Determination of a Raman shift laser power coefficient based on cross correlation.

This work presents a novel, to the best of our knowledge, cross correlation technique for determining the laser heating-induced Raman shift laser power coefficient ψ required for energy transport state-resolved Raman (ET-Raman) methods. The cross correlation method determines the measure of similarity between the experimental intensity data and a varying test Gaussian signal. By circumventing the errors inherent in any curve fittings, the cross correlation method quickly and accurately determines the location where the test Gaussian signal peak is most like the Raman peak, thereby revealing the peak location and ultimately the value of ψ. This method improves the reliability of optothermal Raman-based methods for micro/nanoscale thermal measurements and offers a robust approach to data processing through a global treatment of Raman spectra.

Rapid laser nanomanufacturing and direct patterning of 2D materials on flexible substrates-2DFlex.

Direct synthesis, large-scale integration, and patterning of two-dimensional (2D) quantum materials (e.g. MoS2, WSe2) on flexible and transparent substrates are of high interest for flexible and conformal device applications. However, the growth temperatures (e.g. 850 °C) of the emerging 2D materials in the common gas-phase synthesis methods are well beyond the tolerances limit of flexible substrates, such as polydimethylsiloxane (PDMS). In addition, random nucleation and growth process in most growth systems limits the predicted integration and patterning freedoms. Here, we report a rapid direct laser crystallization and mask-free large-scale patterning of MoS2 and WSe2 crystals on PDMS substrates. A thin layer of stoichiometric amorphous 2D film is first laser-deposited via pulsed laser deposition (PLD) system onto the flexible substrates followed by a controlled crystallization and direct writing process using a tunable nanosecond laser (1064 nm). The influences of pulse duration, number of pulses, and the thickness of the deposited amorphous 2D layer on the crystallization of 2D materials are discussed. Optical spectroscopy and electrical characterizations are performed to confirm the quality of crystallized 2D materials on flexible substrates. This novel method opens up a new opportunity for the crystallization of complex patterns directly from computer-aided design models for the future 2D materials-based wearable, transparent, and flexible devices.

Ultrafast dynamics of exciton formation and decay in two-dimensional tungsten disulfide (2D-WS2) monolayers.

Excitons in two-dimensional transition metal dichalcogenide monolayers (2D-TMDs) are of essential importance due to their key involvement in 2D-TMD-based applications. For instance, exciton dissociation and exciton radiative recombination are indispensible processes in photovoltaic and light-emitting devices, respectively. These two processes depend drastically on the photogeneration efficiency and lifetime of excitons. Here, we incorporate femtosecond pump-probe spectroscopy to investigate the ultrafast dynamics of exciton formation and decay in a single crystal of monolayer 2D tungsten disulfide (WS2). Investigation of the formation dynamics of the lowest exciton (XA) indicated that the formation time linearly increases from ∼150 fs upon resonant excitation, to ∼500 fs following excitation that is ∼1.1 eV above the band-gap. This dependence is attributed to the time it takes highly excited electrons in the conduction band (CB) to relax to the CB minimum (CBM) and contribute to the formation of XA. This is confirmed by infrared measurements of electron intraband relaxation dynamics. Furthermore, pump-probe experiments suggested that the XA ground state depletion recovery dynamics depend on the excitation energy as well. The average recovery time increased from ∼10 ps in the case of resonant excitation to ∼50 ps following excitation well above the band-gap. Having the ability to control whether generating short-lived or long-lived electron-hole pairs in 2D-TMD monolayers opens a new horizon for the application of these materials. For instance, long-lived electron-hole pairs are appropriate for photovoltaic devices, but short-lived excitons are more beneficial for lasers with ultrashort pulses.

Nonequilibrium Synthesis of TiO2 Nanoparticle "Building Blocks" for Crystal Growth by Sequential Attachment in Pulsed Laser Deposition.

Nonequilibrium growth pathways for crystalline nanostructures with metastable phases are demonstrated through the gas-phase formation, attachment, and crystallization of ultrasmall amorphous nanoparticles as building blocks in pulsed laser deposition (PLD). Temporally and spatially resolved gated-intensified charge couple device (ICCD) imaging and ion probe measurements are employed as in situ diagnostics to understand and control the plume expansion conditions for the synthesis of nearly pure fluxes of ultrasmall (∼3 nm) amorphous TiO2 nanoparticles in background gases and their selective delivery to substrates. These amorphous nanoparticles assemble into loose, mesoporous assemblies on substrates at room temperature but dynamically crystallize by sequential particle attachment at higher substrate temperatures to grow nanostructures with different phases and morphologies. Molecular dynamics calculations are used to simulate and understand the crystallization dynamics. This work demonstrates that nonequilibrium crystallization by particle attachment of metastable ultrasmall nanoscale "building blocks" provides a versatile approach for exploring and controlling the growth of nanoarchitectures with desirable crystalline phases and morphologies.

Tailoring Vacancies Far Beyond Intrinsic Levels Changes the Carrier Type and Optical Response in Monolayer MoSe2-x Crystals.

Defect engineering has been a critical step in controlling the transport characteristics of electronic devices, and the ability to create, tune, and annihilate defects is essential to enable the range of next-generation devices. Whereas defect formation has been well-demonstrated in three-dimensional semiconductors, similar exploration of the heterogeneity in atomically thin two-dimensional semiconductors and the link between their atomic structures, defects, and properties has not yet been extensively studied. Here, we demonstrate the growth of MoSe2-x single crystals with selenium (Se) vacancies far beyond intrinsic levels, up to ∼20%, that exhibit a remarkable transition in electrical transport properties from n- to p-type character with increasing Se vacancy concentration. A new defect-activated phonon band at ∼250 cm(-1) appears, and the A1g Raman characteristic mode at 240 cm(-1) softens toward ∼230 cm(-1) which serves as a fingerprint of vacancy concentration in the crystals. We show that post-selenization using pulsed laser evaporated Se atoms can repair Se-vacant sites to nearly recover the properties of the pristine crystals. First-principles calculations reveal the underlying mechanisms for the corresponding vacancy-induced electrical and optical transitions.

Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures.

Photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors, i.e., monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions has attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge-transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure for optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS2) and a single layer of cadmium selenide/zinc sulfide core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that, following electron transfer from the 2D to the 0D, hybrid excitons, wherein the electron resides in the 0D and the hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ∼140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.

Low temperature synthesis of hierarchical TiO2 nanostructures for high performance perovskite solar cells by pulsed laser deposition.

A promising way to advance perovskite solar cells is to improve the quality of the electron transport material -e.g., titanium dioxide (TiO2) - in a direction that increases electron transport and extraction. Although dense TiO2 films are easily grown in solution, efficient electron extraction suffers due to a lack of interfacial contact area with the perovskites. Conversely, mesoporous films do offer high surface-area-to-volume ratios, thereby promoting efficient electron extraction, but their morphology is relatively difficult to control via conventional solution synthesis methods. Here, a pulsed laser deposition method was used to assemble TiO2 nanoparticles into TiO2 hierarchical architectures exhibiting an anatase crystal structure, and prototype solar cells employing these structures yielded power conversion efficiencies of ∼14%. Our approach demonstrates a way to grow high aspect-ratio TiO2 nanostructures for improved interfacial contact between TiO2 and perovskite materials, leading to high electron-hole pair separation and electron extraction efficiencies for superior photovoltaic performance. Compared to previous pulsed laser deposition-synthesized TiO2 mesoporous crystalline networks that needed post-thermal annealing at 500 °C to form mesoporous crystalline networks, our relatively low temperature (300 °C) TiO2 processing method may promote reduced energy-consumption during device fabrication, as well as enable compatibility with flexible polymer substrates such as polyimide.

Low Dielectric Medium for Hyperbolic Phonon Polariton Waveguide in van der Waals Heterostructures.

Polar van der Waals (vdW) crystals, composed of atomic layers held together by vdW forces, can host phonon polaritons-quasiparticles arising from the interaction between photons in free-space light and lattice vibrations in polar materials. These crystals offer advantages such as easy fabrication, low Ohmic loss, and optical confinement. Recently, hexagonal boron nitride (hBN), known for having hyperbolicity in the mid-infrared range, has been used to explore multiple modes with high optical confinement. This opens possibilities for practical polaritonic nanodevices with subdiffractional resolution. However, polariton waves still face exposure to the surrounding environment, leading to significant energy losses. In this work, we propose a simple approach to inducing a hyperbolic phonon polariton (HPhP) waveguide in hBN by incorporating a low dielectric medium, ZrS2. The low dielectric medium serves a dual purpose-it acts as a pathway for polariton propagation, while inducing high optical confinement. We establish the criteria for the HPhP waveguide in vdW heterostructures with various thicknesses of ZrS2 through scattering-type scanning near-field optical microscopy (s-SNOM) and by conducting numerical electromagnetic simulations. Our work presents a feasible and straightforward method for developing practical nanophotonic devices with low optical loss and high confinement, with potential applications such as energy transfer, nano-optical integrated circuits, light trapping, etc.

Time-Resolved Growth of 2D WSe2 Monolayer Crystals.

Understanding and controlling the growth evolution of atomically thin monolayer two-dimensional (2D) materials such as transition metal dichalcogenides (TMDCs) are vital for next-generation 2D electronics and optoelectronic devices. However, their growth kinetics are not fully observed or well understood due to the bottlenecks associated with the existing synthesis methods. This study demonstrates the time-resolved and ultrafast growth of 2D materials by a laser-based synthesis approach that enables the rapid initiation and termination of the vaporization process during crystal growth. The use of stoichiometric powder (e.g., WSe2) minimizes the complex chemistry during the vaporization and growth process, allowing rapid initiation/termination control over the generated flux. An extensive set of experiments is performed to understand the growth evolution, achieving subsecond growth as low as 10 ms along with a 100 µm/s growth rate on a noncatalytic substrate such as Si/SiO2. Overall, this study allows us to observe and understand the 2D crystal evolution and growth kinetics with time-resolved and subsecond time scales.

Effects of TiS2 on Inhibiting Candida albicans Biofilm Formation and Its Compatibility with Human Gingival Fibroblasts in Titanium Implants.

Titanium is widely used in medical devices, such as dental and orthopedic implants, due to its excellent mechanical properties, low toxicity, and biocompatibility. However, the titanium surface has the risk of microbial biofilm formation, which results in infections from species such as Candida albicans (C. albicans). This kind of biofilm prevents antifungal therapy and complicates the treatment of infectious diseases associated with implanted devices. It is critical to developing a feasible surface to decrease microbial growth while not interfering with the growth of the host cells. This study reports the influence of titanium surface modification to titanium disulfide (TiS2) on inhibiting C. albicans biofilm formation while allowing the attachment of human gingival fibroblasts (HGFs) on their surface. The surface of titanium parts is directly converted to structured titanium and TiS2 using direct laser processing and crystal growth methods. C. albicans adhesion and colonization are then investigated on these surfaces by the colony counting assay and reactive oxygen species (ROS) assay, using 2',7'-dichlorofluorescin diacetate (DCFH-DA) and microscopy images. Also, the viability and adhesion of HGFs on these surfaces are investigated to show their adhesion and biocompatibility. Titanium samples with the TiS2 surface show both C. albicans biofilm inhibition and HGF attachment. This study provides insight into designing and manufacturing titanium biomedical implants.

Wafer-Scale Synthesis of 2D Materials by an Amorphous Phase-Mediated Crystallization Approach.

The interest in the wafer-scale growth of two-dimensional (2D) materials, including transition metal dichalcogenides (TMDCs), has been rising for transitioning from lab-scale devices to commercial-scale systems. Among various synthesis techniques, physical vapor deposition, such as pulsed laser deposition (PLD), has shown promise for the wafer-scale growth of 2D materials. However, due to the high volatility of chalcogen atoms (e.g., S and Se), films deposited by PLD usually suffer from a lack of stoichiometry and chalcogen deficiency. To mitigate this issue, excess chalcogen is necessary during the deposition, which results in problems like uniformity or not being repeatable. This study demonstrates a condensed-phase or amorphous phase-mediated crystallization (APMC) approach for the wafer-scale synthesis of 2D materials. This method uses a room-temperature PLD process for the deposition and formation of amorphous precursors with controlled thicknesses, followed by a post-deposition crystallization process to convert the amorphous materials to crystalline structures. This approach maintains the stoichiometry of the deposited materials throughout the deposition and crystallization process and enables the large-scale synthesis of crystalline 2D materials (e.g., MoS2 and WSe2) on Si/SiO2 substrates, which is critical for future wafer-scale electronics. We show that the thickness of the layers can be digitally controlled by the number of laser pulses during the PLD phase. Optical spectroscopy is used to monitor the crystallization dynamics of amorphous layers as a function of annealing temperature. The crystalline quality, domain sizes, and the number of layers were explored using nanoscale and atomistic characterization (e.g., AFM, STEM, and EDS) along with electrical characterization to explore process-structure-performance relationships. This growth technique is a promising method that could potentially be adopted in conventional semiconductor industries for wafer-scale manufacturing of next-generation electronic and optoelectronic devices.

Photoexcitation Dynamics and Long-Lived Excitons in Strain-Engineered Transition Metal Dichalcogenides.

Strain-engineering in 2D transition metal dichalcogenide (TMD) semiconductors has garnered intense research interest in tailoring the optical properties via strain-induced modifications of the electronic bands in TMDs, while its impact on the exciton dynamics remains less understood. To address this, an extensive study of transient optical absorption (TA) of both W- and Mo-based single-crystalline monolayer TMDs grown by a recently developed laser-assisted evaporation method is performed. All spectral features of the monolayers as grown on fused silica substrates exhibit appreciable redshifts relating to the existence of strain due to growth conditions. Moreover, these systems exhibit a dramatic slowing down of exciton dynamics (100s of picoseconds to few nanoseconds) with an increase in carrier densities, which strongly contrasts with the monolayers in their freestanding form as well as in comparison with more traditionally grown TMDs. The observations are related to the modifications of the electronic bands as expected from the strain and associated population of the intervalley dark excitons that can now interplay with intravalley excitations. These findings are consistent across both the Mo- and W-based TMD families, providing key information about the influence of the growth conditions on the nature of optical excitations and fostering emerging optoelectronic applications of monolayer TMDs.

Filling Exciton Trap-States in Two-Dimensional Tungsten Disulfide (WS2) and Diselenide (WSe2) Monolayers.

Two-dimensional transition metal dichalcogenides (2D-TMDs) hold a great potential to platform future flexible optoelectronics. The beating hearts of these materials are their excitons known as XA and XB, which arise from transitions between spin-orbit split (SOS) levels in the conduction and valence bands at the K-point. The functionality of 2D-TMD-based devices is determined by the dynamics of these excitons. One of the most consequential channels of exciton decay on the device functionality is the defect-assisted recombination (DAR). Here, we employ steady-state absorption and emission spectroscopies, and pump density-dependent femtosecond transient absorption spectroscopy to report on the effect of DAR on the lifetime of excitons in monolayers of tungsten disulfide (2D-WS2) and diselenide (2D-WSe2). These pump-probe measurements suggested that while exciton decay dynamics in both monolayers are driven by DAR, in 2D-WS2, defect states near the XB exciton fill up before those near the XA exciton. However, in the 2D-WSe2 monolayer, the defect states fill up similarly. Understanding the contribution of DAR on the lifetime of excitons and the partition of this decay channel between XA and XB excitons may open new horizons for the incorporation of 2D-TMD materials in future optoelectronics.

Two-Dimensional-Material-Based Field-Effect Transistor Biosensor for Detecting COVID-19 Virus (SARS-CoV-2).

The emergence of rapidly expanding infectious diseases such as coronavirus (COVID-19) demands effective biosensors that can promptly detect and recognize the pathogens. Field-effect transistors based on semiconducting two-dimensional (2D) materials (2D-FETs) have been identified as potential candidates for rapid and label-free sensing applications. This is because any perturbation of such atomically thin 2D channels can significantly impact their electronic transport properties. Here, we report the use of FET based on semiconducting transition metal dichalcogenide (TMDC) WSe2 as a promising biosensor for the rapid and sensitive detection of SARS-CoV-2 in vitro. The sensor is created by functionalizing the WSe2 monolayers with a monoclonal antibody against the SARS-CoV-2 spike protein and exhibits a detection limit of down to 25 fg/µL in 0.01X phosphate-buffered saline (PBS). Comprehensive theoretical and experimental studies, including density functional theory, atomic force microscopy, Raman and photoluminescence spectroscopies, and electronic transport properties, were performed to characterize and explain the device performance. The results demonstrate that TMDC-based 2D-FETs can potentially serve as sensitive and selective biosensors for the rapid detection of infectious diseases.

Gas-Phase Formation of Highly Luminescent 2D GaSe Nanoparticle Ensembles in a Nonequilibrium Laser Ablation Process.

Interest in layered two-dimensional (2D) materials has been escalating rapidly over the past few decades due to their promising optoelectronic and photonic properties emerging from their atomically thin 2D structural confinements. When these 2D materials are further confined in lateral dimensions toward zero-dimensional (0D) structures, 2D nanoparticles and quantum dots with new properties can be formed. Here, we report a nonequilibrium gas-phase synthesis method for the stoichiometric formation of gallium selenide (GaSe) nanoparticles ensembles that can potentially serve as quantum dots. We show that the laser ablation of a target in an argon background gas condenses the laser-generated plume, resulting in the formation of metastable nanoparticles in the gas phase. The deposition of these nanoparticles onto the substrate results in the formation of nanoparticle ensembles, which are then post-processed to crystallize or sinter the nanoparticles. The effects of background gas pressures, in addition to crystallization/sintering temperatures, are systematically studied. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy, and time-correlated single-photon counting (TCSPC) measurements are used to study the correlations between growth parameters, morphology, and optical properties of the fabricated 2D nanoparticle ensembles.

Interfacial Thermal Conductance between Monolayer WSe2 and SiO2 under Consideration of Radiative Electron-Hole Recombination.

This work reports the interfacial thermal conductance (G) and radiative recombination efficiency (ß), also known as photoluminescence quantum yield (PL QY), of monolayer WSe2 flakes supported by fused silica substrates via energy-transport state-resolved Raman (ET-Raman). This is the first known work to consider the effect of radiative electron-hole recombination on the thermal transport characteristics of single-layer transition-metal dichalcogenides (TMDs). ET-Raman uses a continuous-wave laser for steady-state heating as well as nanosecond and picosecond lasers for transient energy transport to simultaneously heat the monolayer flakes and extract the Raman signal. The three lasers induce distinct heating phenomena that distinguish the interfacial thermal conductance and radiative recombination efficiency, which can then be determined in tandem with three-dimensional (3D) numerical modeling of the temperature rise from respective laser irradiation. For the five samples measured, G is found to range from 2.10 ± 0.14 to 15.9 ± 5.0 MW m-2 K-1 and ß ranges from 36 ± 6 to 65 ± 7%. These values support the claim that interfacial phenomena such as surface roughness and two-dimensional (2D) material-substrate bonding strength play critical roles in interfacial thermal transport and electron-hole recombination mechanisms in TMD monolayers. It is also determined that low-level defect density enhances the radiative recombination efficiency of single-layer WSe2.

Phase-Selective and Localized TiO2 Coating on Additive and Wrought Titanium by a Direct Laser Surface Modification Approach.

Titanium has been the material of interest in biological implant applications due to its unique mechanical properties and biocompatibility. Their design is now growing rapidly due to the advent of additive manufacturing technology that enables the fabrication of complex and patient-customized parts. Titanium dioxides (TiO2) coatings with different phases (e.g., anatase, rutile) and morphologies have shown to be effective in enhancing osteointegration and antibacterial behavior. This enhanced antibacterial behavior stems from the photocatalytic activity generated from crystalline TiO2 coatings. Anatase has commonly been shown to be a more photocatalytic oxide phase compared to rutile despite its larger band gap. However, more recent studies have suggested that a synergistic effect leading to increased photocatalytic activity may be produced with a combination of oxides containing both anatase and rutile phases. Here, we demonstrate the selective and localized formation of TiO2 nanostructures on additive and wrought titanium parts with anatase, rutile, and mixed phases by a laser-induced transformation approach. Compared to conventional coating processes, this technique produces desired TiO2 phases simply by controlled laser irradiation of titanium parts in an oxygen environment, where needed. The effects of processing conditions such as laser power, scanning speed, laser pulse duration, frequency, and gas flow on the selective transformation were studied. The morphological and structural evolutions were investigated using various characterization techniques. This method is specifically of significant interest in creating phase-selective TiO2 surfaces on titanium-based bioimplants, including those fabricated by additive manufacturing technologies.

Strain tolerance of two-dimensional crystal growth on curved surfaces.

Two-dimensional (2D) crystal growth over substrate features is fundamentally guided by the Gauss-Bonnet theorem, which mandates that rigid, planar crystals cannot conform to surfaces with nonzero Gaussian curvature. Here, we reveal how topographic curvature of lithographically designed substrate features govern the strain and growth dynamics of triangular WS2 monolayer single crystals. Single crystals grow conformally without strain over deep trenches and other features with zero Gaussian curvature; however, features with nonzero Gaussian curvature can easily impart sufficient strain to initiate grain boundaries and fractured growth in different directions. Within a strain-tolerant regime, however, triangular single crystals can accommodate considerable (<1.1%) localized strain exerted by surface features that shift the bandgap up to 150 meV. Within this regime, the crystal growth accelerates in specific directions, which we describe using a growth model. These results present a previously unexplored strategy to strain-engineer the growth directions and optoelectronic properties of 2D crystals.

Photocarrier Transfer across Monolayer MoS2-MoSe2 Lateral Heterojunctions.

In-plane heterojuctions formed from two monolayer semiconductors represent the finest control of electrons in condensed matter and have attracted significant interest. Various device studies have shown the effectiveness of such structures to control electronic processes, illustrating their potentials for electronic and optoelectronic applications. However, information about the physical mechanisms of charge carrier transfer across the junctions is still rare, mainly due to the lack of adequate experimental techniques. Here we show that transient absorption measurements with high spatial and temporal resolution can be used to directly monitor such transfer processes. We studied MoS2-MoSe2 in-plane heterostructures fabricated by chemical vapor deposition and lithographic patterning followed by laser-generated vapor sulfurization. Transient absorption measurements in reflection geometry revealed evidence of exciton transfer from MoS2 to MoSe2. By comparing the experimental data with a simulation, we extracted an exciton transfer velocity of 104 m s-1. These results provide valuable information for understanding and controlling in-plane carrier transfer in two-dimensional lateral heterostructures for their electronic and optoelectronic applications.

Black Anatase Formation by Annealing of Amorphous Nanoparticles and the Role of the Ti2O3 Shell in Self-Organized Crystallization by Particle Attachment.

We use amorphous titania nanoparticle networks produced by pulsed laser vaporization at room temperature as a model system for understanding the mechanism of formation of black titania. Here, we characterize the transformation of amorphous nanoparticles by annealing in pure Ar at 400 °C, the lowest temperature at which black titania was observed. Atomic resolution electron microscopy methods and electron energy loss spectroscopy show that the onset of crystallization occurs by nucleation of an anatase core that is surrounded by an amorphous Ti2O3 shell. The formation of the metastable anatase core before the thermodynamically stable rutile phase occurs according to the Ostwald phase rule. In the second stage the particle size increases by coalescence of already crystallized particles by a self-organized mechanism of crystallization by particle attachment. We show that the Ti2O3 shell plays a critical role in both black titania transformation and functionality. At 400 °C, Ti2O3 hinders the agglomeration of neighboring particles to maintain a high surface-to-volume ratio that is beneficial for enhanced photocatalytic activity. In agreement with previous results, the thin Ti2O3 surface layer acts as a narrow bandgap semiconductor in concert with surface defects to enhance the photocatalytic activity. Our results demonstrate that crystallization by particle attachment can be a highly effective mechanism for optimizing photocatalytic efficiency by controlling the phase, composition, and particle size distribution in a wide range of self-doped defective TiO2 architectures simply by varying the annealing conditions of amorphous nanoparticles.