The large open‐circuit voltage deficit (Voc,def) is the key issue that limits kesterite (Cu2ZnSn(S,Se)4, [CZTSSe]) solar cell performance. Substitution of Cu+ by larger ionic Ag+ ((Ag,Cu)2ZnSn(S,Se)4, [ACZTSSe]) is one strategy to reduce Cu–Zn disorder and improve kesterite Voc. However, the so far reported ACZTSSe solar cell has not demonstrated lower Voc,def than the world record device, indicating that some intrinsic defect properties cannot be mitigated using current approaches. Here, incorporation of Ag into kesterite through a dimethyl sulfoxide (DMSO) solution that can facilitate direct phase transformation grain growth and produce a uniform and less defective kesterite absorber is reported. The same coordination chemistry of Ag+ and Cu+ in the DMSO solution results in the same reaction path of ACZTSSe to CZTSSe, resulting in significant suppression of CuZn defects, its defect cluster [2CuZn + SnZn], and deep level defect CuSn. A champion device with an efficiency of 12.5% (active area efficiency 13.5% without antireflection coating) and a record low Voc,def (64.2% Shockley–Queisser limit) is achieved from ACZTSSe with 5% Ag content.
Leaf senescence in plants involves both positive and negative transcriptional regulation. In this work, we show evidence for the single-stranded DNA-binding protein WHIRLY1 (WHY1) that functions as an upstream suppressor of WRKY53 in a developmental stage-dependent manner during leaf senescence in Arabidopsis (Arabidopsis thaliana). The why1 mutant displayed an early-senescence phenotype. In this background, the expression levels of both WRKY53 and the senescenceassociated protease gene SAG12 increased. WHY1 bound to the sequence region that contains an elicitor response element motif-like sequence, GNNNAAATT, plus an AT-rich telomeric repeat-like sequence in the WRKY53 promoter in in vivo and in vitro mutagenesis assays as well as in a chromatin immunoprecipitation assay. This binding to the promoter of WRKY53 was regulated in a developmental stage-dependent manner, as verified by chromatin immunoprecipitation-polymerase chain reaction assay. This direct interaction was further determined by a transient expression assay in which WHY1 repressed b-GLUCURONIDASE gene expression driven by the WRKY53 promoter. Genetic analysis of double mutant transgenic plants revealed that WHY1 overexpression in the wrky53 mutant (oeWHY1wrky53) had no effect on the stay-green phenotype of the wrky53 mutant, while a WHY1 knockout mutant in the wrky53 mutant background (why1wrky53) generated subtle change in the leaf yellow/green phenotype. These results suggest that WHY1 was an upstream regulator of WRKY53 during leaf senescence.
The limiting factor preventing kesterite (CZTSSe) thin film solar cell performance further improvement is the large open-circuit voltage deficit (Voc,def) issue, which is 0.345V for the current world record device with an efficiency of 12.6%. In this work, SnCl4 and SnCl2•2H2O are respectively used as tin precursor to investigate the Voc,def issue of dimethyl sulfoxide (DMSO) solution processed CZTSSe solar cells. Different complexations of tin compounds with thiourea and DMSO lead to different reaction pathways from solution to absorber material and thus dramatic difference in photovoltaic performance. The coordination of Sn 2+ with Tu leads to the formation of SnS and ZnS and Cu2S in the precursor film, which converted to selenides first and then fused to CZTSSe, resulting in poor film quality and device performance. The highest efficiency obtained from this film is 8.84% with a Voc,def of 0.391V. The coordination of Sn 4+with DMSO facilitates direct formation ofkesterite CZTS phase in the precursor film which directed converted to CZTSSe during selenization, resulting in compositional uniform absorber and high device performance. A device with active area efficiency 12.2% and a Voc,def of 0.344 V was achieved from Sn 4+ solution processed absorber. Furthermore, CZTSSe/CdS heterojunction heat treatment (JHT) significantly improved Sn 4+ device performance but had slightly negative effect on Sn 2+ device. A champion CZTSSe solar cell with a total area efficiency of 12.4% (active are efficiency 13.6%) and low Voc,def of 0.297 V was achieved from Sn 4+ solution. Our results demonstrate the preformed uniform kesterite phase enabled by Sn 4+ precursor is the key in achieving highly efficient kesterite absorber material. The lowest Voc-def and high efficiency achieved here shines new light on the future of kesterite solar cell.
Sensitive electrochemical sensors were fabricated with reduced graphene oxide-supported Au@Pd (Au@Pd-RGO) nanocomposites by one-step synthesis for individual and simultaneous determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA) with low detection limits and wide concentration ranges. From the Au@Pd-RGO-modified electrodes, well-separated oxidation peaks and enhanced peak currents of AA, DA, and UA were observed owing to the superior conductivity of RGO and the excellent catalytic activity of Au@Pd nanoparticles. For individual detection, the linear responses of AA, DA, and UA were in the concentration ranges of 0.1-1000, 0.01-100, and 0.02-500 μM with detection limits of 0.02, 0.002, and 0.005 μM (S/N = 3), respectively. For simultaneous detection by synchronous change of the concentrations of AA, DA, and UA, the linear response ranges were 1-800, 0.1-100, and 0.1-350 μM with detection limits of 0.28, 0.024, and 0.02 μM (S/N = 3), respectively. The fabricated sensors were further applied to the detection of AA, DA, and UA in urine samples. The Au@Pd-RGO nanocomposites have promising applications in highly sensitive and selective electrochemical sensing.
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