Search

The kesterite Cu2ZnSn(S,Se)4(CZTSSe) solar cells have shown a continuous rise in power conversion efficiencies in the past years. However, the encountered interfacial problems with respect to charge recombination and extraction losses at the CdS/CZTSSe heterojunction still hinder their further development. In this work, an additional plasmonic local electric field is imposed into the CdS/CZTSSe interface through the electrostatic assembly of a two-dimensional (2D) ordered Au@SiO2NP array onto an aminosilane-modified surface absorber. The interfacial electric properties are tuned by controlling the coverage particle distance, and the finite-difference time domain (FDTD) simulation demonstrates that the strong near-field enhancement mainly occurs near the p-n junction interface. It is shown that the imposed local electric field leads to interfacial electrostatic potential (Velec) augmentation and improves the charge extraction and recombination processes. These electric benefits enable remarkable improvements in open-circuit voltage (Voc) and short-circuit current (Jsc), leading to the cell efficiency being increased from 10.19 to 11.50%. This work highlights the dramatic role of the plasmonic local electric field and the use of the 2D Au@SiO2NP array to modify a surface absorber instead of the extensively used ion passivation, providing a new strategy for p-n junction engineering in kesterite photovoltaics.

Indium doping of cadmium sulfide (CdS) by chemical bath deposition (CBD) can be an efficient strategy to boost the CIGSSe efficiency. However, limited by the extremely low solubility of In2S3, it is difficult to increase the In doping contents and inhibit the band energy-level regulation for CdS through the traditional CBD process. In this work, we perform a novel CBD method to prepare an indium-doped CdS (In:CdS) buffer, in which the indium source is sequentially slowly added in the growing aqueous solution. In this process, the In ion concentration involved in the real-time deposition is significantly reduced. Thus, compact and uniform In:CdS with higher indium doping content is obtained. Indium doping can elevate the CdS conduction band edge and construct a more favorable spike band alignment with a CIGSSe absorber. Moreover, it introduces efficient carrier transport and reduced interface defect density. As a result, improved CIGSSe heterojunction quality is realized by utilizing In:CdS. Also, the solution-processed CIGSSe device with In:CdS as a buffer yields a high efficiency of 16.4%, with a high VOCof 670 mV and an FF of 75.3%.

Material crystallinity is the overriding factor in the determination of the photoelectric properties of absorber materials and the overall performance of the photovoltaic device. Nevertheless, in the Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic device, the bilayer or trilayer structure for the absorber has been broadly observed, which is generally harmful to the cell performance because the probability of photogenerated carrier recombination at grain boundaries significantly increased. Herein, our experiment reveals that the application of anions to a new family of (Cu,Ag)2ZnSn(S,Se)4(CAZTSSe) materials leads to an increase in grain size and crystallinity. It is inspiring that using acetate starting materials in the precursor solution, a uniform, compact, and pinhole-free CAZTS precursor film was obtained, and the smoothness of the films surpassed that of films fabricated from the oxide route. More importantly, the crystallization of the CAZTSSe film has been considerably enhanced after selenization, and large grains going through the entire absorber layer was successfully obtained. Additionally, it is observed that the Vocaccompanied by excellent crystallinity improved significantly due to the pronouncedly reduced carrier recombination loss at grain boundaries. As a consequence, the power conversion efficiency (PCE) of the CAZTSSe photovoltaic device is successfully increased from 10.35% (oxide route) to 11.32% (acetate route). Importantly, our work attests to the feasibility of tuning the crystallization of the CZTSSe film by simple chemistry.

The partial substitution of Cu+with Ag+into the host lattice of Cu2ZnSn(S,Se)4thin films can reduce the open-circuit voltage deficit (Voc,deficit) of Cu2ZnSn(S,Se)4(CZTSSe) solar cells. In this paper, elemental Cu, Ag, Zn, Sn, S, and Se powders were dissolved in solvent mixture of 1,2-ethanedithiol (edtH2) and 1,2-ethylenediamine (en) and used for the formation of (Cu1–xAgx)2ZnSn(S,Se)4(CAZTSSe) thin films with different Ag/(Ag + Cu) ratios. The key feature of this approach is that the impurity atoms can be absolutely excluded. Further results indicate that the variations of grain size, band gap, and depletion width of the CAZTSSe layer are generally determined by Ag substitution content. Benefiting from the Vocenhancement (∼50 mV), the power conversion efficiency is successfully increased from 7.39% (x= 0) to 10.36% (x= 3%), which is the highest efficiency of Ag substituted devices so far.

Cu2ZnSnSxSe4–x(CZTSSe) counter electrodes (CEs) in dye-sensitized solar cells (DSSCs) are commonly developed with porous structures, but their high surface area could also retard electron transport processes owing to the abundant grain boundaries. Herein, we employed a convenient solution method and a rapid heating process to prepare well crystalline CZTSSe CEs in DSSCs. The influence of crystallization of CZTSSe film on DSSCs performances was discussed in depth. The thermogravimetric analysis, phase morphology, conductivity, and electrochemical characteristics of CZTSSe films were performed. It is found that the rapid heating process is beneficial to the formation of well crystalline film with large grains. As the porosity and grain boundaries in the bulk film are dramatically reduced with the enhanced crystallization, the charge transport process is gradually improved. Using cyclic voltammogram and electrochemical impedance spectroscopy measurements, we propose that the accelerating charge transport is of great importance to the photovoltaic performances of DSSCs due to their superior electrocatalytic activities. As the highest cell efficiency was achieved, well crystalline CZTSSe is an efficient CE catalytic material.