Surface NMR using quantum sensors in diamond.

NMR is a noninvasive, molecular-level spectroscopic technique widely used for chemical characterization. However, it lacks the sensitivity to probe the small number of spins at surfaces and interfaces. Here, we use nitrogen vacancy (NV) centers in diamond as quantum sensors to optically detect NMR signals from chemically modified thin films. To demonstrate the method's capabilities, aluminum oxide layers, common supports in catalysis and materials science, are prepared by atomic layer deposition and are subsequently functionalized by phosphonate chemistry to form self-assembled monolayers. The surface NV-NMR technique detects spatially resolved NMR signals from the monolayer, indicates chemical binding, and quantifies molecular coverage. In addition, it can monitor in real time the formation kinetics at the solid-liquid interface. With our approach, we show that NV quantum sensors are a surface-sensitive NMR tool with femtomole sensitivity for in situ analysis in catalysis, materials, and biological research.

Using Metal-Organic Frameworks to Confine Liquid Samples for Nanoscale NV-NMR.

Atomic-scale magnetic field sensors based on nitrogen vacancy (NV) defects in diamonds are an exciting platform for nanoscale nuclear magnetic resonance (NMR) spectroscopy. The detection of NMR signals from a few zeptoliters to single molecules or even single nuclear spins has been demonstrated using NV centers close to the diamond surface. However, fast molecular diffusion of sample molecules in and out of the nanoscale detection volumes impedes their detection and limits current experiments to solid-state or highly viscous samples. Here, we show that restricting diffusion by confinement enables nanoscale NMR spectroscopy of liquid samples. Our approach uses metal-organic frameworks (MOF) with angstrom-sized pores on a diamond chip to trap sample molecules near the NV centers. This enables the detection of NMR signals from a liquid sample, which would not be detectable without confinement. These results set the route for nanoscale liquid-phase NMR with high spectral resolution.

Optically Induced Long-Lived Chirality Memory in the Color-Tunable Chiral Lead-Free Semiconductor (R)/(S)-CHEA4Bi2BrxI10-x (x = 0-10).

Hybrid organic-inorganic networks that incorporate chiral molecules have attracted great attention due to their potential in semiconductor lighting applications and optical communication. Here, we introduce a chiral organic molecule (R)/(S)-1-cyclohexylethylamine (CHEA) into bismuth-based lead-free structures with an edge-sharing octahedral motif, to synthesize chiral lead-free (R)/(S)-CHEA4Bi2BrxI10-x crystals and thin films. Using single-crystal X-ray diffraction measurements and density functional theory calculations, we identify crystal and electronic band structures. We investigate the materials' optical properties and find circular dichroism, which we tune by the bromide-iodide ratio over a wide wavelength range, from 300 to 500 nm. We further employ transient absorption spectroscopy and time-correlated single photon counting to investigate charge carrier dynamics, which show long-lived excitations with optically induced chirality memory up to tens of nanosecond timescales. Our demonstration of chirality memory in a color-tunable chiral lead-free semiconductor opens a new avenue for the discovery of high-performance, lead-free spintronic materials with chiroptical functionalities.

Modular Assembly of Vibrationally and Electronically Coupled Rhenium Bipyridine Carbonyl Complexes on Silicon.

Hybrid inorganic/organic heterointerfaces are promising systems for next-generation photocatalytic, photovoltaic, and chemical-sensing applications. Their performance relies strongly on the development of robust and reliable surface passivation and functionalization protocols with (sub)molecular control. The structure, stability, and chemistry of the semiconductor surface determine the functionality of the hybrid assembly. Generally, these modification schemes have to be laboriously developed to satisfy the specific chemical demands of the semiconductor surface. The implementation of a chemically independent, yet highly selective, standardized surface functionalization scheme, compatible with nanoelectronic device fabrication, is of utmost technological relevance. Here, we introduce a modular surface assembly (MSA) approach that allows the covalent anchoring of molecular transition-metal complexes with sub-nanometer precision on any solid material by combining atomic layer deposition (ALD) and selectively self-assembled monolayers of phosphonic acids. ALD, as an essential tool in semiconductor device fabrication, is used to grow conformal aluminum oxide activation coatings, down to sub-nanometer thicknesses, on silicon surfaces to enable a selective step-by-step layer assembly of rhenium(I) bipyridine tricarbonyl molecular complexes. The modular surface assembly of molecular complexes generates precisely structured spatial ensembles with strong intermolecular vibrational and electronic coupling, as demonstrated by infrared spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy analysis. The structure of the MSA can be chosen to avoid electronic interactions with the semiconductor substrate to exclusively investigate the electronic interactions between the surface-immobilized molecular complexes.

Revealing Nanoscale Chemical Heterogeneities in Polycrystalline Mo-BiVO4 Thin Films.

The activity of polycrystalline thin film photoelectrodes is impacted by local variations of the material properties due to the exposure of different crystal facets and the presence of grain/domain boundaries. Here a multi-modal approach is applied to correlate nanoscale heterogeneities in chemical composition and electronic structure with nanoscale morphology in polycrystalline Mo-BiVO4 . By using scanning transmission X-ray microscopy, the characteristic structure of polycrystalline film is used to disentangle the different X-ray absorption spectra corresponding to grain centers and grain boundaries. Comparing both spectra reveals phase segregation of V2 O5 at grain boundaries of Mo-BiVO4 thin films, which is further supported by X-ray photoelectron spectroscopy and many-body density functional theory calculations. Theoretical calculations also enable to predict the X-ray absorption spectral fingerprint of polarons in Mo-BiVO4 . After photo-electrochemical operation, the degraded Mo-BiVO4 films show similar grain center and grain boundary spectra indicating V2 O5 dissolution in the course of the reaction. Overall, these findings provide valuable insights into the degradation mechanism and the impact of material heterogeneities on the material performance and stability of polycrystalline photoelectrodes.

Hybrid photoelectrochemical and photovoltaic cells for simultaneous production of chemical fuels and electrical power.

Harnessing solar energy to drive photoelectrochemical reactions is widely studied for sustainable fuel production and versatile energy storage over different timescales. However, the majority of solar photoelectrochemical cells cannot drive the overall photosynthesis reactions without the assistance of an external power source. A device for simultaneous and direct production of renewable fuels and electrical power from sunlight is now proposed. This hybrid photoelectrochemical and photovoltaic device allows tunable control over the branching ratio between two high-value products of solar energy conversion, requires relatively simple modification to existing photovoltaic technologies, and circumvents the photocurrent mismatches that lead to significant loss in tandem photoelectrochemical systems comprising chemically stable photoelectrodes. Our proof-of-concept device is based on a transition metal oxide photoanode monolithically integrated onto silicon that possesses both front- and backside photovoltaic junctions. This integrated assembly drives spontaneous overall water splitting with no external power source, while also producing electricity near the maximum power point of the backside photovoltaic junction. The concept that photogenerated charge carriers can be controllably directed to produce electricity and chemical fuel provides an opportunity to significantly increase the energy return on energy invested in solar fuels systems and can be adapted to a variety of architectures assembled from different materials.

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites.

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH2)2CsPb-halide (FACsPb-) and CH3NH3Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials. However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.

A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes.

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. Here, we demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co3O4/Co(OH)2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. These films comprise compact and continuous nanocrystalline Co3O4 spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH)2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p+n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.

Ultrafast Charge Transfer between Light Absorber and Co3O4 Water Oxidation Catalyst across Molecular Wires Embedded in Silica Membrane.

The mechanism of visible light-induced hole transfer from a molecular light absorber, in the form of a free-base porphyrin, coupled to a Co3O4 nanoparticle catalyst for water oxidation by a molecular wire (p-oligo(phenylenevinylene) featuring three aryl units) is investigated by transient absorption spectroscopy. The wires are covalently anchored on the Co3O4 surface and embedded in a dense, yet ultrathin (2 nm), silica layer that separates light absorber and catalyst. The porphyrin is electrostatically adsorbed on the silica surface, and aqueous colloidal solutions of the core-shell particles are used for transient optical measurements. Pulsed optical excitation of the porphyrin results in rapid injection of the photogenerated hole onto the molecular wire and concurrent formation of reduced light absorber in less than 1 picosecond (ps). Ultrafast charge separation was monitored by transient absorption of the wire radical cation, which is given by bands in the 500 to 600 nm region and at 1130 nm, while formation of reduced porphyrin was characterized by absorption at 700 nm. Forward transfer of the hole to Co3O4 catalyst proceeds in 255 ± 23 ps. Ultrafast transfer of positive charge from the molecular assembly to a metal oxide nanoparticle catalyst for water oxidation is unprecedented. Holes on Co3O4 recombined with electrons of the reduced sensitizer with biphasic kinetics on a much longer time scale of ten to several hundred nanoseconds. The unusually efficient hole transfer coupling of a molecular light absorber with an Earth-abundant metal oxide catalyst by silica-embedded p-oligo(phenylenevinylene) offers an approach for integrated artificial photosystems featuring product separation on the nanoscale.

Understanding the Oxygen Evolution Reaction Mechanism on CoOx using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy.

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co3O4/Co(OH)2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that the catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH)2 and partial conversion of the spinel Co3O4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co3O4 catalyst supports this interpretation and reveals that the presence of Co(OH)2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.

Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1.

Photocatalytic water splitting using particulate semiconductors is a potentially scalable and economically feasible technology for converting solar energy into hydrogen. Z-scheme systems based on two-step photoexcitation of a hydrogen evolution photocatalyst (HEP) and an oxygen evolution photocatalyst (OEP) are suited to harvesting of sunlight because semiconductors with either water reduction or oxidation activity can be applied to the water splitting reaction. However, it is challenging to achieve efficient transfer of electrons between HEP and OEP particles. Here, we present photocatalyst sheets based on La- and Rh-codoped SrTiO3 (SrTiO3:La, Rh; ref. ) and Mo-doped BiVO4 (BiVO4:Mo) powders embedded into a gold (Au) layer. Enhancement of the electron relay by annealing and suppression of undesirable reactions through surface modification allow pure water (pH 6.8) splitting with a solar-to-hydrogen energy conversion efficiency of 1.1% and an apparent quantum yield of over 30% at 419 nm. The photocatalyst sheet design enables efficient and scalable water splitting using particulate semiconductors.

High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites.

Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH3NH3PbI3-xBrx perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ Eg ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells.

Suppression of Photoanodic Surface Oxidation of n-Type 6H-SiC Electrodes in Aqueous Electrolytes.

The photoelectrochemical characterization of silicon carbide (SiC) electrodes is important for enabling a wide range of potential applications for this semiconductor. However, photocorrosion of the SiC surface remains a key challenge, because this process considerably hinders the deployment of this material into functional devices. In this report, we use cyclic voltammetry to investigate the stability of n-type 6H-SiC photoelectrodes in buffered aqueous electrolytes. For measurements in pure Tris buffer, photogenerated holes accumulate at the interface under anodic polarization, resulting in the formation of a porous surface oxide layer. Two possibilities are presented to significantly enhance the stability of the SiC photoelectrodes. In the first approach, redox molecules are added to the buffer solution to kinetically facilitate hole transfer to these molecules, and in the second approach, water oxidation in the electrolyte is induced by depositing a cobalt phosphate catalyst onto the semiconductor surface. Both methods are found to effectively suppress photocorrosion of the SiC electrodes, as confirmed by atomic force microscopy and X-ray photoelectron spectroscopy measurements. The presented study provides straightforward routes to stabilize n-type SiC photoelectrodes in aqueous electrolytes, which is essential for a possible utilization of this material in the fields of photocatalysis and multimodal biosensing.

Assembly and Photocarrier Dynamics of Heterostructured Nanocomposite Photoanodes from Multicomponent Colloidal Nanocrystals.

Multicomponent oxides and their heterostructures are rapidly emerging as promising light absorbers to drive oxidative chemistry. To fully exploit their functionality, precise tuning of their composition and structure is crucial. Here, we report a novel solution-based route to nanostructured bismuth vanadate (BiVO4) that facilitates the assembly of BiVO4/metal oxide (TiO2, WO3, and Al2O3) nanocomposites in which the morphology of the metal oxide building blocks is finely tailored. The combination of transient absorption spectroscopy-spanning from picoseconds to second time scales-and photoelectrochemical measurements reveals that the achieved structural tunability is key to understanding and directing charge separation, transport, and efficiency in these complex oxide heterostructured films.

p-Type Transparent Conducting Oxide/n-Type Semiconductor Heterojunctions for Efficient and Stable Solar Water Oxidation.

Achieving stable operation of photoanodes used as components of solar water splitting devices is critical to realizing the promise of this renewable energy technology. It is shown that p-type transparent conducting oxides (p-TCOs) can function both as a selective hole contact and corrosion protection layer for photoanodes used in light-driven water oxidation. Using NiCo2O4 as the p-TCO and n-type Si as a prototypical light absorber, a rectifying heterojunction capable of light driven water oxidation was created. By placing the charge separating junction in the Si using a np(+) structure and by incorporating a highly active heterogeneous Ni-Fe oxygen evolution catalyst, efficient light-driven water oxidation can be achieved. In this structure, oxygen evolution under AM1.5G illumination occurs at 0.95 V vs RHE, and the current density at the reversible potential for water oxidation (1.23 V vs RHE) is >25 mA cm(-2). Stable operation was confirmed by observing a constant current density over 72 h and by sensitive measurements of corrosion products in the electrolyte. In situ Raman spectroscopy was employed to investigate structural transformation of NiCo2O4 during electrochemical oxidation. The interface between the light absorber and p-TCO is crucial to produce selective hole conduction to the surface under illumination. For example, annealing to produce more crystalline NiCo2O4 produces only small changes in its hole conductivity, while a thicker SiOx layer is formed at the n-Si/p-NiCo2O4 interface, greatly reducing the PEC performance. The generality of the p-TCO protection approach is demonstrated by multihour, stable, water oxidation with n-InP/p-NiCo2O4 heterojunction photoanodes.

Hole selective MoOx contact for silicon solar cells.

Using an ultrathin (∼ 15 nm in thickness) molybdenum oxide (MoOx, x < 3) layer as a transparent hole selective contact to n-type silicon, we demonstrate a room-temperature processed oxide/silicon solar cell with a power conversion efficiency of 14.3%. While MoOx is commonly considered to be a semiconductor with a band gap of 3.3 eV, from X-ray photoelectron spectroscopy we show that MoOx may be considered to behave as a high workfunction metal with a low density of states at the Fermi level originating from the tail of an oxygen vacancy derived defect band located inside the band gap. Specifically, in the absence of carbon contamination, we measure a work function potential of ∼ 6.6 eV, which is significantly higher than that of all elemental metals. Our results on the archetypical semiconductor silicon demonstrate the use of nm-thick transition metal oxides as a simple and versatile pathway for dopant-free contacts to inorganic semiconductors. This work has important implications toward enabling a novel class of junctionless devices with applications for solar cells, light-emitting diodes, photodetectors, and transistors.

Efficient and sustained photoelectrochemical water oxidation by cobalt oxide/silicon photoanodes with nanotextured interfaces.

Plasma-enhanced atomic layer deposition of cobalt oxide onto nanotextured p(+)n-Si devices enables efficient photoelectrochemical water oxidation and effective protection of Si from corrosion at high pH (pH 13.6). A photocurrent density of 17 mA/cm(2) at 1.23 V vs RHE, saturation current density of 30 mA/cm(2), and photovoltage greater than 600 mV were achieved under simulated solar illumination. Sustained photoelectrochemical water oxidation was observed with no detectable degradation after 24 h. Enhanced performance of the nanotextured structure, compared to planar Si, is attributed to a reduced silicon oxide thickness that provides more intimate interfacial contact between the light absorber and catalyst. This work highlights a general approach to improve the performance and stability of Si photoelectrodes by engineering the catalyst/semiconductor interface.

Multifunctional silicon surfaces: reaction of dichlorocarbene generated from Seyferth reagent with hydrogen-terminated silicon (111) surfaces.

Insertion of dichlorocarbene (:CCl2), generated by decomposition of the Seyferth reagent PhHgCCl2Br, into the Si-H bond of a tertiary silane to form a Si-CCl2H group is an efficient homogeneous, molecular transformation. A heterogeneous version of this reaction, between PhHgCCl2Br and a silicon (111) surface terminated by tertiary Si-H bonds, was studied using a combination of surface-sensitive infrared and X-ray photoelectron spectroscopies. The insertion of dichlorocarbene into surface Si-H bonds parallels the corresponding reaction of silanes in solution, to produce surface-bound dichloromethyl groups (Si-CCl2H) covering ∼25% of the silicon surface sites. A significant fraction of the remaining Si-H bonds on the surface was converted to Si-Cl/Br groups during the same reaction, with PhHgCCl2Br serving as a halogen atom source. The presence of two distinct environments for the chlorine atoms (Si-CCl2H and Si-Cl) and one type of bromine atom (Si-Br) was confirmed by Cl 2p, Br 3d, and C 1s X-ray photoelectron spectroscopy. The formation of reactive, halogen-terminated atop silicon sites was also verified by reaction with sodium azide or the Grignard reagent (CH3MgBr), to produce Si-N3 or Si-Me functionalities, respectively. Thus, reaction of a hydrogen-terminated silicon (111) surface with PhHgCCl2Br provides a facile route to multifunctional surfaces possessing both stable silicon-carbon and labile silicon-halogen sites, in a single pot synthesis. The reactive silicon-halogen groups can be utilized for subsequent transformations and, potentially, the construction of more complex organic-silicon hybrid systems.

Nanostructured Black Silicon as a Stable and Surface-Sensitive Platform for Time-Resolved In Situ Electrochemical Infrared Absorption Spectroscopy.

Attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) is a powerful method for probing interfacial chemical processes. However, SEIRAS-active nanostructured metallic thin films for the in situ analysis of electrochemical phenomena are often unstable under biased aqueous conditions. In this work, we present a surface-enhancing structure based on etched black Si internal reflection elements with Au-coatings for in situ electrochemical ATR-SEIRAS. Using electrochemical potential-dependent adsorption and desorption of 4-methoxypyridine on Au, we demonstrate that black Si-based substrates offer advantages over commonly used structures, such as electroless-deposited Au on Si and electrodeposited Au on ITO-coated Si, due to the combination of high stability, sensitivity, and conductivity. These characteristics are especially valuable for time-resolved measurements where stable substrates are required over extended times. Furthermore, the low sheet resistance of Au layers on black Si reduces the RC time constant of the electrochemical cell, enabling a significantly higher time resolution compared to that of traditional substrates. Thus, we employ black Si-based substrates in conjunction with rapid- and step-scan Fourier transform infrared (FTIR) spectroscopy to investigate the adsorption and desorption kinetics of 4-methoxypyridine during in situ electrochemical potential steps. Adsorption is shown to be diffusion-limited, which allows for the determination of the mean molecular area in a fully established monolayer. Moreover, no significant changes in the peak ratios of vibrational modes with different orientations relative to the molecular axis are observed, suggesting a single adsorption mode and no alteration of the average molecular orientation during the adsorption process. Overall, this study highlights the enhanced performance of black Si-based substrates for both steady-state and time-resolved in situ electrochemical ATR-SEIRAS, providing a powerful platform for kinetic and mechanistic investigations of electrochemical interfaces.

Diamond-lattice photonic crystals assembled from DNA origami.

Colloidal self-assembly allows rational design of structures on the micrometer and submicrometer scale. One architecture that can generate complete three-dimensional photonic bandgaps is the diamond cubic lattice, which has remained difficult to realize at length scales comparable with the wavelength of visible or ultraviolet light. In this work, we demonstrate three-dimensional photonic crystals self-assembled from DNA origami that act as precisely programmable patchy colloids. Our DNA-based nanoscale tetrapods crystallize into a rod-connected diamond cubic lattice with a periodicity of 170 nanometers. This structure serves as a scaffold for atomic-layer deposition of high-refractive index materials such as titanium dioxide, yielding a tunable photonic bandgap in the near-ultraviolet.