Morphological-Electrical Property Relation in Cu(In,Ga)(S,Se)2 Solar Cells: Significance of Crystal Grain Growth and Band Grading by Potassium Treatment.

Solution-processed Cu(In,Ga)(S,Se)2  (CIGS) has a great potential for the production of large-area photovoltaic devices at low cost. However, CIGS solar cells processed from solution exhibit relatively lower performance compared to vacuum-processed devices because of a lack of proper composition distribution, which is mainly instigated by the limited Se uptake during chalcogenization. In this work, a unique potassium treatment method is utilized to improve the selenium uptake judiciously, enhancing grain sizes and forming a wider bandgap minimum region. Careful engineering of the bandgap grading structure also results in an enlarged space charge region, which is favorable for electron-hole separation and efficient charge carrier collection. Besides, this device processing approach has led to a linearly increasing electron diffusion length and carrier lifetime with increasing the grain size of the CIGS film, which is a critical achievement for enhancing photocurrent yield. Overall, 15% of power conversion efficiency is achieved in solar cells processed from environmentally benign solutions. This approach offers critical insights for precise device design and processing rules for solution-processed CIGS solar cells.

Electrochemical Fragmentation of Cu2O Nanoparticles Enhancing Selective C-C Coupling from CO2 Reduction Reaction.

In this study, we demonstrate that the initial morphology of nanoparticles can be transformed into small fragmented nanoparticles, which were densely contacted to each other, during electrochemical CO2 reduction reaction (CO2RR). Cu-based nanoparticles were directly grown on a carbon support by using cysteamine immobilization agent, and the synthesized nanoparticle catalyst showed increasing activity during initial CO2RR, doubling Faradaic efficiency of C2H4 production from 27% to 57.3%. The increased C2H4 production activity was related to the morphological transformation over reaction time. Twenty nm cubic Cu2O crystalline particles gradually experienced in situ electrochemical fragmentation into 2-4 nm small particles under the negative potential, and the fragmentation was found to be initiated from the surface of the nanocrystal. Compared to Cu@CuO nanoparticle/C or bulk Cu foil, the fragmented Cu-based NP/C catalyst achieved enhanced C2+ production selectivity, accounting 87% of the total CO2RR products, and suppressed H2 production. In-situ X-ray absorption near edge structure studies showed metallic Cu0 state was observed under CO2RR, but the fragmented nanoparticles were more readily reoxidized at open circuit potential inside of the electrolyte, allowing labile Cu states. The unique morphology, small nanoparticles stacked upon on another, is proposed to promote C-C coupling reaction selectivity from CO2RR by suppressing HER.

Mixed Copper States in Anodized Cu Electrocatalyst for Stable and Selective Ethylene Production from CO2 Reduction.

Oxygen-Cu (O-Cu) combination catalysts have recently achieved highly improved selectivity for ethylene production from the electrochemical CO2 reduction reaction (CO2RR). In this study, we developed anodized copper (AN-Cu) Cu(OH)2 catalysts by a simple electrochemical synthesis method and achieved ∼40% Faradaic efficiency for ethylene production, and high stability over 40 h. Notably, the initial reduction conditions applied to AN-Cu were critical to achieving selective and stable ethylene production activity from the CO2RR, as the initial reduction condition affects the structures and chemical states, crucial for highly selective and stable ethylene production over methane. A highly negative reduction potential produced a catalyst maintaining long-term stability for the selective production of ethylene over methane, and a small amount of Cu(OH)2 was still observed on the catalyst surface. Meanwhile, when a mild reduction condition was applied to the AN-Cu, the Cu(OH)2 crystal structure and mixed states disappeared on the catalyst, becoming more favorable to methane production after few hours. These results show the selectivity of ethylene to methane in O-Cu combination catalysts is influenced by the electrochemical reduction environment related to the mixed valences. This will provide new strategies to improve durability of O-Cu combination catalysts for C-C coupling products from electrochemical CO2 conversion.

Investigation of Surface Sulfurization in CuIn1-x Gax S2-y Sey Thin Films by Using Kelvin Probe Force Microscopy.

CuIn1-x Gax S2-y Sey (CIGSSe) thin films have attracted a great deal of attention as promising absorbing materials for solar cell applications, owing to their favorable optical properties (e.g. a direct band gap and high absorption coefficients) and stable structure. Many studies have sought to improve the efficiency of solar cells using these films, and it has been found that surface modification through post-heat treatment can lead to surface passivation of surface defects and a subsequent increase in efficiency. The surface properties of solution-processed CIGSSe films are considered to be particularly important in this respect, owing to the fact that they are more prone to defects. In this work, CIGSSe thin films with differing S/Se ratios at their surface were synthesized by using a precursor solution and post-sulfurization heat treatment. These CIGSSe thin films were investigated with current-voltage and Kelvin probe force microscope (KPFM) analyses. Surface photovoltage (SPV), which is the difference in the work function in the dark and under illumination, was measured by using KPFM, which can examine the screening and the modification of surface charge through carrier trapping. As the concentration of S increases on the CIGSSe film surface, higher work functions and more positive SPV values were observed. Based on these measurements, we inferred the band-bending behavior of CIGSSe absorber films and proposed reasons for the improvement in solar cell performance.

Charge separation properties of Ta3N5 photoanodes synthesized via a simple metal-organic-precursor decomposition process.

Here, we successfully synthesized a Ta3N5 thin film using a simple metal-organic-precursor decomposition process followed by its conversion to nitride and studied its photoelectrochemical (PEC) properties to understand charge separation on the surface. Newly synthesized Ta3N5 photoanodes showed a significant difference in the PEC activity in relation to the annealing temperature under ammonia flow, although similar light absorption properties or electronic states were obtained. Charge separation related PEC properties were analyzed using intensity modulated photocurrent density spectroscopy (IMPS) and photocurrent measurements in the absence/presence of scavengers. The charge transfer and recombination rate constants which are related to the photogenerated charge-separation dynamics on the Ta3N5 surface were found to be more sensitively influenced by the ammonia annealing temperatures, and low temperature (700 °C) treated Ta3N5 showed a fast recombination rate constant (kr). In addition, high-efficiency charge injection into the electrolyte on the surface was critically associated with the greatly enhanced photocurrent density of Ta3N5 synthesized at a higher temperature (900 °C) of ammonia annealing.

Enhanced Photocurrents with ZnS Passivated Cu(In,Ga)(Se,S)2 Photocathodes Synthesized Using a Nonvacuum Process for Solar Water Splitting.

Chalcopyrite Cu(In,Ga)(Se,S)2 (CIGS) semiconductors are potential candidates for use in photoelectrochemical (PEC) hydrogen generation due to their excellent optical absorption properties and high conduction band edge position. In the present research, CIGS thin film was successfully prepared on a transparent substrate (F:SnO2 glass) using a solution-based process and applied for a photocathode in solar water splitting, which shows control of the surface state associated with sulfurization/selenization process significantly influences on the PEC activity. A ZnS passivation surface layer was introduced, which effectively suppresses charge recombination by surface states of CIGS. The CIGS/ZnS/Pt photocathode exhibited highly enhanced PEC activity (∼24 mA·cm-2 at -0.3 V vs RHE). The performances of our CIGS photocathode on the transparent substrate were also characterized under front/back light illumination, and the incident photon to current conversion efficiency (IPCE) drastically changed depending on the illumination directions showing decreased IPCE especially under UV region with back illumination. The slow minority carrier (electron) transportation is suggested as a limiting factor for the PEC activity of the CIGS photocathode.

Achieving Selective and Efficient Electrocatalytic Activity for CO2 Reduction Using Immobilized Silver Nanoparticles.

Selective electrochemical reduction of CO2 is one of the most sought-after processes because of the potential to convert a harmful greenhouse gas to a useful chemical. We have discovered that immobilized Ag nanoparticles supported on carbon exhibit enhanced Faradaic efficiency and a lower overpotential for selective reduction of CO2 to CO. These electrocatalysts were synthesized directly on the carbon support by a facile one-pot method using a cysteamine anchoring agent resulting in controlled monodispersed particle sizes. These synthesized Ag/C electrodes showed improved activities, specifically decrease of the overpotential by 300 mV at 1 mA/cm(2), and 4-fold enhanced CO Faradaic efficiency at -0.75 V vs RHE with the optimal particle size of 5 nm compared to polycrystalline Ag foil. DFT calculations enlightened that the specific interaction between Ag nanoparticle and the anchoring agents modified the catalyst surface to have a selectively higher affinity to the intermediate COOH over CO, which effectively lowers the overpotential.

Embedding covalency into metal catalysts for efficient electrochemical conversion of CO2.

CO2 conversion is an essential technology to develop a sustainable carbon economy for the present and the future. Many studies have focused extensively on the electrochemical conversion of CO2 into various useful chemicals. However, there is not yet a solution of sufficiently high enough efficiency and stability to demonstrate practical applicability. In this work, we use first-principles-based high-throughput screening to propose silver-based catalysts for efficient electrochemical reduction of CO2 to CO while decreasing the overpotential by 0.4-0.5 V. We discovered the covalency-aided electrochemical reaction (CAER) mechanism in which p-block dopants have a major effect on the modulating reaction energetics by imposing partial covalency into the metal catalysts, thereby enhancing their catalytic activity well beyond modulations arising from d-block dopants. In particular, sulfur or arsenic doping can effectively minimize the overpotential with good structural and electrochemical stability. We expect this work to provide useful insights to guide the development of a feasible strategy to overcome the limitations of current technology for electrochemical CO2 conversion.

Fabrication of solution processed 3D nanostructured CuInGaS2 thin film solar cells.

In this study we demonstrate the fabrication of CuInGaS2 (CIGS) thin film solar cells with a three-dimensional (3D) nanostructure based on indium tin oxide (ITO) nanorod films and precursor solutions (Cu, In and Ga nitrates in alcohol). To obtain solution processed 3D nanostructured CIGS thin film solar cells, two different precursor solutions were applied to complete gap filling in ITO nanorods and achieve the desirable absorber film thickness. Specifically, a coating of precursor solution without polymer binder material was first applied to fill the gap between ITO nanorods followed by deposition of the second precursor solution in the presence of a binder to generate an absorber film thickness of ∼1.3 µm. A solar cell device with a (Al, Ni)/AZO/i-ZnO/CdS/CIGS/ITO nanorod/glass structure was constructed using the CIGS film, and the highest power conversion efficiency was measured to be ∼6.3% at standard irradiation conditions, which was 22.5% higher than the planar type of CIGS solar cell on ITO substrate fabricated using the same precursor solutions.

Band gap grading and photovoltaic performance of solution-processed Cu(In,Ga)S2 thin-film solar cells.

The photophysical properties of CuInxGa1-xS2 (CIGS) thin films, prepared by solution-based coating methods, are investigated to understand the correlation between the optical properties of these films and the electrical characteristics of solar cells fabricated using these films. Photophysical properties, such as the depth-dependent band gap and carrier lifetime, turn out to be at play in determining the energy conversion efficiency of solar cells. A double grading of the band gap in CIGS films enhances solar cell efficiency, even when defect states disturb carrier collection by non-radiative decay. The combinational stacking of different density films leads to improved solar cell performance as well as efficient fabrication because a graded band gap and reduced shunt current increase carrier collection efficiency. The photodynamics of minority-carriers suggests that the suppression of defect states is a primary area of improvement in CIGS thin films prepared by solution-based methods.

Extrinsic hydrophobicity-controlled silver nanoparticles as efficient and stable catalysts for CO2 electrolysis.

To realize economically feasible electrochemical CO2 conversion, achieving a high partial current density for value-added products is particularly vital. However, acceleration of the hydrogen evolution reaction due to cathode flooding in a high-current-density region makes this challenging. Herein, we find that partially ligand-derived Ag nanoparticles (Ag-NPs) could prevent electrolyte flooding while maintaining catalytic activity for CO2 electroreduction. This results in a high Faradaic efficiency for CO (>90%) and high partial current density (298.39 mA cm‒2), even under harsh stability test conditions (3.4 V). The suppressed splitting/detachment of Ag particles, due to the lipid ligand, enhance the uniform hydrophobicity retention of the Ag-NP electrode at high cathodic overpotentials and prevent flooding and current fluctuations. The mass transfer of gaseous CO2 is maintained in the catalytic region of several hundred nanometers, with the smooth formation of a triple phase boundary, which facilitate the occurrence of CO2RR instead of HER. We analyze catalyst degradation and cathode flooding during CO2 electrolysis through identical-location transmission electron microscopy and operando synchrotron-based X-ray computed tomography. This study develops an efficient strategy for designing active and durable electrocatalysts for CO2 electrolysis.

Fabrication of nanocrystal ink based superstrate-type CuInS2 thin film solar cells.

A CuInS2 (CIS) nanocrystal ink was applied to thin film solar cell devices with superstrate-type configuration. Monodispersed CIS nanocrystals were synthesized by a colloidal synthetic route and re-dispersed in toluene to form an ink. A spray method was used to coat CIS films onto conducting glass substrates. Prior to CIS film deposition, TiO2 and CdS thin films were also prepared as a blocking layer and a buffer layer, respectively. We found that both a TiO2 blocking layer and a CdS buffer layer are necessary to generate photoresponses in superstrate-type devices. The best power conversion efficiency (∼1.45%) was achieved by the CIS superstrate-type thin film solar cell device with 200 and 100 nm thick TiO2 and CdS films, respectively.

Silver nanoparticles are assembled only on the two facets of the rod template.

Although the focus of nano-research appears to be shifting to the creation of the secondary structures using primary nanoparticle (NP) building blocks, very complex preparation routes to assemble NPs have been reported so far. In this work, for the first time, we demonstrate that silver NPs can be organized to assemble on the two facets of the 1-dimensional rod template via facile one-step process. This method could potentially be used to prepare assembly of diverse metal, semiconductor, or metal oxide NPs in the one dimensional material form.

Electrode reconstruction strategy for oxygen evolution reaction: maintaining Fe-CoOOH phase with intermediate-spin state during electrolysis.

Computational calculations and experimental studies reveal that the CoOOH phase and the intermediate-spin (IS) state are the key factors for realizing efficient Co-based electrocatalysts for the oxygen evolution reaction (OER). However, according to thermodynamics, general cobalt oxide converts to the CoO2 phase under OER condition, retarding the OER kinetics. Herein, we demonstrate a simple and scalable strategy to fabricate electrodes with maintaining Fe-CoOOH phase and an IS state under the OER. The changes of phase and spin states were uncovered by combining in-situ/operando X-ray based absorption spectroscopy and Raman spectroscopy. Electrochemical reconstruction of chalcogenide treated Co foam affords a highly enlarged active surface that conferred excellent catalytic activity and stability in a large-scale water electrolyzer. Our findings are meaningful in that the calculated results were experimentally verified through the operando analyses. It also proposes a new strategy for electrode fabrication and confirms the importance of real active phases and spin states under a particular reaction condition.

Exploring dopant effects in stannic oxide nanoparticles for CO2 electro-reduction to formate.

The electrosynthesis of formate from CO2 can mitigate environmental issues while providing an economically valuable product. Although stannic oxide is a good catalytic material for formate production, a metallic phase is formed under high reduction overpotentials, reducing its activity. Here, using a fluorine-doped tin oxide catalyst, a high Faradaic efficiency for formate (95% at 100 mA cm-2) and a maximum partial current density of 330 mA cm-2 (at 400 mA cm-2) is achieved for the electroreduction of CO2. Furthermore, the formate selectivity (≈90%) is nearly constant over 7 days of operation at a current density of 100 mA cm-2. In-situ/operando spectroscopies reveal that the fluorine dopant plays a critical role in maintaining the high oxidation state of Sn, leading to enhanced durability at high current densities. First-principle calculation also suggests that the fluorine-doped tin oxide surface could provide a thermodynamically stable environment to form HCOO* intermediate than tin oxide surface. These findings suggest a simple and efficient approach for designing active and durable electrocatalysts for the electrosynthesis of formate from CO2.

Toward economical application of carbon capture and utilization technology with near-zero carbon emission.

Carbon capture and utilization technology has been studied for its practical ability to reduce CO2 emissions and enable economical chemical production. The main challenge of this technology is that a large amount of thermal energy must be provided to supply high-purity CO2 and purify the product. Herein, we propose a new concept called reaction swing absorption, which produces synthesis gas (syngas) with net-zero CO2 emission through direct electrochemical CO2 reduction in a newly proposed amine solution, triethylamine. Experimental investigations show high CO2 absorption rates (>84%) of triethylamine from low CO2 concentrated flue gas. In addition, the CO Faradaic efficiency in a triethylamine supplied membrane electrode assembly electrolyzer is approximately 30% (@-200 mA cm-2), twice higher than those in conventional alkanolamine solvents. Based on the experimental results and rigorous process modeling, we reveal that reaction swing absorption produces high pressure syngas at a reasonable cost with negligible CO2 emissions. This system provides a fundamental solution for the CO2 crossover and low system stability of electrochemical CO2 reduction.

Impact of Absorber Layer Morphology on Photovoltaic Properties in Solution-Processed Chalcopyrite Solar Cells.

Solution-processed chalcopyrite solar cells can be economically produced on a large scale; however, for them to be commercially viable, their low efficiency and detrimental processing have to be overcome. To this end, extensive research efforts have been devoted to boost device efficiency and develop benign solution processes. In this review, relevant processes are categorized into molecular-based and particulate-based solution processes, and progress is evaluated in terms of device performance and processing. To identify strategies for improving device performance, the key parameters affecting the optoelectronic properties of the device are discussed. Interestingly, the authors found an unnoticed fact from previously reported experimental results in literature: short-circuit current density increases and deficit of open-circuit voltage decreases as the average domain size of the absorber layer increases. In addition, the power conversion efficiency increases with the grain size irrespective of the band gap, thickness, and processing conditions. Ensuring a large grain size is specifically elucidated to be necessary to increase the photocurrent generation and reduce the charge carrier recombination in the chalcopyrite solar cells. The findings and related reviews afford critical insight into the absorber film design to improve the performance of solution-processed chalcopyrite solar cells.

Solution-processed near-infrared Cu(In,Ga)(S,Se)2 photodetectors with enhanced chalcopyrite crystallization and bandgap grading structure via potassium incorporation.

Although solution-processed Cu(In,Ga)(S,Se)2 (CIGS) absorber layers can potentially enable the low-cost and large-area production of highly stable electronic devices, they have rarely been applied in photodetector applications. In this work, we present a near-infrared photodetector functioning at 980 nm based on solution-processed CIGS with a potassium-induced bandgap grading structure and chalcopyrite grain growth. The incorporation of potassium in the CIGS film promotes Se uptake in the bulk of the film during the chalcogenization process, resulting in a bandgap grading structure with a wide space charge region that allows improved light absorption in the near-infrared region and charge carrier separation. Also, increasing the Se penetration in the potassium-incorporated CIGS film leads to the enhancement of chalcopyrite crystalline grain growth, increasing charge carrier mobility. Under the reverse bias condition, associated with hole tunneling from the ZnO interlayer, the increasing carrier mobility of potassium-incorporated CIGS photodetector improved photosensitivity and particularly external quantum efficiency more than 100% at low light intensity. The responsivity and detectivity of the potassium-incorporated CIGS photodetector reach 1.87 A W-1 and 6.45 [Formula: see text] 1010 Jones, respectively, and the - 3 dB bandwidth of the device extends to 10.5 kHz under 980 nm near-infrared light.

High crystallinity design of Ir-based catalysts drives catalytic reversibility for water electrolysis and fuel cells.

The voltage reversal of water electrolyzers and fuel cells induces a large positive potential on the hydrogen electrodes, followed by severe system degradation. Applying a reversible multifunctional electrocatalyst to the hydrogen electrode is a practical solution. Ir exhibits excellent catalytic activity for hydrogen evolution reactions (HER), and hydrogen oxidation reactions (HOR), yet irreversibly converts to amorphous IrOx at potentials > 0.8 V/RHE, which is an excellent catalyst for oxygen evolution reactions (OER), yet a poor HER and HOR catalyst. Harnessing the multifunctional catalytic characteristics of Ir, here we design a unique Ir-based electrocatalyst with high crystallinity for OER, HER, and HOR. Under OER operation, the crystalline nanoparticle generates an atomically-thin IrOx layer, which reversibly transforms into a metallic Ir at more cathodic potentials, restoring high activity for HER and HOR. Our analysis reveals that a metallic Ir subsurface under thin IrOx layer can act as a catalytic substrate for the reduction of Ir ions, creating reversibility. Our work not only uncovers fundamental, uniquely reversible catalytic properties of nanoparticle catalysts, but also offers insights into nanocatalyst design.

Achieving over 15% Efficiency in Solution-Processed Cu(In,Ga)(S,Se)2 Thin-Film Solar Cells via a Heterogeneous-Formation-Induced Benign p-n Junction Interface.

Cu(In,Ga)(S,Se)2 (CIGS) thin-film solar cells have attracted considerable interest in the field of photovoltaic devices due to their high efficiency and great potential for diverse applications. While CdS has been the most favorable n-type semiconductor because of its excellent lattice-match and electronic band alignment with p-type CIGS, its narrow optical band gap (∼2.4 eV) has limited light absorption in underlying CIGS absorber films. Reducing the thickness of CdS films to increase the short-circuit current-density has been less effective due to the following decrease in the open-circuit voltage. To overcome this trade-off between the main parameters, we controlled the formation mechanism of CdS films in chemical bath deposition and established its direct correlation with the properties of p-n junctions. Interestingly, a heterogeneous CdS film formation was found to have a synergetic effect with its ammonia bath solution, effectively reducing charge carrier loss from the shunt paths and interface recombination of CIGS/CdS junctions. With these electrical benefits, the trade-off was successfully alleviated and our best device achieved a power conversion efficiency of 15.6%, which is one of the state-of-the-art CIGS thin-film solar cells prepared using solution-processing techniques.