New Solution-Processed Surface Treatment to Improve the Photovoltaic Properties of Electrodeposited Cu(In,Ga)Se2 (CIGSe) Solar Cells.

The surface Ga content for a CIGSe absorber was closely related to variation in the open-circuit voltage (VOC), while it was generally low on a CIGSe surface fabricated by two-step selenization. In this work, a solution-processed surface treatment based on spin-coating GaCl3 solution onto a CIGSe surface was applied to increase the Ga content on the surface. XPS, XRD, Raman spectroscopy, and band gap extraction based on the external quantum efficiency response demonstrated that GaCl3 post deposition treatment (GaCl3-PDT) can be used to enhance the Ga content on the surface of a CIGSe absorber. Meanwhile, a solution-processed surface treatment with KSCN (KSCN-PDT) was employed to form a transmission barrier for holes by moving the valence band maximum downward and decreasing the interface recombination between the CdS and CIGSe layers. Admittance spectroscopy results revealed that deep defects were passivated by GaCl3-PDT or KSCN-PDT. By applying the combination of GaCl3-PDT and KSCN-PDT, a champion device was realized that exhibited an efficiency of 13.5% with an improved VOC of 610 mV. Comparing the efficiency of the untreated CIGSe solar cells (11.7%), the CIGSe device efficiency with GaCl3-PDT and KSCN-PDT exhibited 15% enhancement.

A Novel Metal Precursor Structure for Electrodepositing Ultrathin CIGSe Thin-Film Solar Cell with High Efficiency.

The two-step process of electrodeposition and selenization is one of the most effective methods for producing CIGSe and CZTSe solar cells at a low cost. However, it is difficult to prepare the ultrathin CIGSe absorber by electrodeposition due to the nonuniform deposition of Cu on the Mo substrate. In this study, Cu was deposited on a Sb film instead of a Mo film, and the 3D growth mode of Cu was changed. Uniform and smooth ultrathin Cu films were fabricated on the Sb film using a pulse frequency over a range from 1000 to 10,000 Hz and a pulse current density ranging from 31.25 to 62.5 mA/cm2. Owing to the improved uniformity of Cu/In/Ga films, the thickness of the CIGSe absorber was reduced from 2 to 0.36 µm with Sb incorporation. In addition, the effects of Sb-doping on the CIGSe absorbers and the device performance were investigated. The crystallinity of the CIGSe films was improved, and the interface recombination of the solar cells was reduced by Sb incorporation. Ultimately, CIGSe thin-film solar cells with efficiencies of 5.25 and 11.27% were obtained with CIGSe absorber thicknesses of 0.36 and 1.2 µm, respectively.

Formation of Cl-Doped ZnO Thin Films by a Cathodic Electrodeposition for Use as a Window Layer in CIGS Solar Cells.

Zinc oxide films that are prepared by radio frequency (RF) sputtering are widely used as window layers in copper indium gallium diselenide (CIGS) solar cells. To reduce their production cost, the electrodeposition method for preparing Cl-doped zinc oxide (ZnO:Cl), rather than sputtering, was studied. The electrodeposition parameters of injected current density and the pH of the electrolyte solution were studied. A moderate current density was used to yield high quality zinc oxides. The pH of the electrolyte greatly affected the formation of ZnO films. The pH value of the electrolyte that ensured that zinc oxides of high quality are obtained was close to seven. Electrodeposited ZnO:Cl films had higher transmittance than ZnO:Al films in the near-infrared region and so they can be used to improve the performance of solar cells. Our experiments revealed that the CIGS solar cells with electrodeposited ZnO:Cl films as a window layer were slightly more efficient than those with sputtered ZnO:Al films.

Modified Back Contact Interface of CZTSe Thin Film Solar Cells: Elimination of Double Layer Distribution in Absorber Layer.

Double layer distribution exists in Cu2SnZnSe4 (CZTSe) thin films prepared by selenizing the metallic precursors, which will degrade the back contact of Mo substrate to absorber layer and thus suppressing the performance of solar cell. In this work, the double-layer distribution of CZTSe film is eliminated entirely and the formation of MoSe2 interfacial layer is inhibited successfully. CZTSe film is prepared by selenizing the precursor deposited by electrodeposition method under Se and SnSe x mixed atmosphere. It is found that the insufficient reaction between ZnSe and Cu-Sn-Se phases in the bottom of the film is the reason why the double layer distribution of CZTSe film is formed. By increasing Sn content in the metallic precursor, thus making up the loss of Sn because of the decomposition of CZTSe and facilitate the diffusion of liquid Cu2Se, the double layer distribution is eliminated entirely. The crystallization of the formed thin film is dense and the grains go through the entire film without voids. And there is no obvious MoSe2 layer formed between CZTSe and Mo. As a consequence, the series resistance of the solar cell reduces significantly to 0.14 Ω cm2 and a CZTSe solar cell with efficiency of 7.2% is fabricated.

Effect of Sn Content in a CuSnZn Metal Precursor on Formation of MoSe2 Film during Selenization in Se+SnSe Vapor.

The preparation of Cu2ZnSnSe4 (CZTSe) thin films by the selenization of an electrodeposited copper-tin-zinc (CuSnZn) precursor with various Sn contents in low-pressure Se+SnSex vapor was studied. Scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) measurements revealed that the Sn content of the precursor that is used in selenization in a low-pressure Se+SnSex vapor atmosphere only slightly affects the elemental composition of the formed CZTSe films. However, the Sn content of the precursor significantly affects the grain size and surface morphology of CZTSe films. A metal precursor with a very Sn-poor composition produces CZTSe films with large grains and a rough surface, while a metal precursor with a very Sn-rich composition procures CZTSe films with small grains and a compact surface. X-ray diffraction (XRD) and SEM revealed that the metal precursor with a Sn-rich composition can grow a thicker MoSe2 thin film at CZTSe/Mo interface than one with a Sn-poor composition, possibly because excess Sn in the precursor may catalyze the formation of MoSe2 thin film. A CZTSe solar cell with an efficiency of 7.94%was realized by using an electrodeposited metal precursor with a Sn/Cu ratio of 0.5 in selenization in a low-pressure Se+SnSex vapor.

CZTSe solar cells prepared by electrodeposition of Cu/Sn/Zn stack layer followed by selenization at low Se pressure.

Cu2ZnSnSe4 (CZTSe) thin films are prepared by the electrodeposition of stack copper/tin/zinc (Cu/Sn/Zn) precursors, followed by selenization with a tin source at a substrate temperature of 530°C. Three selenization processes were performed herein to study the effects of the source of tin on the quality of CZTSe thin films that are formed at low Se pressure. Much elemental Sn is lost from CZTSe thin films during selenization without a source of tin. The loss of Sn from CZTSe thin films in selenization was suppressed herein using a tin source at 400°C (A2) or 530°C (A3). A copper-poor and zinc-rich CZTSe absorber layer with Cu/Sn, Zn/Sn, Cu/(Zn + Sn), and Zn/(Cu + Zn + Sn) with metallic element ratios of 1.86, 1.24, 0.83, and 0.3, respectively, was obtained in a selenization with a tin source at 530°C. The crystallized CZTSe thin film exhibited an increasingly (112)-preferred orientation at higher tin selenide (SnSe x ) partial pressure. The lack of any obvious Mo-Se phase-related diffraction peaks in the X-ray diffraction (XRD) diffraction patterns may have arisen from the low Se pressure in the selenization processes. The scanning electron microscope (SEM) images reveal a compact surface morphology and a moderate grain size. CZTSe solar cells with an efficiency of 4.81% were produced by the low-cost fabrication process that is elucidated herein.