Lithium-assisted synergistic engineering of charge transport both in GBs and GI for Ag-substituted Cu2ZnSn(S,Se)4 solar cells

Although silver(Ag) substitution offers several benefits in eliminating bulk defects and facilitating interface type inversion for Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic(PV) technology, its further development is still hindered by the fairly low electrical conductivity due to the significant decrease of acceptors amount.In this work, a versatile Li–Ag co-doping strategy is demonstrated to mitigate the poor electrical conductivity arising from Ag through direct incorporating Li via postdeposition treatment(PDT) on top of the Ag-substituted CZTSSe absorber. Depth characterizations demonstrate that Li incorporation increases ptype carrier concentration, improves the carrier collection within the bulk, reduces the defects energy level as well as inverts the electric field polarity at grain boundaries(GBs) for Ag-substituted CZTSSe system. Benefiting from this lithium-assisted complex engineering of electrical performance both in grain interior(GI) and GBs, the power conversion efficiency(PCE) is finally increased from 9.21% to 10.29%. This systematic study represents an effective way to overcome the challenges encountered in Ag substitution,and these findings support a new aspect that the synergistic effects of double cation dopant will further pave the way for the development of high efficiency kesterite PV technology.

Interfaces of high-efficiency kesterite Cu_2ZnSnS(e)_4 thin film solar cells

Cu2ZnSnS（e）4 （CZTS（e）） solar cells have attracted much attention due to the elemental abundance and the non- toxicity. However, the record efficiency of 12.6% for CuzZnSn（S,Se）4 （CZTSSe） solar cells is much lower than that of Cu（In,Ga）See （CIGS） solar cells. One crucial reason is the recombination at interfaces. In recent years, large amount inves- tigations have been done to analyze the interfacial problems and improve the interfacial properties via a variety of methods. This paper gives a review of progresses on interfaces of CZTS（e） solar cells, including： （i） the band alignment optimization at buffer/CZTS（e） interface, （ii） tailoring the thickness of MoS（e）2 interfacial layers between CZTS（e） absorber and Mo back contact, （iii） the passivation of rear interface, （iv） the passivation of front interface, and （v） the etching of secondary phases.

Precisely tuning Ge substitution for efficient solution-processed Cu_2ZnSn(S,Se)_4 solar cells

The kesterite Cu2ZnSn（S,Se）4 （CZTSSe） solar cells have yielded a prospective conversion efficiency among all thin- film photovoltaic technology. However, its further development is still hindered by the lower open-circuit voltage （Voc）, and the non-ideal bandgap of the absorber is an important factor affecting this issue. The substitution of Sn with Ge provides a unique ability to engineer the bandgap of the absorber film. Herein, a simple precursor solution approach was successfully developed to fabricate Cu2Zn（SnyGel_y）（SxSe~ x）4 （CZTGSSe） solar cells. By precisely adjusting the Ge content in a small range, the Voc and Jsc are enhanced simultaneously. Benefitting from the optimized bandgap and the maintained spike structure and light absorption, the 10% Ge/（Ge＋Sn） content device with a bandgap of approximately 1.1 eV yields the highest efficiency of 9.36%. This further indicates that a precisely controlled Ge content could further improve the cell performance for efficient CZTGSSe solar cells.

First-principles study on the alkali chalcogenide secondary compounds in Cu(In,Ga)Se_2 and Cu_2ZnSn(S,Se)_4 thin film solar cells

The beneficial effect of the alkali metals such as Na and K on the Cu（In.Ga）Se2 （CIGS） and Cu2ZnSn（S,Se）4 （CZTSSe） solar cells has been extensively investigated in the past two decades, however, in most of the studies the alkali metals were treated as dopants. Several recent studies have showed that the alkali metals may not only act as dopants but also form secondary phases in the absorber layer or on the surfaces of the films. Using the first-principles calculations, we screened out the most probable secondary phases of Na and K in CIGS and CZTSSe, and studied their electronic structures and optical properties. We found that all these alkali chalcogenide compounds have larger band gaps and lower VBM levels than CIGS and CZTSSe, because the existence of strong p-d coupling in CIS and CZTS pushes the valence band maximum （VBM） level up and reduces the band-gaps, while there is no such p-d coupling in these alkali chalcogenides. This band alignment repels the photo-generated holes from the secondary phases and prevents the electron-hole recombination. Moreover, the study on the optical properties of the secondary phases showed that the absorption coefficients of these alkali chalcogenides are much lower than those of CIGS and CZTSSe in the energy range of 0-3.4eV, which means that the alkali chalcogenides may not influence the absorption of solar light. Since the alkali metal dopants can passivate the grain boundaries and increase the hole carrier concentration, and meanwhile their related secondary phases have innocuous effect on the optical absorption and band alignment, we can understand why the alkali metal dopants can improve the CIGS and CZTSSe solar cell performance.

Theoretical study on the kesterite solar cells based on Cu_2ZnSn(S,Se)_4 and related photovoltaic semiconductors

The kesterite thin film solar cells based on the quaternary Cu2ZnSnS4 and Cu2ZnSnSe4 and their alloys Cu2ZnSn（S,Se）4 have been considered as environment-friendly and non-toxic alternatives to the currently commercialized CdTe and Cu（In,Ga）Se2 thin film solar cells. From the theoretical point of view, we will review how the group I2-II-IV-VI4 quaternary compound semiconductors are derived from the binary CdTe and the ternary CuInSe2 or CuGaSe2 through the cation mutation, and how the crystal structure and electronic band structure evolve as the component elements change. The increased structural and chemical freedom in these quaternary semiconductors opens up new possibility for the tailoring of material properties and design of new light-absorber semiconductors. However, the increased freedom also makes the development of high-efficiency solar cells more challenging because much more intrinsic point defects, secondary phases, surfaces, and grain-boundaries can exist in the thin films and influence the photovoltaic performance in a way different from that in the conventional CdTe and Cu（In,Ga）Se2 solar cells. The experimental characterization of the properties of defects, secondary phase, and grain-boundaries is currently not very efficient and direct, especially for these quaternary compounds. First-principles calculations have been successfully used in the past decade for studying these properties. Here we will review the theoretical progress in the study of the mixed-cation and mixed-anion alloys of the group I2-II-IV- VI4 semiconductors, defects, alkaline dopants, and grain boundaries, which provided very important information for the optimization of the kesterite solar cell performance.

Impact of Cu-rich growth on the Cu2ZnSnSe4 surface morphology and related solar cells behavior

Inorderto study the influence ofCu-rich growth on the performance ofthe Cu2ZnSnSe4 （CZTSe）thin film solar cells, a multi-stage co-evaporation process is applied. The CZTSe films are grown at a lower substrate temperature to reduce the existence time of Cux Sey at the first period caused by the volatility of SnSex. This study examines the surface morphology and device performance in Cu-rich growth and close-to-stoichiometric growth. Although the grain size of Cu-rich growth film increases a little, the difference was not dramatic as the results of CIGS reported previously. A model based on the grain boundary migration theory is proposed to explain the experimental results. The mechanisms of Cu-rich growth between CZTSe and CIGS might be different.

Cu2ZnSn（S,Se）4 thin film solar cells fabricated with benign solvents

Cu2ZnSn（S,Se）4 （CZTSSe） is considered as the promising absorbing layer materials for solar cells due to its earth-abundant constituents and excellent semiconductor properties. Through solution-processing, such as various printing methods, the fabrication of high perfor- mance CZTSSe solar cell could be applied to mass production with extremely low manufacturing cost and high yield speed. To better fulfill this goal, environmentalfriendly inks/solutions are optimum for further reducing the capital investment on instrument, personnel and environmental safety. In this review, we summarized the recent development of CZTSSe thin films solar cells fabricated with benign solvents, such as water and ethanol. The disperse system can be classified to the true solution （consisting of molecules） and the colloidal suspension （consisting ofnanoparticles）.Three strategies for stabilization （i.e., physical method, chemical capping and self- stabilization） are proposed to prepare homogeneous and stable colloidal nanoinks. The one-pot self-stabilization method stands as an optimum route for preparing benign inks for its low impurity involvement and simple procedure. As-prepared CZTSSe inks would be deposited onto substrates to form thin films through spin-coating, spraying, electrodeposition or successive ionic layer adsorption and reaction （SILAR） method, followed by annealing in a chalcogen （S- or Se-containing） atmosphere to fabricate absorber. The efficiency of CZTSSe solar cell fabricated with benign solvents can also be enhanced by constituent adjustments, doping, surface treatments and blocking layers modifications, etc., and the deeper research will promise it a comparable performance to the non- benign CZTSSe systems.

(Ag,Cu)_(2)ZnSn(S,Se)_(4)太阳能电池的制备及表征

采用简单的溶胶-凝胶法制备出高质量的(Ag,Cu)_(2)ZnSn(S,Se)_(4)(ACZTSSe)薄膜.利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、紫外-可见分光光度计(UV-Vis)等研究了ACZTSSe薄膜的物理化学性质.实验结果表明,在Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)吸收层中掺杂Ag后薄膜可以获得较高的迁移率和光电转换效率(PCE).与CZTSSe太阳能电池相比,观察到8%-(Ag,Cu)_(2)ZnSn(S,Se)_(4)(8%-ACZTSSe)太阳能电池的开路电压(V_(oc))增加了100 mV,PCE也从2.31%增加到4.33%.因此,在CZTSSe层掺杂Ag不仅是一种可以获得具有较高的V_(oc)和PCE的CZTSSe基太阳能电池的方法,还是一种可以促进晶粒的生长、提高薄膜质量的途径.

Influence of selenium evaporation temperature on the structure of Cu_2ZnSnSe_4 thin film deposited by a co-evaporation process

Cu2ZnSnSe4 （CZTSe） thin film solar cells have been fabricated using a one-step co-evaporation technique. The structural properties of polycrystalline CZTSe films deposited at different selenium evaporation temperatures （TSe） have been investigated using X-ray diffraction spectra, scanning electron microscopy, and atomic force microscopy. A relationship between TSe and the secondary phases deposited in the initial stage is established to explain the experimental observations. The Se flux is not necessarily increased too much to reduce Sn loss and the consumption of Se during fabrication could also be reduced. The best solar cell, with an efficiency of 2.32%, was obtained at a medium Tse of 230 ℃ （active area 0.34 cm2）.