RESUMO
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 (V OC) 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 ËC, 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%.
RESUMO
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.
RESUMO
The growth in efficiency of earth-abundant kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells has slowed, due in part to the intrinsic limitations imposed by the band tailing attributed primarily to I-II antisite exchange. In this study, density functional theory simulations show that when Ag is substituted for Cu to form kesterite Ag2ZnSnSe4 (AZTSe), the I-II isolated antisite formation energy becomes 3.7 times greater than in CZTSSe, resulting in at least an order of magnitude reduction in I-II antisite density. Experimental evidence of an optoelectronically improved material is also provided. Comparison of the low-temperature photoluminescence (PL) structure of Cu(In,Ga)Se2 (CIGSe), CZTSSe, and AZTSe shows that AZTSe has a shallow defect structure with emission significantly closer to the band edge than CZTSe. Existence of suppressed band tailing is found in the proximity of the room-temperature PL peak of AZTSe to its measured band gap. The results are consistent with AZTSe being a promising alternative to CZTSSe and CIGSe for thin film photovoltaics.
