Publications

Direct optical lithography presents a promising patterning method for colloidal quantum dots (QDs). However, additional care needs to be taken to prevent deterioration of the optical properties of QDs upon the patterning process, especially for InP-based QDs. This study proposes an efficient method for high-resolution patterning of InP-based QDs using a photoacid generator, while preserving their optical properties. Specifically, our solid-state ligand exchange strategy, replacing chloride ligands with long-chain amine/carboxylate pair-ligands, successfully recovered the photoluminescence quantum yield (PLQY) of the patterned InP-based QD films to ~67% of the original PLQY. Upon examining the origins of the PLQY reduction during patterning, we concluded that the formation of deep traps caused by the exchanged chloride ligands was the primary cause. Finally, we fabricated high-resolution (feature size: 1 µm), multicolored patterns of InP-based QDs, thereby demonstrating the potential of the proposed patterning method for next-generation high-resolution displays and optoelectronic devices.

Quantum dots couple to form artificial molecules that allow for variable colour emission in response to an electric field.

Atoms as the building blocks of matter and the chemical bonds between atoms remain fundamental concepts in chemistry. Covalent and ionic bonds between atoms were elegantly described by Linus Pauling’s notion of electronegativity, which was further developed by Robert Mulliken who introduced the molecular orbital theory. Now, with the advancement of nanoscience, it may become possible to expand and generalize the concepts of ‘atom’ and ‘chemical bond’. Quantum dots (QDs), which are nanometre-sized semiconductor crystals, are sometimes referred to as ‘artificial atoms’ owing to their discrete electronic energy levels that closely resemble electronic states of atoms. The electronic structure of QDs can be continuously varied, something that cannot be done with traditional atoms found in the periodic table. There now exists an opportunity to develop a paradigm that uses QDs with precisely engineered sizes, shapes, compositions and concomitant electronic structures for building ‘artificial molecules’ and ‘artificial solids’. Just as atoms combine to form molecules with properties dramatically different from those of the atomic constituents, electronic bonding of QDs will lead to new structures that can be called colloidal quantum dot molecules (CQDMs). Now, writing in Nature Materials, Ossia et al. report that QDs coupled together into a CQDM can demonstrate optoelectronic signatures of an artificial bond that forms between two colloidal QDS.

Colloidal nanoparticles of semiconductors, metals, magnets, and other functional materials have been actively researched for several decades by both academic and industrial scientists and engineers. Colloidal nanoparticles offer insights into the peculiarities of nucleation and growth and the reactivity of surfaces, while the industry sees in nanoparticles a unique opportunity to combine functionalities typical for inorganic solids with structural flexibility and processability of polymers. Central to both of these pursuits is the interface between the inorganic nanoparticle core and the surface ligands that are covalently or electrostatically bound to the core surface. These surface ligands are integral components of nanomaterials. They direct nanoparticle formation, influence their chemical reactivity and electronic structure, and mediate interactions with the environment. The study of core–ligand interaction and the design of new ways to diversify the ligands is therefore an area of study that is inextricably linked to nanoscience.

Semiconductor-based biointerfaces are typically established either on the surface of the plasma membrane or within the cytoplasm. In Gram-negative bacteria, the periplasmic space, characterized by its confinement and the presence of numerous enzymes and peptidoglycans, offers additional opportunities for biomineralization, allowing for nongenetic modulation interfaces. We demonstrate semiconductor nanocluster precipitation containing single- and multiple-metal elements within the periplasm, as observed through various electron- and x-ray-based imaging techniques. The periplasmic semiconductors are metastable and display defect-dominant fluorescent properties. Unexpectedly, the defect-rich (i.e., the low-grade) semiconductor nanoclusters produced in situ can still increase adenosine triphosphate levels and malate production when coupled with photosensitization. We expand the sustainability levels of the biohybrid system to include reducing heavy metals at the primary level, building living bioreactors at the secondary level, and creating semi-artificial photosynthesis at the tertiary level. The biomineralization-enabled periplasmic biohybrids have the potential to serve as defect-tolerant platforms for diverse sustainable applications.

Semiconductors are commonly divided into materials with direct or indirect band gaps based on the relative positions of the top of the valence band and the bottom of the conduction band in crystal momentum (k) space. It has, however, been debated if k is a useful quantum number to describe the band structure in quantum-confined nanocrystalline systems, which blur the distinction between direct and indirect gap semiconductors. In bulk III–V semiconductor alloys like In_1–xGa_xP, the band structure can be tuned continuously from the direct- to indirect-gap by changing the value of x. The effect of strong quantum confinement on the direct-to-indirect transition in this system has yet to be established because high-quality colloidal nanocrystal samples have remained inaccessible. Herein, we report one of the first systematic studies of ternary III–V nanocrystals by utilizing an optimized molten-salt In-to-Ga cation exchange protocol to yield bright In_1–xGa_xP/ZnS core–shell particles with photoluminescence quantum yields exceeding 80%. We performed two-dimensional solid-state NMR studies to assess the alloy homogeneity and the extent of surface oxidation in In_1–xGa_xP cores. The radiative decay lifetime for In_1–xGa_xP/ZnS monotonically increases with higher gallium content. Transient absorption studies on In_1–xGa_xP/ZnS nanocrystals demonstrate signatures of direct- and indirect-like behavior based on the presence or absence, respectively, of excitonic bleach features. Atomistic electronic structure calculations based on the semi-empirical pseudopotential model are used to calculate absorption spectra and radiative lifetimes and evaluate band-edge degeneracy; the resulting calculated electronic properties are consistent with experimental observations. By studying photoluminescence characteristics at elevated temperatures, we demonstrate that a reduced lattice mismatch at the III–V/II–VI core–shell interface can enhance the thermal stability of emission. These insights establish cation exchange in molten inorganic salts as a viable synthetic route to nontoxic, high-quality In_1–xGa_xP/ZnS QD emitters with desirable optoelectronic properties.

Two-dimensional (2D) transition-metal carbides and nitrides (MXenes) show impressive performance in applications, such as supercapacitors, batteries, electromagnetic interference shielding, or electrocatalysis. These materials combine the electronic and mechanical properties of 2D inorganic crystals with chemically modifiable surfaces, and surface-engineered MXenes represent an ideal platform for fundamental and applied studies of interfaces in 2D functional materials. A natural step in structural engineering of MXene compounds is the development and understanding of MXenes with various organic functional groups covalently bound to inorganic 2D sheets. Such hybrid structures have the potential to unite the tailorability of organic molecules with the unique electronic properties of inorganic 2D solids. Here, we introduce a new family of hybrid MXenes (h-MXenes) with amido- and imido-bonding between organic and inorganic parts. The description of h-MXene structure requires an intricate mix of concepts from the fields of coordination chemistry, self-assembled monolayers (SAMs) and surface science. The optical properties of h-MXenes reveal coherent coupling between the organic and inorganic components. h-MXenes also show superior stability against hydrolysis in aqueous solutions.

Stretchable light-emitting materials are the key components for realizing skin-like displays and optical biostimulation. All the stretchable emitters reported to date, to the best of our knowledge, have been based on electroluminescent polymers that only harness singlet excitons, limiting their theoretical quantum yield to 25%. Here we present a design concept for imparting stretchability onto electroluminescent polymers that can harness all the excitons through thermally activated delayed fluorescence, thereby reaching a near-unity theoretical quantum yield. We show that our design strategy of inserting flexible, linear units into a polymer backbone can substantially increase the mechanical stretchability without affecting the underlying electroluminescent processes. As a result, our synthesized polymer achieves a stretchability of 125%, with an external quantum efficiency of 10%. Furthermore, we demonstrate a fully stretchable organic light-emitting diode, confirming that the proposed stretchable thermally activated delayed fluorescence polymers provide a path towards simultaneously achieving desirable electroluminescent and mechanical characteristics, including high efficiency, brightness, switching speed and stretchability as well as low driving voltage.

MXenes have the potential for efficient light-to-heat conversion in photothermal applications. To effectively utilize MXenes in such applications, it is important to understand the underlying nonequilibrium processes, including electron−phonon and phonon−phonon couplings. Here, we use transient electron and X-ray diffraction to investigate the heating and cooling of photoexcited MXenes at femtosecond to nanosecond time scales. Our results show extremely strong electron−phonon coupling in Ti₃C₂-based MXenes, resulting in lattice heating within a few hundred femtoseconds. We also systematically study heat dissipation in MXenes with varying film thicknesses, chemical surface terminations, flake sizes, and annealing conditions. We find that the thermal boundary conductance (TBC) governs the thermal relaxation in films thinner than the optical penetration depth. We achieve a 2-fold enhancement of the TBC, reaching 20 MW m⁻² K⁻¹ by controlling the flake size or chemical surface termination, which is promising for engineering heat dissipation in photothermal and thermoelectric applications of the MXenes.

We report spin-polarized transient absorption for colloidal CdSe nanoplatelets as functions of thickness (2–6 monolayer thickness) and core/shell motif. Using electro-optical modulation of co- and cross-polarization pump–probe combinations, we sensitively observe spin-polarized transitions. Core-only nanoplatelets exhibit few-picosecond spin lifetimes that weakly increase with layer thickness. The spectral content of differenced spin-polarized signals indicate biexciton binding energies that decrease with increasing thickness and smaller values than previously reported. Shell growth of CdS with controlled thicknesses, which partially delocalize the electron from the hole, significantly increases the spin lifetime to ∼49 ps at room temperature. Implementation of ZnS shells, which do not alter delocalization but do alter surface termination, increased spin lifetimes up to ∼100 ps, bolstering the interpretation that surface termination heavily influences spin coherence, likely due to passivation of dangling bonds. Spin precession in magnetic fields both confirms long coherence lifetime at room temperature and yields the excitonic g factor.

Two-dimensional transition metal carbides and nitrides (MXenes) are a large family of materials actively studied for various applications, especially in the field of energy storage. MXenes are commonly synthesized by etching the layered ternary compounds, MAX phases. We demonstrate a direct synthetic route for scalable and atom-economic synthesis of MXenes, including phases that have not been synthesized from MAX phases, by the reactions of metals and metal halides with graphite, methane, or nitrogen. The direct synthesis enables chemical vapor deposition growth of MXene carpets and complex spherulite-like morphologies that form through buckling and release of MXene carpet to expose fresh surface for further reaction. The directly synthesized MXenes showed excellent energy storage capacity for Li-ion intercalation.

Group III nitrides are of great technological importance for electronic devices. These materials have been widely manufactured via high-temperature methods such as physical vapor transport (PVT), chemical vapor deposition (CVD), and hydride vapor phase epitaxy (HVPE). The preparation of group III nitrides by colloidal synthesis methods would provide significant advantages in the form of optical tunability via size and shape control and enable cost reductions through scalable solution-based device integration. Solution syntheses of III-nitride nanocrystals, however, have been scarce, and the quality of the synthesized products has been unsatisfactory for practical use. Here, we report that incorporating a molten salt phase in solution synthesis can provide a viable option for producing crystalline III-nitride nanomaterials. Crystalline GaN and AlN nanomaterials can be grown in a biphasic molten-salt/organic-solvent mixture under an ammonia atmosphere at moderate temperatures (less than 300 °C) and stabilized under ambient conditions by postsynthetic treatment with organic surface ligands. We suggest that microscopic reversibility of monomer attachment, which is essential for crystalline growth, can be achieved in molten salt during the nucleation and the growth of the III-nitride nanocrystals. We also show that increased ammonia pressure increases the size of the GaN nanocrystals produced. This work demonstrates that use of molten salt and high-pressure reactants significantly expands the chemical scope of solution synthesis of inorganic nanomaterials.

All-inorganic nanocrystals (NCs) are of great importance in a range of electronic devices. However, current all-inorganic NCs suffer from limitations in their optical properties, such as low fluorescence efficiencies. Here, we develop a general surface treatment strategy to obtain intensely luminescent all-inorganic NCs (ILANs) by using designed metal salts with noncoordinating anions that play a dual role in the surface treatment process: (i) removing the original organic ligands and (ii) binding to unpassivated Lewis basic sites to preserve the photoluminescent (PL) properties of the NCs. The absolute photoluminescence quantum yields (PLQYs) of red-emitting CdSe/ZnS NCs, green-emitting CdSe/CdZnSeS/ZnS NCs and blue-emitting CdZnS/ZnS NCs in polar solvents are 97%, 80% and 72%, respectively. Further study reveals that the passivated Lewis basic sites of ILANs by metal cations boost the efficiency of radiative recombination of electron-hole pairs. While the passivation of Lewis basic sites leads to a high PLQY of ILANs, the exposed Lewis acidic sites provide the possibility for in situ tuning of the functions of NCs, creating opportunities for direct optical patterning of functional NCs with high resolution.

Conducting organic materials, such as doped organic polymers, molecular conductors and emerging coordination polymers, underpin technologies ranging from displays to flexible electronics. Realizing high electrical conductivity in traditionally insulating organic materials necessitates tuning their electronic structure through chemical doping. Furthermore, even materials that are intrinsically conductive, such as single-component molecular conductors, require crystallinity for metallic behaviour. However, conducting polymers are often amorphous to aid durability and processability. Using molecular design to produce high conductivity in undoped amorphous materials would enable tunable and robust conductivity in many applications, but there are no intrinsically conducting organic materials that maintain high conductivity when disordered. Here we report an amorphous coordination polymer, Ni tetrathiafulvalene tetrathiolate, which displays markedly high electronic conductivity (up to 1,200 S cm⁻¹) and intrinsic glassy-metallic behaviour. Theory shows that these properties are enabled by molecular overlap that is robust to structural perturbations. This unusual set of features results in high conductivity that is stable to humid air for weeks, pH 0–14 and temperatures up to 140 °C. These findings demonstrate that molecular design can enable metallic conductivity even in heavily disordered materials, raising fundamental questions about how metallic transport can exist without periodic structure and indicating exciting new applications for these materials.

​Photothermoelectric (PTE) materials are promising candidates for solar energy harvesting and photodetection applications, especially for near-infrared (NIR) wavelengths. Although the processability and tunability of organic materials are highly advantageous, examples of organic PTE materials are comparatively rare and their PTE performance is typically limited by poor photothermal (PT) conversion. Here, we report the use of redox-active Sn complexes of tetrathiafulvalene-tetrathiolate (TTFtt) as transmetalating agents for the synthesis of presynthetically redox tuned NiTTFtt materials. Unlike the neutral material NiTTFtt, which exhibits n-type glassy-metallic conductivity, the reduced materials Li_1.2Ni_0.4[NiTTFtt] and [Li(THF)_1.5]_1.2Ni_0.4[NiTTFtt] (THF = tetrahydrofuran) display physical characteristics more consistent with p-type semiconductors. The broad spectral absorption and electrically conducting nature of these TTFtt-based materials enable highly efficient NIR-thermal conversion and good PTE performance. Furthermore, in contrast to conventional PTE composites, these NiTTFtt coordination polymers are notable as single-component PTE materials. The presynthetically tuned metal-to-insulator transition in these NiTTFtt systems directly modulates their PT and PTE properties.

Microscale patterning of colloidal nanocrystal (NC) films is important for their integration in devices. Here, we introduce the direct optical patterning of all-inorganic NCs without the use of additional photosensitive ligands or additives. We determined that photoexposure of ligand-stripped, “bare” NCs in air significantly reduces their solubility in polar solvents due to photo-oxidation of surface ions. Doses as low as 20 mJ/cm² could be used; the only obvious criterion for material selection is that the NCs need to have significant absorption at the irradiation wavelength. However, transparent NCs can still be patterned by mixing them with suitably absorbing NCs. This approach enabled the patterning of bare ZnSe, CdSe, ZnS, InP, CeO₂, CdSe/CdS, and CdSe/ZnS NCs as well as mixtures of ZrO₂ or HfO₂ NCs with ZnSe NCs. Optical, X-ray photoelectron, and infrared spectroscopies show that solubility loss results from desorption of bound solvent due to photo-oxidation of surface ions. We also demonstrate two approaches, compatible with our patterning method, for modulating the porosity and refractive index of NC films. Block copolymer templating decreases the film density, and thus the refractive index, by introducing mesoporosity. Alternatively, hot isostatic pressing increases the packing density and refractive index of NC layers. For example, the packing fraction of a ZnS NC film can be increased from 0.51 to 0.87 upon hot isostatic pressing at 450 °C and 15 000 psi. Our findings demonstrate that direct lithography by photo-oxidation of bare NC surfaces is an accessible patterning method for facilitating the exploration of more complex NC device architectures while eliminating the influence of bulky or insulating surfactants.

The ability to fabricate custom three-dimensional (3D) objects on demand has revolutionized prototyping and small-scale manufacturing processes. From low-cost filament extruders that a hobbyist can use to replace a plastic battery cover, to laser sintering machines for metal spacecraft parts, the reach of 3D printing technologies in low- and high-end markets continues to broaden. A crucial part of this progress has been the expansion of the library of materials that can be 3D-printed. Nanocrystals have many functional properties, but their integration with 3D printing has been limited, mostly relying on the use of polymer material as a scaffolding. In this issue, Liu et al. demonstrate the 3D printing of nanocrystals using a method known as two-photon lithography. The intense beam of an infrared femtosecond laser induces simultaneous absorption of two photons in a very small volume, triggering photochemical reactions at nanocrystal surfaces.

The goal of this work is to determine the kinetic factors that govern isovalent cation exchange in III–V colloidal quantum dots using molten salts as the solvent and cation source. We focus on the reactions of InP + GaI₃→ In_1–xGa_xP and InAs + GaI₃→ In_1–xGa_xAs to create technologically important ternary III–V phases. We find that the molten salt reaction medium causes the transformation of nearly spherical InP nanocrystals to tetrahedron-shaped In_1–xGa_xP nanocrystals. Furthermore, we determine that the activation energy for the cation exchange reaction is 0.9 eV for incorporation of Ga into InP and 1.2 eV for incorporation of Ga into InAs, both much lower than the measured values in bulk semiconductors. Next, we use powder XRD simulations to constrain our understanding of the structure of the In_1–xGa_xP nanocrystals. Together our results reveal several important features of molten salt-mediated cation exchange and provide guidance for future development of these materials.

The magnetoresistance of HgTe quantum dot films, exhibiting a well-defined 1S_e state charging and a relatively high mobility (1–10 cm² V⁻¹ s⁻¹), is measured as a function of temperature down to 10 K and controlled occupation of the first electronic state. There is a positive-quadratic magnetoresistance which can be several 100% at low temperature and scales like x(1 − x) where x is the filling fraction of the lowest quantum dot state in the conduction band, 1S_e. This positive magnetoresistance is orders of magnitude larger than the effect estimated from mobile carriers and it is attributed to the increased confinement induced by the magnetic field. There is also a negative magnetoresistance of 1–20% from 300 K to 10 K which is rather independent of the fractional occupation, and which follows a negative exponential dependence with the magnetic field. It can be empirically fit with an effective g-factor of ∼55 and it is tentatively attributed to the reduction of barrier heights by the Zeeman splitting of the 1S_e state.

Roll-to-roll (R2R) device fabrication using solution-processed materials is a cheap and versatile approach that has attracted widespread interest over the past 2 decades. Here, we systematically introduce and investigate R2R-friendly modifications in the fabrication of ultrathin, sintered CdTe nanocrystal (NC) solar cells. These include (1) scalable deposition techniques such as spray-coating and doctor-blading, (2) a bath-free, controllable sintering of CdTe NCs by quantitative addition of a sintering agent, and (3) radiative heating with an infrared lamp. The impact of each modification on the CdTe nanostructure and solar cell performance was first independently studied and compared to the standard, non-R2R-friendly procedure involving spin-coating the NCs, soaking in a CdCl₂ bath, and annealing on a hot plate. The R2R-friendly techniques were then combined into a single, integrated process, yielding devices that reach 10.4% power conversion efficiency with a V_oc, J_sc, and FF of 697 mV, 22.2 mA/cm², and 67%, respectively, after current/light soaking. These advances reduce the barrier for large-scale manufacturing of solution-processed, ultralow-cost solar cells on flexible or curved substrates.

Microscale patterning of solution-processed nanomaterials is important for integration in functional devices. Colloidal lead halide perovskite (LHP) nanocrystals (NCs) can be particularly challenging to pattern due to their incompatibility with polar solvents and lability of surface ligands. Here, we introduce a direct photopatterning approach for LHP NCs through the binding and subsequent cleavage of a photosensitive oxime sulfonate ester (−C═N–OSOO−). The photosensitizer binds to the NCs through its sulfonate group and is cleaved at the N–O bond during photoirradiation with 405 nm light. This bond cleavage decreases the solubility of the NCs, which allows patterns to emerge upon development with toluene. Postpatterning ligand exchange results in photoluminescence quantum yields of up to 79%, while anion exchange provides tunability in the emission wavelength. The patterned NC films show photoconductive behavior, demonstrating that good electrical contact between the NCs can be established.

In quantum-confined semiconductor nanostructures, electrons exhibit distinctive behavior compared with that in bulk solids. This enables the design of materials with tunable chemical, physical, electrical, and optical properties. Zero-dimensional semiconductor quantum dots (QDs) offer strong light absorption and bright narrowband emission across the visible and infrared wavelengths and have been engineered to exhibit optical gain and lasing. These properties are of interest for imaging, solar energy harvesting, displays, and communications. Here, we offer an overview of advances in the synthesis and understanding of QD nanomaterials, with a focus on colloidal QDs, and discuss their prospects in technologies such as displays and lighting, lasers, sensing, electronics, solar energy conversion, photocatalysis, and quantum information.

The structure, chemistry, and charge of interfaces between materials and aqueous fluids play a central role in determining properties and performance of numerous water systems. Sensors, membranes, sorbents, and heterogeneous catalysts almost uniformly rely on specific interactions between their surfaces and components dissolved or suspended in the water—and often the water molecules themselves—to detect and mitigate contaminants. Deleterious processes in these systems such as fouling, scaling (inorganic deposits), and corrosion are also governed by interfacial phenomena. Despite the importance of these interfaces, much remains to be learned about their multiscale interactions. Developing a deeper understanding of the molecular- and mesoscale phenomena at water/solid interfaces will be essential to driving innovation to address grand challenges in supplying sufficient fit-for-purpose water in the future. In this Review, we examine the current state of knowledge surrounding adsorption, reactivity, and transport in several key classes of water/solid interfaces, drawing on a synergistic combination of theory, simulation, and experiments, and provide an outlook for prioritizing strategic research directions.

Quasi-two-dimensional semiconductor nanoplatelets (NPLs) are intriguing systems for studying the influence of Auger recombination processes on the multiexciton emission efficiencies in the weak in-plane confinement regime. We investigate CdSe/CdS core/shell NPLs using cryogenic temperature single particle spectroscopy and observe bright biexciton emission at high excitation powers. The average binding energy of the biexcitons is determined to be 16.5 meV. The observed switching between the biexciton and trion states indicates charging-decharging dynamics of the NPLs mediated by the Auger ionization process. These findings are highly relevant for harvesting efficient biexciton emission for energy, lighting, and quantum applications.

Investigating the impact of nanoscale heterogeneity on heat transport requires a spatiotemporal probe of temperature on the length and time scales intrinsic to heat navigating nanoscale defects. Here, we use stroboscopic optical scattering microscopy to visualize nanoscale heat transport in disordered films of gold nanocrystals. We find that heat transport appears subdiffusive at the nanoscale. Finite element simulations show that tortuosity of the heat flow underlies the subdiffusive transport, owing to a distribution of nonconductive voids. Thus, while heat travels diffusively through contiguous regions of the film, the tortuosity causes heat to navigate circuitous pathways that make the observed mean-squared expansion of an initially localized temperature distribution appear subdiffusive on length scales comparable to the voids. Our approach should be broadly applicable to uncover the impact of both designed and unintended heterogeneities in a wide range of materials and devices that can affect more commonly used spatially averaged thermal transport measurements.

Single-photon superradiance can emerge when a collection of identical emitters are spatially separated by distances much less than the wavelength of the light they emit, and is characterized by the formation of a superradiant state that spontaneously emits light with a rate that scales linearly with the number of emitters. This collective phenomena has only been demonstrated in a few nanomaterial systems, all requiring temperatures below 10K. Here, we rationally design a single colloidal nanomaterial that hosts multiple (nearly) identical emitters that are impervious to the fluctuations which typically inhibit room temperature superradiance in other systems such as molecular aggregates. Specifically, by combining molecular dynamics, atomistic electronic structure calculations, and model Hamiltonian methods, we show that the faces of a heterostructure nanocuboid mimic individual quasi-2D nanoplatelets and can serve as the robust emitters required to realize superradiant phenomena at room temperature. Leveraging layer-by-layer colloidal growth techniques to synthesize a nanocuboid, we demonstrate single-photon superfluorescence via single-particle time-resolved photoluminescence measurements at room temperature. This robust observation of both superradiant and subradiant states in single nanocuboids opens the door to ultrafast single-photon emitters and provides an avenue to entangled multi-photon states via superradiant cascades.

Spatially patterned dielectric materials are ubiquitous in electronic, photonic, and optoelectronic devices. These patterns are typically made by subtractive or additive approaches utilizing vapor-phase reagents. On the other hand, recent advances in solution-phase synthesis of oxide nanomaterials have unlocked a materials library with greater compositional, microstructural, and interfacial tunability. However, methods to pattern and integrate these nanomaterials in real-world devices are less established. In this work, we directly optically pattern oxide nanoparticles (NPs) by mixing them with photosensitive diazo-2-naphthol-4-sulfonic acid and irradiating with widely available 405 nm light. We demonstrate the direct optical lithography of ZrO2, TiO2, HfO2, and ITO NPs and investigate the chemical and physical changes responsible for this photoinduced decrease in solubility. For example, micron-thick layers of amorphous ZrO2 NPs were patterned with micron resolution and shown to allow 2pi phase control of visible light. We also show multilayer patterning and use it to fabricate features with different thicknesses and distinct structural colors. Upon annealing at 400 C, the deposited structures have excellent optical transparency across a wide wavelength range (0.3 – 10 um), a high refractive index (n = 1.84 at 633 nm) and are optically smooth. We then fabricate diffractive optical elements, such as binary phase diffraction gratings, that show efficient diffractive behavior and good thermal stability. Different oxide NPs can also be mixed prior to patterning, providing a high level of material tunability. This work demonstrates a general patterning approach that harnesses the processability and diversity of colloidal oxide nanomaterials for use in photonic applications.