Alternative nano-lithographic tools for shell-isolated nanoparticle enhanced Raman spectroscopy substrates.

Chemically synthesized metal nanoparticles (MNPs) have been widely used as surface-enhanced Raman spectroscopy (SERS) substrates for monitoring catalytic reactions. In some applications, however, the SERS MNPs, besides being plasmonically active, can also be catalytically active and result in Raman signals from undesired side products. The MNPs are typically insulated with a thin (∼3 nm), in principle pin-hole-free shell to prevent this. This approach, which is known as shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), offers many advantages, such as better thermal and chemical stability of the plasmonic nanoparticle. However, having both a high enhancement factor and ensuring that the shell is pin-hole-free is challenging because there is a trade-off between the two when considering the shell thickness. So far in the literature, shell insulation has been successfully applied only to chemically synthesized MNPs. In this work, we alternatively study different combinations of chemical synthesis (bottom-up) and lithographic (top-down) routes to obtain shell-isolated plasmonic nanostructures that offer chemical sensing capabilities. The three approaches we study in this work include (1) chemically synthesized MNPs + chemical shell, (2) lithographic substrate + chemical shell, and (3) lithographic substrate + atomic layer deposition (ALD) shell. We find that ALD allows us to fabricate controllable and reproducible pin-hole-free shells. We showcase the ability to fabricate lithographic SHINER substrates which report an enhancement factor of 7.5 × 103 ± 17% for our gold nanodot substrates coated with a 2.8 nm aluminium oxide shell. Lastly, by introducing a gold etchant solution to our fabricated SHINER substrate, we verified that the shells fabricated with ALD are truly pin-hole-free.

Tailoring the facet distribution on copper with chloride.

Electrocatalytic reactions are sensitive to the catalyst surface structure. Therefore, finding methods to determine active surface sites with different geometry is essential to address the structure-electrocatalytic performance relationships. In this work, we propose a simple methodology to tune and quantify the surface structure on copper catalysts. We tailor the distribution and ratio of facets on copper by electrochemically oxidizing and reducing the surface in chloride-rich aqueous solutions. We then address the formation of new facets with voltammetric lead (Pb) underpotential deposition (UPD). We first record the voltammetric lead UPD on different single facets, which have intense peaks at different potential values. We use this data to decouple each facet peak-contribution in the lead (Pb) UPD curves of the tailored and multifaceted copper surfaces and determine the geometry of the active sites. We combine experiments with density functional theory (DFT) calculations to assess the ligand effect of chloride anions on the copper facet distribution during the surface oxidation/electrodeposition treatment. Our experiments and Wulff constructions suggest that chloride preferentially adsorbs on the (310) facet, reducing the number of (111) sites and inducing the growth of (310) or n(100) × (110) domains. Our work provides a tool to correlate active sites with copper geometries, which is needed to assess the structure-performance relationships in electrocatalysis. We also demonstrate an easy method for selectively tailoring the facet distribution of copper, which is essential to design a well-defined nanostructured catalyst.

Mapping Temperature Heterogeneities during Catalytic CO2 Methanation with Operando Luminescence Thermometry.

Controlling and understanding reaction temperature variations in catalytic processes are crucial for assessing the performance of a catalyst material. Local temperature measurements are challenging, however. Luminescence thermometry is a promising remote-sensing tool, but it is cross-sensitive to the optical properties of a sample and other external parameters. In this work, we measure spatial variations in the local temperature on the micrometer length scale during carbon dioxide (CO2) methanation over a TiO2-supported Ni catalyst and link them to variations in catalytic performance. We extract local temperatures from the temperature-dependent emission of Y2O3:Nd3+ particles, which are mixed with the CO2 methanation catalyst. Scanning, where a near-infrared laser locally excites the emitting Nd3+ ions, produces a temperature map with a micrometer pixel size. We first designed the Y2O3:Nd3+ particles for optimal temperature precision and characterized cross-sensitivity of the measured signal to parameters other than temperature, such as light absorption by the blackened sample due to coke deposition at elevated temperatures. Introducing reaction gases causes a local temperature increase of the catalyst of on average 6-25 K, increasing with the reactor set temperature in the range of 550-640 K. Pixel-to-pixel variations in the temperature increase show a standard deviation of up to 1.5 K, which are attributed to local variations in the catalytic reaction rate. Mapping and understanding such temperature variations are crucial for the optimization of overall catalyst performance on the nano- and macroscopic scale.

Spatiotemporal Mapping of Local Heterogeneities during Electrochemical Carbon Dioxide Reduction.

The activity and selectivity of a copper electrocatalyst during the electrochemical CO2 reduction reaction (eCO2RR) are largely dominated by the interplay between local reaction environment, the catalyst surface, and the adsorbed intermediates. In situ characterization studies have revealed many aspects of this intimate relationship between surface reactivity and adsorbed species, but these investigations are often limited by the spatial and temporal resolution of the analytical technique of choice. Here, Raman spectroscopy with both space and time resolution was used to reveal the distribution of adsorbed species and potential reaction intermediates on a copper electrode during eCO2RR. Principal component analysis (PCA) of the in situ Raman spectra revealed that a working electrocatalyst exhibits spatial heterogeneities in adsorbed species, and that the electrode surface can be divided into CO-dominant (mainly located at dendrite structures) and C-C dominant regions (mainly located at the roughened electrode surface). Our spectral evaluation further showed that in the CO-dominant regions, linear CO was observed (as characterized by a band at ∼2090 cm-1), accompanied by the more classical Cu-CO bending and stretching vibrations located at ∼280 and ∼360 cm-1, respectively. In contrast, in the C-C directing region, these three Raman bands are suppressed, while at the same time a band at ∼495 cm-1 and a broad Cu-CO band at ∼2050 cm-1 dominate the Raman spectra. Furthermore, PCA revealed that anodization creates more C-C dominant regions, and labeling experiments confirmed that the 495 cm-1 band originates from the presence of a Cu-C intermediate. These results indicate that a copper electrode at work is very dynamic, thereby clearly displaying spatiotemporal heterogeneities, and that in situ micro-spectroscopic techniques are crucial for understanding the eCO2RR mechanism of working electrocatalyst materials.

Low-Variance Surface-Enhanced Raman Spectroscopy Using Confined Gold Nanoparticles over Silicon Nanocones.

Surface-enhanced Raman spectroscopy (SERS) substrates are of utmost interest in the analyte detection of biological and chemical diagnostics. This is primarily due to the ability of SERS to sensitively measure analytes present in localized hot spots of the SERS nanostructures. In this work, we present the formation of 67 ± 6 nm diameter gold nanoparticles supported by vertically aligned shell-insulated silicon nanocones for ultralow variance SERS. The nanoparticles are obtained through discrete rotation glancing angle deposition of gold in an e-beam evaporating system. The morphology is assessed through focused ion beam tomography, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. The optical properties are discussed and evaluated through reflectance measurements and finite-difference time-domain simulations. Lastly, the SERS activity is measured by benzenethiol functionalization and subsequent Raman spectroscopy in the surface scanning mode. We report a homogeneous analytical enhancement factor of 2.2 ± 0.1 × 107 (99% confidence interval for N = 400 grid spots) and made a comparison to other lithographically derived assemblies used in SERS. The strikingly low variance (4%) of our substrates facilitates its use for many potential SERS applications.

How Temperature Affects the Selectivity of the Electrochemical CO2 Reduction on Copper.

Copper is a unique catalyst for the electrochemical CO2 reduction reaction (CO2RR) as it can produce multi-carbon products, such as ethylene and propanol. As practical electrolyzers will likely operate at elevated temperatures, the effect of reaction temperature on the product distribution and activity of CO2RR on copper is important to elucidate. In this study, we have performed electrolysis experiments at different reaction temperatures and potentials. We show that there are two distinct temperature regimes. From 18 up to ∼48 °C, C2+ products are produced with higher Faradaic efficiency, while methane and formic acid selectivity decreases and hydrogen selectivity stays approximately constant. From 48 to 70 °C, it was found that HER dominates and the activity of CO2RR decreases. Moreover, the CO2RR products produced in this higher temperature range are mainly the C1 products, namely, CO and HCOOH. We argue that CO surface coverage, local pH, and kinetics play an important role in the lower-temperature regime, while the second regime appears most likely to be related to structural changes in the copper surface.

Restructuring of titanium oxide overlayers over nickel nanoparticles during catalysis.

Reducible supports can affect the performance of metal catalysts by the formation of suboxide overlayers upon reduction, a process referred to as the strong metal-support interaction (SMSI). A combination of operando electron microscopy and vibrational spectroscopy revealed that thin TiOx overlayers formed on nickel/titanium dioxide catalysts during 400°C reduction were completely removed under carbon dioxide hydrogenation conditions. Conversely, after 600°C reduction, exposure to carbon dioxide hydrogenation reaction conditions led to only partial reexposure of nickel, forming interfacial sites in contact with TiOx and favoring carbon-carbon coupling by providing a carbon species reservoir. Our findings challenge the conventional understanding of SMSIs and call for more-detailed operando investigations of nanocatalysts at the single-particle level to revisit static models of structure-activity relationships.

Elucidating the Roles of Nafion/Solvent Formulations in Copper-Catalyzed CO2 Electrolysis.

Nafion ionomer, composed of hydrophobic perfluorocarbon backbones and hydrophilic sulfonic acid side chains, is the most widely used additive for preparing catalyst layers (CLs) for electrochemical CO2 reduction, but its impact on the performance of CO2 electrolysis remains poorly understood. Here, we systematically investigate the role of the catalyst ink formulation on CO2 electrolysis using commercial CuO nanoparticles as the model pre-catalyst. We find that the presence of Nafion is essential for achieving stable product distributions due to its ability to stabilize the catalyst morphology under reaction conditions. Moreover, the Nafion content and solvent composition (water/alcohol fraction) regulate the internal structure of Nafion coatings, as well as the catalyst morphology, thereby significantly impacting CO2 electrolysis performance, resulting in variations of C2+ product Faradaic efficiency (FE) by >3×, with C2+ FE ranging from 17 to 54% on carbon paper substrates. Using a combination of ellipsometry and in situ Raman spectroscopy during CO2 reduction, we find that such selectivity differences stem from changes to the local reaction microenvironment. In particular, the combination of high water/alcohol ratios and low Nafion fractions in the catalyst ink results in stable and favorable microenvironments, increasing the local CO2/H2O concentration ratio and promoting high CO surface coverage to facilitate C2+ production in long-term CO2 electrolysis. Therefore, this work provides insights into the critical role of Nafion binders and underlines the importance of optimizing Nafion/solvent formulations as a means of enhancing the performance of electrochemical CO2 reduction systems.

Near-Unity Electrochemical CO2 to CO Conversion over Sn-Doped Copper Oxide Nanoparticles.

Bimetallic electrocatalysts have emerged as a viable strategy to tune the electrocatalytic CO2 reduction reaction (eCO2RR) for the selective production of valuable base chemicals and fuels. However, obtaining high product selectivity and catalyst stability remain challenging, which hinders the practical application of eCO2RR. In this work, it was found that a small doping concentration of tin (Sn) in copper oxide (CuO) has profound influence on the catalytic performance, boosting the Faradaic efficiency (FE) up to 98% for carbon monoxide (CO) at -0.75 V versus RHE, with prolonged stable performance (FE > 90%) for up to 15 h. Through a combination of ex situ and in situ characterization techniques, the in situ activation and reaction mechanism of the electrocatalyst at work was elucidated. In situ Raman spectroscopy measurements revealed that the binding energy of the crucial adsorbed *CO intermediate was lowered through Sn doping, thereby favoring gaseous CO desorption. This observation was confirmed by density functional theory, which further indicated that hydrogen adsorption and subsequent hydrogen evolution were hampered on the Sn-doped electrocatalysts, resulting in boosted CO formation. It was found that the pristine electrocatalysts consisted of CuO nanoparticles decorated with SnO2 domains, as characterized by ex situ high-resolution scanning transmission electron microscopy and X-ray photoelectron spectroscopy measurements. These pristine nanoparticles were subsequently in situ converted into a catalytically active bimetallic Sn-doped Cu phase. Our work sheds light on the intimate relationship between the bimetallic structure and catalytic behavior, resulting in stable and selective oxide-derived Sn-doped Cu electrocatalysts.

Probing the Dynamics of Low-Overpotential CO2-to-CO Activation on Copper Electrodes with Time-Resolved Raman Spectroscopy.

Oxide-derived copper electrodes have displayed a boost in activity and selectivity toward valuable base chemicals in the electrochemical carbon dioxide reduction reaction (CO2RR), but the exact interplay between the dynamic restructuring of copper oxide electrodes and their activity and selectivity is not fully understood. In this work, we have utilized time-resolved surface-enhanced Raman spectroscopy (TR-SERS) to study the dynamic restructuring of the copper (oxide) electrode surface and the adsorption of reaction intermediates during cyclic voltammetry (CV) and pulsed electrolysis (PE). By coupling the electrochemical data to the spectral features in TR-SERS, we study the dynamic activation of and reactions on the electrode surface and find that CO2 is already activated to carbon monoxide (CO) during PE (10% Faradaic efficiency, 1% under static applied potential) at low overpotentials (-0.35 VRHE). PE at varying cathodic bias on different timescales revealed that stochastic CO is dominant directly after the cathodic bias onset, whereas no CO intermediates were observed after prolonged application of low overpotentials. An increase in cathodic bias (-0.55 VRHE) resulted in the formation of static adsorbed CO intermediates, while the overall contribution of stochastic CO decreased. We attribute the low-overpotential CO2-to-CO activation to a combination of selective Cu(111) facet exposure, partially oxidized surfaces during PE, and the formation of copper-carbonate-hydroxide complex intermediates during the anodic pulses. This work sheds light on the restructuring of oxide-derived copper electrodes and low-overpotential CO formation and highlights the power of the combination of electrochemistry and time-resolved vibrational spectroscopy to elucidate CO2RR mechanisms.

Waste-Derived Copper-Lead Electrocatalysts for CO2 Reduction.

It remains a real challenge to control the selectivity of the electrocatalytic CO2 reduction (eCO2R) reaction to valuable chemicals and fuels. Most of the electrocatalysts are made of non-renewable metal resources, which hampers their large-scale implementation. Here, we report the preparation of bimetallic copper-lead (CuPb) electrocatalysts from industrial metallurgical waste. The metal ions were extracted from the metallurgical waste through simple chemical treatment with ammonium chloride, and CuxPby electrocatalysts with tunable compositions were fabricated through electrodeposition at varying cathodic potentials. X-ray spectroscopy techniques showed that the pristine electrocatalysts consist of Cu0, Cu1+ and Pb2+ domains, and no evidence for alloy formation was found. We found a volcano-shape relationship between eCO2R selectivity toward two electron products, such as CO, and the elemental ratio of Cu and Pb. A maximum Faradaic efficiency towards CO was found for Cu9.00Pb1.00, which was four times higher than that of pure Cu, under the same electrocatalytic conditions. In situ Raman spectroscopy revealed that the optimal amount of Pb effectively improved the reducibility of the pristine Cu1+ and Pb2+ domains to metallic Cu and Pb, which boosted the selectivity towards CO by synergistic effects. This work provides a framework of thinking to design and tune the selectivity of bimetallic electrocatalysts for CO2 reduction through valorization of metallurgical waste.

Sub-Second Time-Resolved Surface-Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper.

The electrocatalytic carbon dioxide (CO2 ) reduction reaction (CO2 RR) into hydrocarbons is a promising approach for greenhouse gas mitigation, but many details of this dynamic reaction remain elusive. Here, time-resolved surface-enhanced Raman spectroscopy (TR-SERS) is employed to successfully monitor the dynamics of CO2 RR intermediates and Cu surfaces with sub-second time resolution. Anodic treatment at 1.55 V vs. RHE and subsequent surface oxide reduction (below -0.4 V vs. RHE) induced roughening of the Cu electrode surface, which resulted in hotspots for TR-SERS, enhanced time resolution (down to ≈0.7 s) and fourfold improved CO2 RR efficiency toward ethylene. With TR-SERS, the initial restructuring of the Cu surface was followed (<7 s), after which a stable surface surrounded by increased local alkalinity was formed. Our measurements revealed that a highly dynamic CO intermediate, with a characteristic vibration below 2060 cm-1 , is related to C-C coupling and ethylene production (-0.9 V vs. RHE), whereas lower cathodic bias (-0.7 V vs. RHE) resulted in gaseous CO production from isolated and static CO surface species with a distinct vibration at 2092 cm-1 .

Stabilization effects in binary colloidal Cu and Ag nanoparticle electrodes under electrochemical CO2 reduction conditions.

Nanoparticle modified electrodes constitute an attractive way to tailor-make efficient carbon dioxide (CO2) reduction catalysts. However, the restructuring and sintering processes of nanoparticles under electrochemical reaction conditions not only impedes the widespread application of nanoparticle catalysts, but also misleads the interpretation of the selectivity of the nanocatalysts. Here, we colloidally synthesized metallic copper (Cu) and silver (Ag) nanoparticles with a narrow size distribution (<10%) and utilized them in electrochemical CO2 reduction reactions. Monometallic Cu and Ag nanoparticle electrodes showed severe nanoparticle sintering already at low overpotential of -0.8 V vs. RHE, as evidenced by ex situ SEM investigations, and potential-dependent variations in product selectivity that resemble bulk Cu (14% for ethylene at -1.3 V vs. RHE) and Ag (69% for carbon monoxide at -1.0 V vs. RHE). However, by co-deposition of Cu and Ag nanoparticles, a nanoparticle stabilization effect was observed between Cu and Ag, and the sintering process was greatly suppressed at CO2 reducing potentials (-0.8 V vs. RHE). Furthermore, by varying the Cu/Ag nanoparticle ratio, the CO2 reduction reaction (CO2RR) selectivity towards methane (maximum of 20.6% for dense Cu2.5-Ag1 electrodes) and C2 products (maximum of 15.7% for dense Cu1-Ag1 electrodes) can be tuned, which is attributed to a synergistic effect between neighbouring Ag and Cu nanoparticles. We attribute the stabilization of the nanoparticles to the positive enthalpies of Cu-Ag solid solutions, which prevents the dissolution-redeposition induced particle growth under CO2RR conditions. The observed nanoparticle stabilization effect enables the design and fabrication of active CO2 reduction nanocatalysts with high durability.

Quantitative Electrochemical Control over Optical Gain in Quantum-Dot Solids.

Solution-processed quantum dot (QD) lasers are one of the holy grails of nanoscience. They are not yet commercialized because the lasing threshold is too high: one needs >1 exciton per QD, which is difficult to achieve because of fast nonradiative Auger recombination. The threshold can, however, be reduced by electronic doping of the QDs, which decreases the absorption near the band-edge, such that the stimulated emission (SE) can easily outcompete absorption. Here, we show that by electrochemically doping films of CdSe/CdS/ZnS QDs, we achieve quantitative control over the gain threshold. We obtain stable and reversible doping of more than two electrons per QD. We quantify the gain threshold and the charge carrier dynamics using ultrafast spectroelectrochemistry and achieve quantitative agreement between experiments and theory, including a vanishingly low gain threshold for doubly doped QDs. Over a range of wavelengths with appreciable gain coefficients, the gain thresholds reach record-low values of ∼1 × 10-5 excitons per QD. These results demonstrate a high level of control over the gain threshold in doped QD solids, opening a new route for the creation of cheap, solution-processable, low-threshold QD lasers.

Trapping and Detrapping in Colloidal Perovskite Nanoplatelets: Elucidation and Prevention of Nonradiative Processes through Chemical Treatment.

Metal-halide perovskite nanocrystals show promise as the future active material in photovoltaics, lighting, and other optoelectronic applications. The appeal of these materials is largely due to the robustness of the optoelectronic properties to structural defects. The photoluminescence quantum yield (PLQY) of most types of perovskite nanocrystals is nevertheless below unity, evidencing the existence of nonradiative charge-carrier decay channels. In this work, we experimentally elucidate the nonradiative pathways in CsPbBr3 nanoplatelets, before and after chemical treatment with PbBr2 that improves the PLQY. A combination of picosecond streak camera and nanosecond time-correlated single-photon counting measurements is used to probe the excited-state dynamics over 6 orders of magnitude in time. We find that up to 40% of the nanoplatelets from a synthesis batch are entirely nonfluorescent and cannot be turned fluorescent through chemical treatment. The other nanoplatelets show fluorescence, but charge-carrier trapping leads to losses that are prevented by chemical treatment. Interestingly, even without chemical treatment, some losses due to trapping are mitigated because trapped carriers spontaneously detrap on nanosecond-to-microsecond timescales. Our analysis shows that multiple nonradiative pathways are active in perovskite nanoplatelets, which are affected differently by chemical treatment with PbBr2. More generally, our work highlights that in-depth studies using a combination of techniques are necessary to understand nonradiative pathways in fluorescent nanocrystals. Such understanding is essential to optimize synthesis and treatment procedures.

Operando Nanoscale Sensors in Catalysis: All Eyes on Catalyst Particles.

An era of circularity requires robust and flexible catalysts and reactors. We need profound knowledge of catalytic surface reactions on the local scale (i.e., angstrom-nanometer), whereas the reaction conditions, such as reaction temperature and pressure, are set and controlled on the macroscale (i.e., millimeter-meter). Nanosensors operating on all relevant length scales can supply this information in real time during operando working conditions. In this Perspective, we demonstrate the potential of nanoscale sensors, with special emphasis on local molecular sensing with shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) and local temperature sensing with luminescence thermometry, to acquire new insights of the reaction pathways. We also argue that further developments should be focused on local pressure measurements and on expanding the applications of these local sensors in other areas, such as liquid-phase catalysis, electrocatalysis, and photocatalysis. Ideally, a combination of sensors will be applied to monitor catalyst and reactor "health" and serve as feedback to the reactor conditions.

Overcoming the exciton binding energy in two-dimensional perovskite nanoplatelets by attachment of conjugated organic chromophores.

In this work we demonstrate a novel approach to achieve efficient charge separation in dimensionally and dielectrically confined two-dimensional perovskite materials. Two-dimensional perovskites generally exhibit large exciton binding energies that limit their application in optoelectronic devices that require charge separation such as solar cells, photo-detectors and in photo-catalysis. Here, we show that by incorporating a strongly electron accepting moiety, perylene diimide organic chromophores, on the surface of the two-dimensional perovskite nanoplatelets it is possible to achieve efficient formation of mobile free charge carriers. These free charge carriers are generated with ten times higher yield and lifetimes of tens of microseconds, which is two orders of magnitude longer than without the peryline diimide acceptor. This opens a novel synergistic approach, where the inorganic perovskite layers are combined with functional organic chromophores in the same material to tune the properties for specific applications.

Electrochemical Modulation of the Photophysics of Surface-Localized Trap States in Core/Shell/(Shell) Quantum Dot Films.

In this work, we systematically study the spectroelectrochemical response of CdSe quantum dots (QDs), CdSe/CdS core/shell QDs with varying CdS shell thicknesses, and CdSe/CdS/ZnS core/shell/shell QDs in order to elucidate the influence of localized surface trap states on the optoelectronic properties. By correlating the differential absorbance and the photoluminescence upon electrochemically raising the Fermi level, we reveal that trap states near the conduction band (CB) edge give rise to nonradiative recombination pathways regardless of the CdS shell thickness, evidenced by quenching of the photoluminescence before the CB edge is populated with electrons. This points in the direction of shallow trap states localized on the CdS shell surface that give rise to nonradiative recombination pathways. We suggest that these shallow trap states reduce the quantum yield because of enhanced hole trapping when the Fermi level is raised electrochemically. We show that these shallow trap states are removed when additional wide band gap ZnS shells are grown around the CdSe/CdS core/shell QDs.

Tailoring Cu+ for Ga3+ Cation Exchange in Cu2-xS and CuInS2 Nanocrystals by Controlling the Ga Precursor Chemistry.

Nanoscale cation exchange (CE) has resulted in colloidal nanomaterials that are unattainable by direct synthesis methods. Aliovalent CE is complex and synthetically challenging because the exchange of an unequal number of host and guest cations is required to maintain charge balance. An approach to control aliovalent CE reactions is the use of a single reactant to both supply the guest cation and extract the host cation. Here, we study the application of GaCl3-L complexes [L = trioctylphosphine (TOP), triphenylphosphite (TPP), diphenylphosphine (DPP)] as reactants in the exchange of Cu+ for Ga3+ in Cu2-xS nanocrystals. We find that noncomplexed GaCl3 etches the nanocrystals by S2- extraction, whereas GaCl3-TOP is unreactive. Successful exchange of Cu+ for Ga3+ is only possible when GaCl3 is complexed with either TPP or DPP. This is attributed to the pivotal role of the Cu2-xS-GaCl3-L activated complex that forms at the surface of the nanocrystal at the onset of the CE reaction, which must be such that simultaneous Ga3+ insertion and Cu+ extraction can occur. This requisite is only met if GaCl3 is bound to a phosphine ligand, with a moderate bond strength, to allow facile dissociation of the complex at the nanocrystal surface. The general validity of this mechanism is demonstrated by using GaCl3-DPP to convert CuInS2 into (Cu,Ga,In)S2 nanocrystals, which increases the photoluminescence quantum yield 10-fold, while blue-shifting the photoluminescence into the NIR biological window. This highlights the general applicability of the mechanistic insights provided by our work.

On the Stability of Permanent Electrochemical Doping of Quantum Dot, Fullerene, and Conductive Polymer Films in Frozen Electrolytes for Use in Semiconductor Devices.

Semiconductor films that allow facile ion transport can be electronically doped via electrochemistry, where the amount of injected charge can be controlled by the potential applied. To apply electrochemical doping to the design of semiconductor devices, the injected charge has to be stabilized to avoid unintentional relaxation back to the intrinsic state. Here, we investigate methods to increase the stability of electrochemically injected charges in thin films of a wide variety of semiconductor materials, namely inorganic semiconductors (ZnO NCs, CdSe NCs, and CdSe/CdS core/shell NCs) and organic semiconductors (P3DT, PCBM, and C60). We show that by charging the semiconductors at elevated temperatures in solvents with melting points above room temperature, the charge stability at room temperature increases greatly, from seconds to days. At reduced temperature (-75 °C when using succinonitrile as electrolyte solvent) the injected charge becomes entirely stable on the time scale of our experiments (up to several days). Other high melting point solvents such as dimethyl sulfone, ethylene carbonate, and poly(ethylene glycol) (PEG) also offer increased charge stability at room temperature. Especially the use of PEG increases the room temperature charge stability by several orders of magnitude compared to using acetonitrile. We discuss how this improvement of the charge stability is related to the immobilization of electrolyte ions and impurities. While the electrolyte ions are immobilized, conductivity measurements show that electrons in the semiconductor films remain mobile. These results highlight the potential of using solidified electrolytes to stabilize injected charges, which is a promising step toward making semiconductor devices based on electrochemically doped semiconductor thin films.