Improvement of Performance of CZTSSe Solar Cells by the Synergistic Effect of Back Contact Modification and Ag Doping.

To improve the performance of Cu2ZnSn(S,Se)4 solar cells, a strategy is proposed to improve the quality of absorber and back interface simultaneously by substituting V-doped Mo (Mo:V) for a conventional Mo back electrode and incorporating Ag into the Cu2ZnSn(S,Se)4 (ACZTSSe) absorber in this work. Since p+-type V-doped MoSe2 (MoSe2:V) is formed in the site between the absorber and Mo:V during selenization, the conventional Mo/n-MoSe2 back contact is modified to Mo:V/p+-MoSe2:V, a back surface passivation field (BSPF) is established at the back interface, the band bending of MoSe2:V is downward and that of bottom of the absorber is upward. Further investigation reveals that the back contact modification and Ag doping have a synergistic effect on inhibiting carrier recombination, decreasing series resistance and increasing shunt resistance, thereby leading to the PCE of device without antireflection coating increased from 8.61 to 10.98%, which is larger than the sum of increase in PCE induced by Ag doping alone (8.61 to 9.66%) and back contact modification alone (8.61 to 9.63%). It is demonstrated that the synergistic effect stems mainly from the strengthened BSPF and the further reduced back contact barrier height. The former is due to the increased difference in work function (WF) between MoSe2:V and absorber induced by the reduced WF of the absorber after Ag doping and the raised WF of MoSe2:V after V doping. The latter is due to the downshifted valence band maximum of absorber after Ag doping. This work highlights the synergistic effect of back contact modification and Ag doping on improving the performance of CZTSSe solar cells and also provides an effective way to suppress carrier recombination.

Improvement of Efficiency in Kesterite Solar Cells by Intentionally Inserting a Thin MoS2 Layer into the Back Interface.

A Mo(S,Se)2 interfacial layer is formed inevitably and uncontrollably between the Mo electrode and Cu2ZnSn(S,Se)4 (CZTSSe) absorber during the selenization process, which significantly influences the performance of CZTSSe solar cells. In this work, an ultrathin MoS2 layer is intentionally inserted into Mo/CZTSSe to reduce the recombination and thus optimize the interface quality. It is revealed that the absorber exhibits a continuous and compact morphology with bigger grains and remarkably without pinholes across the surface or cross-sectional regions after MoS2 modification. Benefitting from this, the shunt resistance (RSh) of the device increased evidently from ∼395 to ∼634 Ω·cm2, and simultaneously, the reverse saturation current density (J0) realized an effective depression. As a result, the power conversion efficiency (PCE) of the MoS2-modified device reaches 9.64% via the optimization of the thickness of the MoS2 layer, indicating performance improvements with respect to the MoS2-free case. Furthermore, the main contribution to the performance improvement is derived and analyzed in detail from the increased RSh, decreased J0, and diode ideality factor. Our results suggest that the Mo/CZTSSe interface quality and performance of CZTSSe solar cells can be modulated and improved by appropriately designing and optimizing the thickness of the inserted MoS2 layer.

Modulation of Field-Effect Passivation at the Back Electrode Interface Enabling Efficient Kesterite-Type Cu2ZnSn(S,Se)4 Thin-Film Solar Cells.

For further efficiency improvement in kesterite-type Cu2ZnSn(S,Se)4 (CZTSSe) solar cells, it is essential to address the carrier recombination issue at the back electrode interface (BEI) caused by the undesirable built-in potential orientation toward an absorber as an n-MoSe2 interfacial layer formed. In this regard, back surface field (BSF) incorporation, i.e., field-effect passivation, shows promise for dealing with this issue due to its positive effect in decreasing recombination at the BEI. In this study, the BSF was realized with the p-type conduction transition in interfacial layer MoSe2 by incorporating Nb into the back electrode. The BSF width can be tuned via modulating the carrier concentration of the absorber, which has been demonstrated by capacitance-voltage characterization. A beyond 7% efficiency BSF-applied CZTSSe solar cell is prepared, and the effects of a tunable BSF and the mechanism underpinning device performance improvement have been investigated in detail. The wider BSF distribution in the absorber induces a decrease in reverse saturation current density (J0) due to the stronger BSF effect in suppressing BEI recombination. As a result, an accompanying increase in open-circuit voltage (VOC) and short-circuit current density (JSC) is achieved as compared to the BSF-free case. This study offers an alternative strategy to address the BEI recombination issue and also broadens the interface passivation research scope of potentially competitive kesterite solar cells.

Self-Organized Back Surface Field to Improve the Performance of Cu2ZnSn(S,Se)4 Solar Cells by Applying P-Type MoSe2:Nb to the Back Electrode Interface.

Cu2ZnSn(S,Se)4 (CZTSSe) thin-film solar cells have been encountering a bottleneck period since the champion power conversion efficiency (PCE) of 12.7% was achieved by Kim et al. in 2014. One of the critical factors that impede its further development is the relatively low open-circuit voltage (VOC) caused by serious interface carrier recombination. In this regard, back surface field (BSF) employment is a feasible strategy to address the VOC issue of CZTSSe solar cells to some extent. Here, we demonstrated a self-organized BSF introduced by prompting interfacial MoSe2 layer transition from inherent n-type to desirable p-type with Nb doping (p-MoSe2:Nb). The BSF application can significantly reduce the carrier recombination at the back electrode interface (BEI) and lower down the back contact barrier height. The PCE of the corresponding cell was improved from 4.72 to 7.15% because of the enhancement of VOC and fill factor, primarily stemming from the doubling aspects of increased shunt resistance (RSh), decreased series resistance (RS), and alleviative recombination velocity of the BEI induced by the BSF. Our results suggest that introducing a BSF fulfilled with p-MoSe2:Nb is a facile and promising route to improve the performance of CZTSSe thin-film solar cells.

Shallow Acceptor State in Mg-Doped CuAlO2 and Its Effect on Electrical and Optical Properties: An Experimental and First-Principles Study.

Shallow acceptor states in Mg-doped CuAlO2 and their effect on structural, electrical, and optical properties are investigated by combining first-principles calculations and experiments. First-principles calculations demonstrate that Mg substituting at the Al site in CuAlO2 plays the role of shallow acceptor and has a low formation energy, suggesting that Mg doping can increase hole concentration and improve the conductivity of CuAlO2. Hall effect measurements indicate that the hole concentration of the Mg-doped CuAlO2 thin film is 2 orders of magnitude higher than that of undoped CuAlO2. The best room temperature conductivity of 8.0 × 10-2 S/cm is obtained. A band gap widening is observed in the optical absorption spectra of Mg-doped CuAlO2, which is well supported by the results from first-principles electronic structure calculations.

Influencing Mechanism of the Selenization Temperature and Time on the Power Conversion Efficiency of Cu2ZnSn(S,Se)4-Based Solar Cells.

Cu2ZnSn(S,Se)4 (CZTSSe) films were deposited on the Mo-coated glass substrates, and the CZTSSe-based solar cells were successfully fabricated by a facile solution method and postselenization technique. The influencing mechanisms of the selenization temperature and time on the power conversion efficiency (PCE), short-circuit current density (Jsc), open-circuit voltage (Voc), and fill factor (FF) of the solar cell are systematically investigated by studying the change of the shunt conductance (Gsh), series resistance (Rs), diode ideal factor (n), and reversion saturation current density (J0) with structure and crystal quality of the CZTSSe film and CZTSSe/Mo interface selenized at various temperatures and times. It is found that a Mo(S1-x,Sex)2 (MSSe) layer with hexagonal structure exists at the CZTSSe/Mo interface at the temperature of 500 °C, and its thickness increases with increasing selenization temperature and time. The MSSe has a smaller effect on the Rs, but it has a larger influence on the Gsh, n, and J0. The PCE, Voc, and FF change dominantly with Gsh, n, and J0, while Jsc changes with Rs and Gsh, but not Rs. These results suggest that the effect of the selenization temperature and time on the PCE is dominantly contributed to the change of the CZTSSe/CdS p-n junction and CZTSSe/MSSe interface induced by variation of the quality of the CZTSSe film and thickness of MSSe in the selenization process. By optimizing the selenization temperature and time, the highest PCE of 7.48% is obtained.

A Protocol to Fabricate Nanostructured New Phase: B31-Type MnS Synthesized under High Pressure.

Synthesis of nanomaterials with target crystal structures, especially those new structures that cannot be crystallized in their bulk counterparts, is of considerable interest owing to their strongly structure-dependent properties. Here, we have successfully synthesized and identified new-phase nanocrystals (NCs) associated with orthorhombic MnP-type (B31) MnS by utilizing an effective high-pressure technique. It is particularly worth noting that the generated new structured MnS NCs were captured as expected by quenching the high-pressure phase to the ambient conditions at room temperature. Likewise, the commercially available bulk rocksalt (RS) MnS material underwent unambiguously a reversible phase transition when the pressure was released completely. First-principles calculations further supported that the B31-MnS was more energetically preferable than the RS one under high pressure, which can be plausibly interpreted by the structural buckling with respect to zigzagged arrangements within B31 unit cell. Our findings represent a significant step forward in a deeper understanding of the high-pressure phase diagram of MnS and even provide a promising strategy to prepare desired nanomaterials with new structures that do not exist in their bulk counterparts, thus greatly increasing the choice of materials for a variety of applications.

Alternative Spectral Photoresponse in a p-Cu2ZnSnS4/n-GaN Heterojunction Photodiode by Modulating Applied Voltage.

We report alternative visible and ultraviolet light response spectra in a p-Cu2ZnSnS4 (p-CZTS)/n-GaN heterojunction photodiode. A CZTS film was deposited on an n-GaN/sapphire substrate using a magnetron sputtering method. Current-voltage characteristic of the p-CZTS/n-GaN heterojunction photodiode showed a good rectifying behavior. The spectral response measurements indicate that the response wavelength of the photodiode can be tuned from ultraviolet to visible regions via applying zero and reverse bias. A band alignment at the interface of the p-CZTS/n-GaN heterojunction was proposed to interpret the spectral response of the device.