Low‐cost solution‐processed CdTe nanocrystal (NC) solar cells always suffer from a high interface energy barrier and unbalanced hole/electron transport as well as anisotropic atom diffusion on the CdTe surface due to the limited amount of hole/electron interface materials or the difficulty in interface processing. In this work, a novel strategy is first adopted with gradient electron transport layer (CdS/CdSe) modification in the cathode and a new crosslinkable hole transport polymer (P‐TPA) implantation in the anode. The carrier recombination at interfaces is greatly decreased and thus the carrier collection is increased. Moreover, the light harvesting is improved both in short and long wavelength regions, making Jsc and Voc increase simultaneously. A champion solar cell shows a very high power conversion efficiency of 9.2% and an outstanding Jsc of 25.31 mA cm−2, which are among the highest values for all solution‐processed CdTe NC solar cells with a superstrate structure, and the latter value is even higher than that of traditional thick CdTe thin‐film solar cells (2 µm) via the high temperature close space sublimation method. This work demonstrates that facile surface modifications in both the cathode and anode with stepped extraction and organic–inorganic hybridization are very promising in constructing next‐generation highly efficient NC photovoltaic devices.

CdTe nanocrystal (NC) solar cells have received much attention in recent years due to their low cost and environmentally friendly fabrication process. Nowadays, the back contact is still the key issue for further improving device performance. It is well known that, in the case of CdTe thin-film solar cells prepared with the close-spaced sublimation (CSS) method, Cu-doped CdTe can drastically decrease the series resistance of CdTe solar cells and result in high device performance. However, there are still few reports on solution-processed CdTe NC solar cells with Cu-doped back contact. In this work, ZnTe:Cu or Cu:Au back contact layer (buffer layer) was deposited on the CdTe NC thin film by thermal evaporation and devices with inverted structure of ITO/ZnO/CdSe/CdTe/ZnTe:Cu (or Cu)/Au were fabricated and investigated. It was found that, comparing to an Au or Cu:Au device, the incorporation of ZnTe:Cu as a back contact layer can improve the open circuit voltage (Voc) and fill factor (FF) due to an optimized band alignment, which results in enhanced power conversion efficiency (PCE). By carefully optimizing the treatment of the ZnTe:Cu film (altering the film thickness and annealing temperature), an excellent PCE of 6.38% was obtained, which showed a 21.06% improvement compared with a device without ZnTe:Cu layer (with a device structure of ITO/ZnO/CdSe/CdTe/Au).

Interface engineering has led to significant progress in solution-processed CdTe nanocrystal (NC) solar cells in recent years. High performance solar cells can be fabricated by introducing a hole transfer layer (HTL) between CdTe and a back contact electrode to reduce carrier recombination by forming interfacial dipole effect at the interface. Here, we report the usage of a commercial product 2,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (Spiro) as a hole transfer layer to facilitate the hole collecting for CdTe nanocrystal solar cells. It is found that heat treatment on the hole transfer layer has significant influence on the NC solar cells performance. The Jsc, Voc, and power conversion efficiency (PCE) of NC solar cells are simultaneously increased due to the decreased contact resistance and enhanced built-in electric field. We demonstrate solar cells that achieve a high PCE of 8.34% for solution-processed CdTe NC solar cells with an inverted structure by further optimizing the HTL annealing temperature, which is among the highest value in CdTe NC solar cells with the inverted structure.

Nanocrystal solar cells (NCs) allow for large scale solution processing under ambient conditions, permitting a promising approach for low-cost photovoltaic products. Although an up to 10% power conversion efficiency (PCE) has been realized with the development of device fabrication technologies, the open circuit voltage (Voc) of CdTe NC solar cells has stagnated below 0.7 V, which is significantly lower than most CdTe thin film solar cells fabricated by vacuum technology (around 0.8 V~0.9 V). To further improve the NC solar cells’ performance, an enhancement in the Voc towards 0.8–1.0 V is urgently required. Given the unique processing technologies and physical properties in CdTe NC, the design of an optimized band alignment and improved junction quality are important issues to obtain efficient solar cells coupled with high Voc. In this work, an efficient method was developed to improve the performance and Voc of solution-processed CdTe nanocrystal/TiO2 hetero-junction solar cells. A thin layer of solution-processed CdS NC film (~5 nm) as introduced into CdTe NC/TiO2 to construct hetero-junction solar cells with an optimized band alignment and p-n junction quality, which resulted in a low dark current density and reduced carrier recombination. As a result, devices with improved performance (5.16% compared to 2.63% for the control device) and a Voc as high as 0.83 V were obtained; this Voc value is a record for a solution-processed CdTe NC solar cell.

Achieving stable and low-resistance interfaces for hole transport layers with well-matched energy levels is crucial to maximize the performance of solution-processed CdTe nanocrystal (NC) based solar cells.