Versatile and Low-Toxic Solution Approach to Binary, Ternary, and Quaternary Metal Sulfide Thin Films and Its Application in Cu₂ZnSn(S,Se)₄ Solar Cells

Abstract

We developed a versatile and environmentally friendly solution approach for the fabrication of a variety of metal sulfide nanocrystal thin films. Metal oxides, metal hydroxides, metal chlorides, metal acetates, and metal acetylacetonates can be used as the starting materials and dissolved in thioglycolic acid and ethanolamine, forming many types of metal–organic precursor solutions. High quality CdS, SnS, CuInS2, CuSbS2, Cu2ZnSnS4, Cu­(In0.7Ga0.3)­S2, and luminescent Ag-doped Zn x Cd1–x S nanocrystal thin films have been successfully prepared by spin-coating their corresponding metal precursor solutions. Cu2ZnSn­(S,Se)4 thin film solar cell with a power conversion efficiency of 6.83% has been realized by this versatile method.

Significantly Enhancing Grain Growth in Cu2ZnSn(S,Se)4 Absorber Layers by Insetting Sb2S3, CuSbS2, and NaSb5S8 Thin Films

“…The devices of CZTSSe, CZTSSe/Sb 2 S 3 , CZTSSe/CuSbS 2 , and CZTSSe/NaSb 5 S 8 solar cells were prepared using the standard procedures described in our previously published papers. 22,23 Characterizations. The XRD patterns were recorded using a Bruker D8 X-ray diffractometer.…”

“…28 More interestingly, Agrawal and co-workers indicated that the use of wurtzite-derived CZTS nanoparticles has the potential to remove the unsintered layer in kesterite CZTSSe solar cells. 29 For the CZTSSe solar cells fabricated by the nanocrystal-based ink method and the non-hydrazine molecular precursor solution approach, there is always a largegrain self-termination problem during the selenization processes, [15][16][17][18]22,23 which will lead to an undesirable smallgrained bottom layer; therefore, it is highly urgent to develop a low-cost and facile approach to overcome the fine-grained layers in selenized CZTSSe films. In this paper, we present a simple and powerful strategy to significantly enhance grain growth in CZTSSe absorber layers by insetting Sb 2 S 3 , CuSbS 2 , and NaSb 5 S 8 thin films.…”

Fabrication of Cu2ZnSn(S,Se)4photovoltaic devices with 10% efficiency by optimizing the annealing temperature of precursor films

“…Therefore, some low-toxic solvents have been adopted for fabricating CZTSSe lms, such as dimethyl sulfoxide (DMSO), 5,6 1,3-dimethyl-2-imidazolidinone (DMI) 7 and 2-methoxyethanol. [8][9][10] Besides, in order to stabilize the CZTSSe precursor system, some organic ligands (i.e. thioglycolic acid) are also introduced to coordinate to Cu/Zn/Sn atoms.…”

“…4(f) further shows that the CZTSSe lm has a bilayer structure as the most works reported. 9,22 Below the 800 nm-thick large grains, there is a ne crystal layer with a thickness of about 900 nm. The crystallinity of the selenized lms are further explored by grazing XRD.…”

Solution-Processed Cu2ZnSn(S,Se)4 Thin-Film Solar Cells Using Elemental Cu, Zn, Sn, S, and Se Powders as Source

“…However, as a result of the high toxicity and dangerous instability of explosible hydrazine, the non-hydrazine solvent is more desirable for practical application. Therefore, some non-hydrazine solvents, such as the mixtures of ethanol and water and amine-thiol mixture, have been tried presently to dissolve the metallic oxide or metal salt for preparing the CZTS precursor solution [26][27][28].…”