopy (AFM) were employed to characterize the physiochemical properties and morphology of the different surfaces.

Synthesis of polymer bead nano-necklaces on aligned carbon nanotube scaffolds.

Here, we report the fabrication of aligned carbon nanotube (A-CNT)/conducting polymer (CP) heterostructures with both uniform conformal and periodic beaded polymer morphologies via oxidative chemical vapor deposition of poly(ethylenedioxythiophene). Periodic beaded CP morphologies are realized utilizing the Plateau-Rayleigh instability to transform the original uniform conformal film, yielding a beaded CP morphology with a >50% enhancement in specific surface area (SSA). Modeling indicates that this SSA increase originates from the internal volume of the A-CNTs becoming available for adsorption, and that these internal A-CNT surfaces, if they could be made accessible to electrolyte ions, could lead to >30% enhancement of specific gravimetric and volumetric capacitances of current state-of-the-art A-CNT/CP heterostructures.

Fabrication and Characterization of a Porous Silicon Drug Delivery System with an Initiated Chemical Vapor Deposition Temperature-Responsive Coating.

This paper reports on the fabrication of a pSi-based drug delivery system, functionalized with an initiated chemical vapor deposition (iCVD) polymer film, for the sustainable and temperature-dependent delivery of drugs. The devices were prepared by loading biodegradable porous silicon (pSi) with a fluorescent anticancer drug camptothecin (CPT) and coating the surface with temperature-responsive poly(N-isopropylacrylamide-co-diethylene glycol divinyl ether) (pNIPAM-co-DEGDVE) or non-stimulus-responsive poly(aminostyrene) (pAS) via iCVD. CPT released from the uncoated oxidized pSi control with a burst release fashion (∼21 nmol/(cm(2) h)), and this was almost identical at temperatures both above (37 °C) and below (25 °C) the lower critical solution temperature (LCST) of the switchable polymer used, pNIPAM-co-DEGDVE (28.5 °C). In comparison, the burst release rate from the pSi-pNIPAM-co-DEGDVE sample was substantially slower at 6.12 and 9.19 nmol/(cm(2) h) at 25 and 37 °C, respectively. The final amount of CPT released over 16 h was 10% higher at 37 °C compared to 25 °C for pSi coated with pNIPAM-co-DEGDVE (46.29% vs 35.67%), indicating that this material can be used to deliver drugs on-demand at elevated temperatures. pSi coated with pAS also displayed sustainable drug delivery profiles, but these were independent of the release temperature. These data show that sustainable and temperature-responsive delivery systems can be produced by functionalization of pSi with iCVD polymer films. Benefits of the iCVD approach include the application of the iCVD coating after drug loading without causing degradation of the drug commonly caused by exposure to factors such as solvents or high temperatures. Importantly, the iCVD process is applicable to a wide array of surfaces as the process is independent of the surface chemistry and pore size of the nanoporous matrix being coated.

iCVD Cyclic Polysiloxane and Polysilazane as Nanoscale Thin-Film Electrolyte: Synthesis and Properties.

A group of crosslinked cyclic siloxane (Si-O) and silazane (Si-N) polymers are synthesized via solvent-free initiated chemical vapor deposition (iCVD). Notably, this is the first report of cyclic polysilazanes synthesized via the gas-phase iCVD method. The deposited nanoscale thin films are thermally stable and chemically inert. By iCVD, they can uniformly and conformally cover nonplanar surfaces having complex geometry. Although polysiloxanes are traditionally utilized as dielectric materials and insulators, our research shows these cyclic organosilicon polymers can conduct lithium ions (Li(+) ) at room temperature. The conformal coating and the room temperature ionic conductivity make these cyclic organosilicon polymers attractive for use as thin-film electrolytes in solid-state batteries. Also, their synthesis process and properties have been systemically studied and discussed.

Zwitterionic Antifouling Coatings for the Purification of High-Salinity Shale Gas Produced Water.

Fouling refers to the undesirable attachment of organic molecules and microorganisms to submerged surfaces. It is an obstacle to the purification of shale gas produced water and is currently without an effective solution due to the highly contaminated nature of produced water. Here, we demonstrate the direct vapor application of a robust zwitterionic coating to a variety of substrates. The coating remains unprecedentedly hydrophilic, smooth, and effectively antifouling in extremely high salinity solutions (with salt concentration of 200,000 ppm). The fouling resistance is assessed rapidly and quantitatively with a molecular force spectroscopy-based method and corroborated using quartz crystal microbalance system with dissipation monitoring. Grazing angle attenuated total reflectance Fourier transform infrared is used in combination with X-ray photoelectron spectroscopy, atomic force microscope, and in situ spectroscopic ellipsometry to lend insight into the underlying mechanism for the exceptional stability and effectiveness of the zwitterionic coating under high-salinity conditions. A unique coating architecture, where the surface is concentrated with mobile zwitterionic moieties while the bulk is cross-linked to enhance coating durability, was discovered to be the origin of its stable fouling resistance under high salinity. Combined with previously reported exceptional stability in highly oxidative environments and strong fouling resistance to oil and grease, the zwitterionic surface here has the potential to enable low-cost, membrane-based techniques for the purification of produced water and to eventually balance the favorable economics and the concerning environmental impacts of the hydraulic fracturing industry.

Investigation into the Formation and Adhesion of Cyclopentane Hydrates on Mechanically Robust Vapor-Deposited Polymeric Coatings.

Blockage of pipelines by formation and accumulation of clathrate hydrates of natural gases (also called gas hydrates) can compromise project safety and economics in oil and gas operations, particularly at high pressures and low temperatures such as those found in subsea or arctic environments. Cyclopentane (CyC5) hydrate has attracted interest as a model system for studying natural gas hydrates, because CyC5, like typical natural gas hydrate formers, is almost fully immiscible in water; and thus CyC5 hydrate formation is governed not only by thermodynamic phase considerations but also kinetic factors such as the hydrocarbon/water interfacial area, as well as mass and heat transfer constraints, as for natural gas hydrates. We present a macroscale investigation of the formation and adhesion strength of CyC5 hydrate deposits on bilayer polymer coatings with a range of wettabilities. The polymeric bilayer coatings are developed using initiated chemical vapor deposition (iCVD) of a mechanically robust and densely cross-linked polymeric base layer (polydivinylbenzene or pDVB) that is capped with a covalently attached thin hydrate-phobic fluorine-rich top layer (poly(perfluorodecyl acrylate) or pPFDA). The CyC5 hydrates are formed from CyC5-in-water emulsions, and differential scanning calorimetry (DSC) is used to confirm the thermal dissociation properties of the solid hydrate deposits. We also investigate the adhesion of the CyC5 hydrate deposits on bare and bilayer polymer-coated silicon and steel substrates. Goniometric measurements with drops of CyC5-in-water emulsions on the coated steel substrates exhibit advancing contact angles of 148.3 ± 4.5° and receding contact angles of 142.5 ± 9.8°, indicating the strongly emulsion-repelling nature of the iCVD coatings. The adhesion strength of the CyC5 hydrate deposits is reduced from 220 ± 45 kPa on rough steel substrates to 20 ± 17 kPa on the polymer-coated steel substrates. The measured strength of CyC5 hydrate adhesion is found to correlate very well with the work of adhesion between the emulsion droplets used to form the CyC5 hydrate and the underlying substrates.

Water-Assisted Vapor Deposition of PEDOT Thin Film.

The synthesis and characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) using water-assisted vapor phase polymerization (VPP) and oxidative chemical vapor deposition (oCVD) are reported. For the VPP PEDOT, the oxidant, FeCl3 , is sublimated onto the substrate from a heated crucible in the reactor chamber and subsequently exposed to 3,4-ethylenedioxythiophene (EDOT) monomer and water vapor in the same reactor. The oCVD PEDOT was produced by introducing the oxidant, EDOT monomer, and water vapor simultaneously to the reactor. The enhancement of doping and crystallinity is observed in the water-assisted oCVD thin films. The high doping level observed at UV-vis-NIR spectra for the oCVD PEDOT, suggests that water acts as a solubilizing agent for oxidant and its byproducts. Although the VPP produced PEDOT thin films are fully amorphous, their conductivities are comparable with that of the oCVD produced ones.

Cross-linking and ultrathin grafted gradation of fluorinated polymers synthesized via initiated chemical vapor deposition to prevent surface reconstruction.

Poly(fluoroalkyl acrylate)s with long perfluorooctyl pendant groups have been found to lead to the release of biopersistent perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Those with no more than six perfluorinated carbons in pedant groups do not cause such problems. They, however, give poor dynamic water repellency due to extensive reorganization of surface fluorinated groups when exposed to the water interface. In this work, thin films exhibiting improved dynamic water repellency, as evidenced by water contact angle (WCA) measurements, were synthesized via substrate-independent initiated chemical vapor deposition (iCVD) from 1H,1H,2H,2H-perfluorooctyl acrylate (C6PFA) and divinylbenzene (DVB) using two methods: copolymerization and ultrathin grafted gradation. The copolymerization between C6PFA and the cross-linker, DVB, was confirmed by Fourier transform infrared (FTIR) spectroscopy. The cross-linking is concluded to hinder the reorganization of surface fluorinated groups. The grafted gradation, consisting of an ultrathin pC6PFA top layer and a pDVB base layer, was characterized by angle-resolved X-ray photoelectron spectroscopy (ARXPS) measurements, which indicated that the top layer of pC6PFA is <2.5 nm thick to achieve the best dynamic water repellency. The outmost surface of this structure is fully covered by fluorinated groups, giving hydrophobicity. Concurrently, thanks to the interlayer grafting and the ultrathinness of the top layer, the fluorinated groups' tendency to migrate away from water interface is sterically blocked by the highly cross-linked pDVB base layer. The proposed approaches effectively reduced WCA hysteresis of C6PFA-based thin film to as low as 26.9° while maintaining sufficient hydrophobicity (advanced WCA of 119.6°). Due to the conformal and substrate-independent nature of iCVD technique, the films could be used to coat textured surfaces to generate superhydrophobicity.

Closed batch initiated chemical vapor deposition of ultrathin, functional, and conformal polymer films.

A modified fabrication process based on initiated chemical vapor deposition (iCVD) has been developed for producing ultrathin and uniform polymer films. This so-called "closed batch" (CB) iCVD process provides fine-tuning of the thickness and deposition rate of polymeric materials while using significantly less reactant material than the conventional continuous flow (CF) iCVD process. Four different polymers, poly(N-isopropylacrylamide), poly(trivinyltrimethylcyclotrisiloxane), poly(1H,1H,2H,2H-perfluorodecyl acrylate), and poly(ε-caprolactone), were synthesized by both CB and traditional CF iCVD. The resulting CB iCVD polymers are functionally identical to CF iCVD and solution-polymerized materials. Additionally, the new CB process retains the desirable ability to achieve conformal coverage over microstructures. Ultrathin (<30 nm) films can be controllably and reproducibly deposited; no prior optimization process is required to obtain excellent film thickness uniformity. The CB iCVD films are also extremely smooth, exhibiting RMS roughness values between 0.4 and 0.7 nm. Use of the CB process improves reaction yield by factors of 10-200 for the four different film chemistries and decreases material cost per 100 nm of film by 1-2 orders of magnitude.

Initiated chemical vapor deposition and light-responsive cross-linking of poly(vinyl cinnamate) thin films.

The first vapor-phase deposition of poly(vinyl cinnamate) (PVCin) is reported. Initiated chemical vapor deposition (iCVD) is used to synthesize PVCin thin films with an average thickness of 100 nm. Free radical polymerization and cyclization reactions compete during the deposition process, with approximately 45% of the repeat units undergoing cyclization. Exposure to UV light (λ = 254 nm) induces dimerization (cross-linking) of the PVCin, which is quantified using spectroscopic techniques. Approximately 90% of the free cinnamate moieties are dimerized at a UV dose of 300 mJ cm(-2) . PVCin is also incorporated into a copolymer with N-isopropylacrylamide, which exhibits a characteristic change in hydrophilicity with temperature. The copolymer is selectively cross-linked through a mask, and reversible swelling of patterns with 30 µm resolution is demonstrated by submerging the film in water.

Microworm optode sensors limit particle diffusion to enable in vivo measurements.

There have been a variety of nanoparticles created for in vivo uses ranging from gene and drug delivery to tumor imaging and physiological monitoring. The use of nanoparticles to measure physiological conditions while being fluorescently addressed through the skin provides an ideal method toward minimally invasive health monitoring. Here we create unique particles that have all the necessary physical characteristics to serve as in vivo reporters, but with minimized diffusion from the point of injection. These particles, called microworms, have a cylindrical shape coated with a biocompatible porous membrane that possesses a large surface-area-to-volume ratio while maintaining a large hydrodynamic radius. We use these microworms to create fluorescent sodium sensors for use as in vivo sodium concentration detectors after subcutaneous injection. However, the microworm concept has the potential to extend to the immobilization of other types of polymers for continuous physiological detection or delivery of molecules.

Designing Organic and Hybrid Surfaces and Devices with Initiated Chemical Vapor Deposition (iCVD).

The initiated chemical vapor deposition (iCVD) technique is an all-dry method for designing organic and hybrid polymers. Unlike methods utilizing liquids or line-of-sight arrival, iCVD provides conformal surface modification over intricate geometries. Uniform, high-purity, and pinhole-free iCVD films can be grown with thicknesses ranging from >15 µm to <5 nm. The mild conditions permit damage-free growth directly onto flexible substrates, 2D materials, and liquids. Novel iCVD polymer morphologies include nanostructured surfaces, nanoporosity, and shaped particles. The well-established fundamentals of iCVD facilitate the systematic design and optimization of polymers and copolymers. The functional groups provide fine-tuning of surface energy, surface charge, and responsive behavior. Further reactions of the functional groups in the polymers can yield either surface modification, compositional gradients through the layer thickness, or complete chemical conversion of the bulk film. The iCVD polymers are integrated into multilayer device structures as desired for applications in sensing, electronics, optics, electrochemical energy storage, and biotechnology. For these devices, hybrids offer higher values of refractive index and dielectric constant. Multivinyl monomers typically produce ultrasmooth and pinhole-free and mechanically deformable layers and robust interfaces which are especially promising for electronic skins and wearable optoelectronics.

CVD of polymeric thin films: applications in sensors, biotechnology, microelectronics/organic electronics, microfluidics, MEMS, composites and membranes.

Polymers with their tunable functionalities offer the ability to rationally design micro- and nano-engineered materials. Their synthesis as thin films have significant advantages due to the reduced amounts of materials used, faster processing times and the ability to modify the surface while preserving the structural properties of the bulk. Furthermore, their low cost, ease of fabrication and the ability to be easily integrated into processing lines, make them attractive alternatives to their inorganic thin film counterparts. Chemical vapor deposition (CVD) as a polymer thin-film deposition technique offers a versatile platform for fabrication of a wide range of polymer thin films preserving all the functionalities. Solventless, vapor-phase deposition enable the integration of polymer thin films or nanostructures into micro- and nanodevices for improved performance. In this review, CVD of functional polymer thin films and the polymerization mechanisms are introduced. The properties of the polymer thin films that determine their behavior are discussed and their technological advances and applications are reviewed.

Co-polymer clad design for high performance athermal photonic circuits.

Ubiquitous, low power consumption and high bandwidth density communication will require passive athermal optical filters for WDM transceivers in Si-CMOS architecture. Two silicon-polymer composite structures, deposited using initiated chemical vapor deposition (iCVD), poly(perfluorodecyl acrylate) (pPFDA) and poly(perfluorodecyl acrylate-co-divinyl benzene) p(PFDA-co-DVB), are analyzed as candidates for thermal compensation. The addition of DVB to a fluorinated acrylate backbone reduces the C-F bond density, increases the density in the copolymer and thereby increases refractive index. The addition of DVB also increases the volume expansion coefficient of the copolymer, resulting in an increased thermo-optic (TO) coefficient for the copolymer system. The increased index and TO coefficient of the co-polymer gives improved bend loss, footprint and FSR performance for athermal silicon photonic circuits.

Ultrathin antifouling coatings with stable surface zwitterionic functionality by initiated chemical vapor deposition (iCVD).

Antifouling thin films of poly[N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl)-co-2-(dimethylamino)ethyl methacrylate-co-ethylene glycol dimethacrylate] (PDDE) were synthesized via a substrate-independent and all-dry-initiated chemical vapor deposition (iCVD) technique followed by a diffusion-limited vapor-phase reaction with 1,3-propane sultone. Coated surfaces exhibited very low absorption of various foulants including bovine serum albumin (BSA), humic acid (HA), and sodium alginate (SA), as measured with the quartz crystal microbalance with dissipation monitoring (QCM-D). The fouling by humic acid was dependent on the presence of divalent cations such as Ca(2+). Both depth profiling and angle-resolved X-ray photoelectron spectroscopy (XPS) measurements indicated that the zwitterionic groups were highly concentrated in the top ~3 nm of the film. The contact angle measurements revealed a limited degree of surface chain reorganization upon contacting water. The dynamic contact angles remained unchanged after 100 days of storage in air, indicating the stability of the interface. The coating was substrate-independent, and the film was conformal on surface nanostructures including trenches, reverse osmosis membranes, and electrospun nanofiber mats.

Multijunction organic photovoltaics with a broad spectral response.

We demonstrate series-integrated multijunction organic photovoltaics fabricated monolithically by vapor-deposition in a transposed subcell order with the near-infrared-absorbing subcell in front of the green-absorbing subcell. This transposed subcell order is enabled by the highly complementary absorption spectra of a near-infrared-absorbing visibly-transparent subcell and a visible-absorbing subcell and motivated by the non-spatially-uniform optical intensity in nanoscale photovoltaics. The subcell order and thicknesses are optimized via transfer-matrix formalism and short-circuit current simulations. An efficient charge recombination zone consisting of layers of BCP/Ag/MoOx leads to negligible voltage and series-resistance losses. Under 1-sun illumination the multijunction solar cells exhibit a power conversion efficiency of 5.5 ± 0.2% with an FF of 0.685 ± 0.002 and a V(OC) of 1.65 ± 0.02 V, corresponding to the sum of the V(OC) of the component subcells. These devices exhibit a broad spectral response (in the wavelength range of 350 nm to 850 nm) but are limited by subcell external quantum efficiencies between 20% and 30% over the photoactive spectrum.