Priscilla D. Antunez

Nanoscale Characterization of Back Surfaces and Interfaces in Thin-Film Kesterite Solar Cells

Combinations of sub 1 μm absorber films with high-work-function back surface contact layers are expected to induce large enough internal fields to overcome adverse effects of bulk defects on thin-film photovoltaic performance, particularly in earth-abundant kesterites. However, there are numerous experimental challenges involving back surface engineering, which includes exfoliation, thinning, and contact layer optimization. In the present study, a unique combination of nanocharacterization tools, including nano-Auger, Kelvin probe force microscopy (KPFM), and cryogenic focused ion beam measurements, are employed to gauge the possibility of surface potential modification in the absorber back surface via direct deposition of high-work-function metal oxides on exfoliated surfaces. Nano-Auger measurements showed large compositional nonuniformities on the exfoliated surfaces, which can be minimized by a brief bromine-methanol etching step. Cross-sectional nano-Auger and KPFM measurements on Au/MoO3/Cu2ZnSn(S,Se)4 (CZTSSe) showed an upward band bending as large as 400 meV within the CZTSSe layer, consistent with the high work function of MoO3, despite Au incorporation into the oxide layer. Density functional theory simulations of the atomic structure for bulk amorphous MoO3 demonstrated the presence of large voids within MoO3 enabling Au in-diffusion. With a less diffusive metal electrode such as Pt or Pd, upward band bending beyond this level is expected to be achieved.

Ultrathin high band gap solar cells with improved efficiencies from the world’s oldest photovoltaic material

Selenium was used in the first solid state solar cell in 1883 and gave early insights into the photoelectric effect that inspired Einstein’s Nobel Prize work; however, the latest efficiency milestone of 5.0% was more than 30 years ago. The recent surge of interest towards high-band gap absorbers for tandem applications led us to reconsider this attractive 1.95 eV material. Here, we show completely redesigned selenium devices with improved back and front interfaces optimized through combinatorial studies and demonstrate record open-circuit voltage (VOC) of 970 mV and efficiency of 6.5% under 1 Sun. In addition, Se devices are air-stable, non-toxic, and extremely simple to fabricate. The absorber layer is only 100 nm thick, and can be processed at 200 ˚C, allowing temperature compatibility with most bottom substrates or sub-cells. We analyze device limitations and find significant potential for further improvement making selenium an attractive high-band-gap absorber for multi-junction device applications.Wide band gap semiconductors are important for the development of tandem photovoltaics. By introducing buffer layers at the front and rear side of solar cells based on selenium; Todorov et al., reduce interface recombination losses to achieve photoconversion efficiencies of 6.5%.

Passivation and thickness control of highly efficient kesterite solar cells

Kesterite Cu2ZnSn(SxSe1−x)4 (CZTSSe) is an attractive photovoltaic absorber material because of its tunable bandgap, earth abundance, and low toxicity. However, efficiency and open circuit voltage remain significantly below theoretical limits. We recently showed that back-contact engineering with MoO3/Au on exfoliated vapor-deposited kesterite solar cells can improve device performance. Here, we demonstrate more promising results, which translate into high power conversion efficiencies of up to 12.2% for solution-deposited CZTSe with thicknesses as low as 1.1 μm. Time-resolved terahertz spectroscopy of exfoliated films showed significantly faster recombination at the back surface than at the front. When atomic layer deposited Al2O3 was used to passivate the exposed back surface of exfoliated films, front and back surfaces showed nearly identical recombination dynamics. After thermally depositing high work function MoO3 and reflective Au as the back contact on the Al2O3-passivated absorber, we obtained devices with efficiencies of up to 11.6%. Applying the same strategy of exfoliating working devices and engineering the back contact resulted in efficiencies of up to 12.2% for passivation with a 10 nm layer of Se instead of Al2O3. Further development of such passivation and back-contact engineering approaches may lead to higher efficiency devices with absorber thicknesses below 1 μm.

Optimization of Silver-alloying for improved photovoltaic properties of CZTSSe

Cu2ZnSn(SxSe1-x)4 (CZTSSe) photovoltaic devices are primarily limited by low open-circuit voltages, believed to be caused in part by disorder on the Cu/Zn sublattice. We show that band tailing in the absorber can be addressed by alloying Ag into CZTSSe to replace Cu. We fabricate thin films across the full alloy range of pure-Cu to pure-Ag and show that as Ag is alloyed into the CZTSe system, the gap between the PL and optical bandgap shrinks from ~110 meV for pure CZTSe, to 0 meV for the pure Ag compound. Improved device efficiencies up to 10.2% are achieved with low Ag-ACZTSe samples. Unlike CZTSSe champion devices the current record ACZTSe device appears to be limited by the interface rather than bulk defects. To achieve optimal efficiency, the annealing conditions were modified to accommodate the significantly lower melting point of the Ag-containing compound. The range of optimal temperatures across the Cu-Ag-alloy range are shared to accelerate improved device efficiencies.