Kesterite Cu2ZnSn(S,Se)4 solar cells fabricated from DMSO molecular solutions exhibit very different open circuit voltage (Voc) when tin precursor has different oxidation state (Sn2+ vs Sn4 ). Here, the grain...
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.
The
reaction rates and selectivity of many metal-catalyzed reactions
depend on the size of the metal particles in the nanoscale range.
Primary amines are important platform molecules in the chemical industry.
In this work, the catalytic performance of nonsupported Ru nanoparticles
with sizes from 2 to 9 nm was investigated in direct amination of
octanol and other alcohols into primary amines in the presence of
ammonia. The 90% selectivity to octylamine was obtained over small
Ru nanoparticles (d = 2 nm) even at 92% conversion,
whereas for larger Ru nonsupported and supported nanoparticles, the
octylamine selectivity dropped as the octanol conversion approached
70–80%. The primary reaction of alcohol amination into octylamine
was found to be nearly a structure-insensitive reaction. The selectivity
to primary amine drops over large Ru particles at higher conversions,
because of the secondary highly structure-sensitive reaction of amine
self-coupling. Over small metal nanoparticles, amine self-coupling
is hindered, because of suppression of secondary imine hydrogenation.
Similar structure sensitivities of the reactions involved in alcohol
amination were observed for different substrates.
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