(Invited) Engineering of Nickel Oxide Hole Transport Layer for Inverted Perovskite Solar Cells
Authors: Shibayama Naoyuki , Ito Seigo 
Published: February 2020

Introduction

The NiOx layer is actively used as hole extraction layer for inverted structure perovskite solar cells. However, clear guidelines on NiOx chemical composition, manufacturing methods, energy levels, and the hole-transport process remain unclear.
In this conference, high-density NiOx layers with various manufacturing temperatures are produced with Nickel acetylacetonate using the SPD method in order to improve the performances of inverted perovskite solar cells. The chemical composition of the NiOx is investigated using XPS, and GIXRD. Furthermore, the influence of Na+ ions in the valence band of the NiOx layer is investigated by vacuum ultraviolet photoelectron spectroscopy using synchrotron radiation. The results showed that the conversion efficiency of the perovskite solar cell is high as the crystallite size of NiOx is large. The highest perovskite solar cell conversion efficiency was obtained at a NiOx layer production temperature of 550 °C. Inverted perovskite solar cells were fabricated with over 16.1% conversion efficiency.

Conversion efficiency of solar cell

The conversion efficiencies of the perovskite solar cells using NiOx films with various deposition temperatures are summarized in Table 1. The perovskite solar cells conversion efficiency increased along with the NiOx layer production temperature to 550 and 600 °C; however, it decreased slightly when the temperature increased further to 600 °C. As a result, the perovskite solar cell conversion efficiency reached its peak when the NiOx layer production temperature was 500 °C. To highlight the performance change, we herein investigated the composition, structure and the band state of the NiOx layers.

Influence of valence band and valence of Ni ion of the NiOx layers

To investigate the states of the regions near the edges of the valence bands of the NiOx layers, PES measurements were carried out with a BL-07B at the NewSUBARU synchrotron radiation facility, and the results are shown in Figure 1. The regions near the edges of the valence bands of the NiOx correspond to Ni 3d (label A), O 2p (label B), and the charge transfer transition from an O 2p level to Ni 3d photoionization (label C). From the PES measurement results, the region (around 4-5 eV) corresponding to O 2p was stronger at 300 and 600 °C than at 500 °C. This is because the influence of the O 2p orbital increased because the proportion of oxygen in NiOx increased owing to the loss of Ni ions. Although the ratio of Ni2+ to Ni3+ ions affects the energy levels in the vicinity of the HOMO, a change in these energy levels does not contribute to hole extraction in perovskite solar cells. From these results, it was found that the valence of the Ni ions has little influence on the performance of the solar cells.

Crystal analysis of the NiOx layers

Both the structures and crystallite sizes of the thin NiOx films formed by SPD were investigated via GIXRD, as shown in Figure 2. The five peaks that appeared at 2θ values of approximately 37.6° 43.6°, 63.3°, 75.6°, and 79.6° were assigned to the 111, 200, 220, 311, and 222 planes, respectively, and then attributed to the randomly oriented NiOx crystal. At 250 °C, no diffraction peaks were observed because the NiOx film did not crystallise. This implies that crystallised NiOx films formed with annealing temperatures above 300 °C.
The NiOx crystallite sizes were calculated from the intensities of the 200 peaks using the Scherrer equation, and the results are shown in Figure 1, which indicates that their sizes increased with increasing SPD temperatures. The size of a NiOx crystallite and the tendency of conversion efficiency were consistent, except at 550 and 600 °C, where the FTO layer broke beyond the glass transition point. In other words, as a guideline for manufacturing high-performance inverted perovskite solar cells, it is important to enlarge the crystallites in the NiOx film.

Conclusions

We demonstrated that it is related to the NiOx crystallite size and the conversion efficiency of the perovskite solar cells, which can be used as a guideline to achieve high performance. The highest perovskite solar cell conversion efficiency was obtained at a NiOx layer production temperature of 500 °C. In the inverse perovskite solar cell, the conversion efficiency exceeded 16.1%, and hysteresis was not observed. Moreover, the measurements of the valence band using synchrotron radiation indicated that the ratio of Ni2+ to Ni+3 had little effect on the solar cell performance. This is an important guideline for improving the performance of perovskite solar cells.

Acknowledgement

This work was supported by New energy and industrial Technology Development Organization (NEDO), Japan.