Oki Gunawan

Thermally evaporated Cu2ZnSnS4 solar cells

High efficiency Cu2ZnSnS4 solar cells have been fabricated on glass substrates by thermal evaporation of Cu, Zn, Sn, and S. Solar cells with up to 6.8% efficiency were obtained with absorber layer thicknesses less than 1 μm and annealing times in the minutes. Detailed electrical analysis of the devices indicate that the performance of the devices is limited by high series resistance, a “double diode” behavior of the current voltage characteristics, and an open circuit voltage that is limited by a carrier recombination process with an activation energy below the band gap of the material.

Band tailing and efficiency limitation in kesterite solar cells

We demonstrate that a fundamental performance bottleneck for hydrazine processed kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells with efficiencies reaching above 11% can be the formation of band-edge tail states, which quantum efficiency and photoluminescence data indicate is roughly twice as severe as in higher-performing Cu(In,Ga)(S,Se)2 devices. Low temperature time-resolved photoluminescence data suggest that the enhanced tailing arises primarily from electrostatic potential fluctuations induced by strong compensation and facilitated by a lower CZTSSe dielectric constant. We discuss the implications of the band tails for the voltage deficit in these devices.

High Efficiency Cu2ZnSn(S,Se)4 Solar Cells by Applying a Double In2S3/CdS Emitter

High-efficiency Cu2ZnSn(S,Se)4 solar cells are reported by applying In2S3/CdS double emitters. This new structure offers a high doping concentration within the Cu2ZnSn(S,Se)4 solar cells, resulting in a substantial enhancement in open-circuit voltage. The 12.4% device is obtained with a record open-circuit voltage deficit of 593 mV.

Loss mechanisms in hydrazine-processed Cu2ZnSn(Se,S)4 solar cells

We present a device characterization study for hydrazine-processed kesterite Cu2ZnSn(Se,S)4 (CZTSSe) solar cells with a focus on pinpointing the main loss mechanisms limiting device efficiency. Temperature-dependent study and time-resolved photoluminescence spectroscopy on these cells, in comparison to analogous studies on a reference Cu(In,Ga)(Se,S)2 (CIGS) cell, reveal strong recombination loss at the CZTSSe/CdS interface, very low minority-carrier lifetimes, and high series resistance that diverges at low temperature. These findings help identify the key areas for improvement of these CZTSSe cells in the quest for a high-performance indium- and tellurium-free solar cell.

Band alignment at the Cu2ZnSn(SxSe1−x)4/CdS interface

Energy band alignments between CdS and Cu2ZnSn(SxSe1−x)4 (CZTSSe) grown via solution-based and vacuum-based deposition routes were studied as a function of the [S]/[S+Se] ratio with femtosecond laser ultraviolet photoelectron spectroscopy, photoluminescence, medium energy ion scattering, and secondary ion mass spectrometry. Band bending in the underlying CZTSSe layer was measured via pump/probe photovoltage shifts of the photoelectron spectra and offsets were determined with photoemission under flat band conditions. Increasing the S content of the CZTSSe films produces a valence edge shift to higher binding energy and increases the CZTSSe band gap. In all cases, the CdS conduction band offsets were spikes.

Low band gap liquid-processed CZTSe solar cell with 10.1% efficiency

A low band gap liquid-processed Cu2ZnSn(Se1−xSx)4 (CZTSSe) kesterite solar cell with x ≈ 0.03 is prepared from earth abundant metals, yielding 10.1% power conversion efficiency. This champion cell shows a band gap of 1.04 eV, higher minority-carrier lifetime, lower series resistance and lower Voc deficit compared to our previously reported higher band gap (Eg = 1.15 eV; x ≈ 0.4) cell with similar record efficiency. The ability to vary the CZTSSe band gap using sulfur content (i.e., varying x) facilitates the examination of factors limiting performance in the current generation of CZTSSe devices, as part of the thrust to achieve operational parity with CdTe and Cu(In,Ga)(S,Se)2 (CIGSSe) analogs.

Optical designs that improve the efficiency of Cu2ZnSn(S,Se)4 solar cells

We present an optical-design approach that improves the short-circuit current and efficiency of Cu2ZnSn(S,Se)4 (CZTSSe) solar cells by tuning the thickness of the upper-device layers in order to maximize transmission into the CZTSSe absorber. The design approach combines optical modeling of idealized planar devices with a semi-empirical approach for treating the impact of surface roughness. Experimentally, we demonstrate that the new device architecture — which emphasizes thinner CdS and transparent-conducting layers — increases short-circuit current by about 10% in champion-caliber devices. These improvements are directly realized in the power-conversion efficiencies of CZTSSe devices, resulting in a certified improvement in the overall record power-conversion efficiency for CZTSSe from 11.1% to 12.0%. We also report comparable improvements for devices with band gaps in the range of 1.1–1.3 eV.

Electronic properties of the Cu2ZnSn(Se,S)4 absorber layer in solar cells as revealed by admittance spectroscopy and related methods

Admittance spectra and drive-level-capacitance profiles of several high performance Cu2ZnSn(Se,S)4 (CZTSSe) solar cells with bandgap ∼1.0–1.5 eV are reported. In contrast to the case for Cu(In,Ga)(S,Se)2, the CZTSSe capacitance spectra exhibit a dielectric freeze out to the geometric capacitance plateau at moderately low frequencies and intermediate temperatures (120–200 K). These spectra reveal important information regarding the bulk properties of the CZTSSe films, such as the dielectric constant and a dominant acceptor with energy level of 0.13–0.2 eV depending on the bandgap. This deep acceptor leads to a carrier freeze out effect that quenches the CZTSSe fill factor and efficiency at low temperatures.

Prospects and performance limitations for Cu–Zn–Sn–S–Se photovoltaic technology

While cadmium telluride and copper–indium–gallium–sulfide–selenide (CIGSSe) solar cells have either already surpassed (for CdTe) or reached (for CIGSSe) the 1 GW yr−1 production level, highlighting the promise of these rapidly growing thin-film technologies, reliance on the heavy metal cadmium and scarce elements indium and tellurium has prompted concern about scalability towards the terawatt level. Despite recent advances in structurally related copper–zinc–tin–sulfide–selenide (CZTSSe) absorbers, in which indium from CIGSSe is replaced with more plentiful and lower cost zinc and tin, there is still a sizeable performance gap between the kesterite CZTSSe and the more mature CdTe and CIGSSe technologies. This review will discuss recent progress in the CZTSSe field, especially focusing on a direct comparison with analogous higher performing CIGSSe to probe the performance bottlenecks in Earth-abundant kesterite devices. Key limitations in the current generation of CZTSSe devices include a shortfall in open circuit voltage relative to the absorber band gap and secondarily a high series resistance, which contributes to a lower device fill factor. Understanding and addressing these performance issues should yield closer performance parity between CZTSSe and CdTe/CIGSSe absorbers and hopefully facilitate a successful launch of commercialization for the kesterite-based technology.

Perovskite-kesterite monolithic tandem solar cells with high open-circuit voltage

We report a monolithic tandem photovoltaic device with earth-abundant solution processed absorbers. Kesterite Cu2ZnSn(S,Se)4 and perovskite CH3NH3PbI3 solar cells were fabricated monolithically on a single substrate without layer transfer. The resulting devices exhibited a high open circuit voltage (Voc) of 1350 mV, close to the sum of single-absorber reference cells voltages and outperforms any monolithic tandem chalcogenide device (including Cu(In,Ga)Se2) reported to date. Ongoing optimization of several device elements including the severely limiting top contact electrode is expected to yield superior currents and efficiency. Importantly, our device architecture demonstrates the compatibility and synergistic potential of two of the most promising emerging photovoltaic materials and provides a path for optimization towards >20% efficiency.