† Corresponding author. E-mail:
Project supported by the National Natural Science Foundation of China (Grant Nos. 51572132, 61674082, and 61774089), the National Key Research and Development Program of China (Grant No. 2018YFB1500202), the Tianjin Natural Science Foundation of Key Project of China (Grant Nos. 16JCZDJC30700 and 18JCZDJC31200), and the 111 Project, China (Grant No. B16027).
Cd-free kesterite structured solar cells are currently attracting attention because they are environmentally friendly. It is reported that Zn(O,S) can be used as a buffer layer in these solar cells. However, the band alignment is not clear and the carrier concentration of Zn(O,S) layer is low. In this study, the band alignment of the Zn(O,S)/Cu2ZnSnSe4 p–n junction solar cell and the effect of In2S3/Zn(O,S) double buffer layer are studied by numerically simulation with wxAMPS software. By optimizing the band gap structure between Zn(O,S) buffer layer and Cu2ZnSnSe4 absorber layer and enhancing the carrier concentration of Zn(O,S) layer, the device efficiency can be improved greatly. The value of CBO is in a range of 0 eV–0.4 eV for S/(S + O)
Kesterite structured Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) materials have received extensive attention due to their non-toxicity, large absorption coefficient (
Owing to these disadvantages, alternative buffer materials are used to replace the CdS buffer layer. Among them, Zn(O,S) is a promising alternative material due to its non-toxicity and large band gap which can be modified from 2.6 eV to 3.8 eV, depending on the S/(S + O) ratio in Zn(O,S).[13,14] Many groups have reported the kesterite structure-based device with Zn(O,S) serving as a buffer layer. Among them, Grenet et al. have reported that the barrier at the CZTSSe/Zn(O,S) interface decreased after light soaking treatment, and the device efficiency was increased to 5.8%.[15] Neuschitzer et al. optimized the band alignment between CZTSe absorber layer and Zn(O,S) buffer layer by changing the thiourea concentration in the CBD process. The device efficiency was increased up to 6.5% which was close to that of CdS reference device.[16] Recently, our group eliminated the secondary phases existing in the as-grown Zn(O,S) by sequential concentrated ammonium solution etching and low temperature annealing treatment. Finally, the Zn(O,S)/CZTSe efficiency was increased to 7.2% by our group recently.[17] However, we found that the band offset between Zn(O,S) and CZTSe is higher than 1 eV, which is very difficult for the carrier transport. After the temperature-dependent I–V study, we deduce that the carrier transport in such a system should be realized by a defect energy level close to Fermi level which acts as a shortcut for the carrier transport.
The performance of the Zn(O,S)/CZTSe device also suffers the low conductivity.[18,19] The efficiency of the device is seriously deteriorated with low buffer carrier concentration. The most commonly used method to enhance the carrier concentration is element doping. Many groups have improved the carrier concentration of the TCO by doping the group III elements like indium into ZnO.[20–23] Indium acts as a dopant since it has a similar atomic radius to Zn2+. It can substitute Zn2+ in ZnO to form
Kesterite structured solar cells with Zn(O,S) have made considerable progress. However, the study of detailed understanding of the CZTSe/Zn(O,S) is still rare. In this study, we investigate the band alignment between Zn(O,S) layer and CZTSe layer. The effect of the carrier concentration variation in the buffer on the performance of CZTSe solar cells is also studied. We find that double buffer layer In2S3/Zn(O,S) mainly increases the carrier concentration.
The devices are simulated by wxAMPS software, which is updated from the original AMPS program.[28] Based on the main physical principles of AMPS, the wxAMPS software induces two new tunneling models and improves the algorithm by combining the Newton method and the Gummel method. Compared with other simulation software, the wxAMPS provides a good stability and running speed, and is very suitable for simulating materials with defect densities, band tails.[29] The device parameters used in the simulation process are listed in Table
![]() | Table 1.
Device parameters used in simulation. . |
The band gap of Zn(O,S) can be adjusted from 2.6 eV to 3.8 eV by modifying the S/(S + O) ratio.[13,14] Sharbati S et al. reported that the band gap of the Zn(O,S) first decreases and then increases, and the value of the conduction band and the valence band both change with S fraction variety in the Zn(O,S).[30] The variation of electron affinity (
As the band gap and the electron affinity of Zn(O,S) vary with the S fraction,[32] the S/(S + O) ratio becomes a key factor to affect the conduction band offset (CBO) at the interface between CZTSe absorber layer and Zn(O,S) buffer layer.[31] The Zn(O,S) electron affinity tends to slide downward as the S fraction increases (fig.
Figure
The optimal band gap of Zn(O,S) simulation (2.8 eV) is larger than that of CdS (2.4 eV). Consequently, the absorption loss in the short-wavelength region of the visible spectrum is reduced by using the Zn(O,S) film to replace the traditional CdS buffer material, thus improving the short circuit current of the device. The EQE responses of the devices with different buffer layers (CdS layer and Zn(O,S) layer) are showed in Fig.
Figure
![]() | Fig. 6. Curves of (a) Jsc and (b) FF of Zn(O,S)/CZTSe solar cells versus Zn(O,S) layer thickness with different Zn(O,S) carrier concentrations. |
Similarly, we can see from Fig.
The In2S3/Zn(O,S) double buffer layer is selected for simulation. Obviously, In3+ ions will diffuse into Zn(O,S) buffer layer. As a consequence, the carrier concentration of Zn(O,S) is improved due to the dopant of the n-type
![]() | Fig. 8. Conduction band alignments of Zn(O,S)/CZTSe devices with different Zn(O,S) carrier concentrations. |
![]() | Table 2.
Performances of Zn(O,S)/CZTSe cells with different Zn(O,S) carrier concentrations. . |
Some In2S3 layers ineluctably remain on the surface of Zn(O,S)/CZTSe solar cell in experiment. The effect of residual In2S3 layers should be further considered. The band gap of In2S3 is tunable from 2.1 eV to 2.9 eV, which should be attributed to the variation of the temperature and the oxygen content doped into the In2S3 layer.[35–37] Furthermore, the electron affinity of In2S3 will change with the variation of band gap.[38] The relationship between the band gap and electron affinity is shown below.[38]
![]() | Table 3.
Performances of Zn(O,S)/In2S3/CZTSe devices with 2.7-eV band gap In2S3 layer. . |
Figure
![]() | Fig. 11. J–V curves of devices for ![]() ![]() ![]() ![]() |
![]() | Table 4.
Performances of devices for |
In summary, we have analyzed the performance of Zn(O,S)/CZTSe device from the perspective of band structure and carrier concentration by numerical simulation. The band alignment between Zn(O,S) layer and CZTSe layer is +0.2 eV and the carrier concentration of Zn(O,S) layer is improved by In2S3 doping. The efficiency of Zn(O,S)/CZTSe device is improved to 16.18%, when no In2S3 layer remains on CZTSe layer.
In this study, the Zn(O,S)/CZTSe solar cell performance is simulated and studied by using the wxAMPS software. To achieve the optimal performance, the S/(S + O) ratio in Zn(O,S), Zn(O,S) thickness, and carrier concentration are discussed. By numerical simulation, the optimum S fraction is about 0.7, here the value of CBO in the Zn(O,S)/CZTSe interface is about +0.2 eV. The CBO is in a range of 0 eV–0.4 eV as S/(S + O) =0.6–0.8 in Zn(O,S). Meanwhile, the In2S3/Zn(O,S) double buffer layer is innovatively induced into the CZTSe device. The carrier concentration of the Zn(O,S) layer is improved by employing the In2S3/Zn(O,S) double buffer layer on CZTSe absorber layer upon annealing treatment. The device efficiency increases to 16.18% when the carrier concentration of Zn(O,S) layer is improved without any remaining In2S3. The efficiency of Zn(O,S)/5 nm-In2S3/CZTSe and 5 nm-In2S3/Zn(O,S)/CZTSe devices decrease to 15.71% and 15.48%, respectively. However, they are still higher than that of device without In2S3 layer (14.93%). These promising results indicate that the performance of Zn(O,S)/CZTSe device has great potential improvement and they provide guidance for further study of CZTSe solar cells.
[1] | |
[2] | |
[3] | |
[4] | |
[5] | |
[6] | |
[7] | |
[8] | |
[9] | |
[10] | |
[11] | |
[12] | |
[13] | |
[14] | |
[15] | |
[16] | |
[17] | |
[18] | |
[19] | |
[20] | |
[21] | |
[22] | |
[23] | |
[24] | |
[25] | |
[26] | |
[27] | |
[28] | |
[29] | |
[30] | |
[31] | |
[32] | |
[33] | |
[34] | |
[35] | |
[36] | |
[37] | |
[38] |