(Invited) Engineering of Nickel Oxide Hole Transport Layer for Inverted Perovskite Solar Cells

As a low-cost, high stable hole transport material, nickel oxide has been widely used in inverted structure perovskite solar cells in recent years. By far, the most common method of preparing nickel oxide hole transport layers is spin-coating pre-prepared nickel oxide nanoparticles (NiO<sub><i>x</i></sub> NPs), which puts forward high requirement for the particle sizes and solution processing capabilities of NiO<sub><i>x</i></sub> NPs. In this work, the sizes of NiO<sub><i>x</i></sub> NPs are precisely controlled by adjusting the pH value of the system in the synthesis process, and high-quality nickel oxide hole transport layers are then prepared. The experimental results exhibit that the NiO<i>x</i> NPs with sizes of 5–10 nm are obtained at a pH value in a range of 9.5–9.8. More interestingly, the obtained NiO<sub><i>x</i></sub> NPs have good dispersion stability and can achieve long-term dispersion in aqueous solution. Furthermore, the structural composition analysis of NiO<sub><i>x</i></sub> NPs shows that the pH value of the synthesis system does not have a significant effect on the material structure nor composition of the NiO<sub><i>x</i></sub> NP. Surface morphological analysis shows that the NiO<sub><i>x</i></sub> film prepared by the pH-controlled NiO<sub><i>x</i></sub> NPs is rather dense and particularly flat with small surface roughness. It is also found that the film exhibits good hole extraction capability. We also fabricate an inverted perovskite solar cell based on the NiO<sub><i>x</i></sub> film. The device structure is ITO/NiO<sub><i>x</i></sub>/CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub>/PC61BM/Bphen/Ag. It yields a good photovoltaic conversion efficiency (17.39%). In addition, the device is almost hysteresis-free. Our experimental results exhibit that the performance of perovskite solar cells can be effectively improved by precisely controlling the sizes of NiO<sub><i>x</i></sub> NPs through pH values. Our work is expected to facilitate the development of NiO<sub><i>x</i></sub>-based perovskite solar cells.

As a low-cost, high stable hole transport material, nickel oxide has been widely used in inverted structure perovskite solar cells in recent years. By far, the most common method of preparing nickel oxide hole transport layers is spin-coating pre-prepared nickel oxide nanoparticles (NiO<sub><i>x</i></sub> NPs), which puts forward high requirement for the particle sizes and solution processing capabilities of NiO<sub><i>x</i></sub> NPs. In this work, the sizes of NiO<sub><i>x</i></sub> NPs are precisely controlled by adjusting the pH value of the system in the synthesis process, and high-quality nickel oxide hole transport layers are then prepared. The experimental results exhibit that the NiO<i><sub>x</sub></i> NPs with sizes of 5–10 nm are obtained at a pH value in a range of 9.5–9.8. More interestingly, the obtained NiO<sub><i>x</i></sub> NPs have good dispersion stability and can achieve long-term dispersion in aqueous solution. Furthermore, the structural composition analysis of NiO<sub><i>x</i></sub> NPs shows that the pH value of the synthesis system does not have a significant effect on the material structure nor composition of the NiO<sub><i>x</i></sub> NP. Surface morphological analysis shows that the NiO<sub><i>x</i></sub> film prepared by the pH-controlled NiO<sub><i>x</i></sub> NPs is rather dense and particularly flat with small surface roughness. It is also found that the film exhibits good hole extraction capability. We also fabricate an inverted perovskite solar cell based on the NiO<sub><i>x</i></sub> film. The device structure is ITO/NiO<sub><i>x</i></sub>/CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub>/PC<sub>61</sub>BM/Bphen/Ag. It yields a good photovoltaic conversion efficiency (17.39%). In addition, the device is almost hysteresis-free. Our experimental results exhibit that the performance of perovskite solar cells can be effectively improved by precisely controlling the sizes of NiO<sub><i>x</i></sub> NPs through pH values. Our work is expected to facilitate the development of NiO<sub><i>x</i></sub>-based perovskite solar cells.

This paper presents the effect of a composite poly(3,4-ethylenedioxythiophene) polystyrene sulfonate PEDOT:PSS and copper-doped nickel oxide (Cu:NiOx) hole transport layer (HTL) on the performance of perovskite solar cells (PSCs). Thin films of Cu:NiOx were spin-coated onto fluorine-doped tin oxide (FTO) glass substrates using a blend of nickel acetate tetrahydrate, 2-methoxyethanol and monoethanolamine (MEA) and copper acetate monohydrate. The prepared solution was stirred at 65 °C for 4 h and spin-coated onto the FTO substrates at 3000 rpm for 30 s in a nitrogen glovebox. The Cu:NiOx/FTO/glass structure was then annealed in air at 400 °C for 30 min. A mixture of PEDOT:PSS and isopropyl alcohol (IPA) (in 1:0.05 wt%) was spun onto the Cu:NiOx/FTO/glass substrate at 4000 rpm for 60 s. The multilayer structure was annealed at 130 °C for 15 min. Subsequently, the perovskite precursor (0.95 M) of methylammonium iodide (MAI) to lead acetate trihydrate (Pb(OAc)2·3H2O) was spin-coated at 4000 rpm for 200 s and thermally annealed at 80 °C for 12 min. The inverted planar perovskite solar cells were then fabricated by the deposition of a photoactive layer (CH3NH3PbI3), [6,6]-phenyl C61-butyric acid methyl ester (PCBM), and a Ag electrode. The mechanical behavior of the device during the fabrication of the Cu:NiOx HTL was modeled with finite element simulations using Abaqus/Complete Abaqus Environment CAE. The results show that incorporating Cu:NiOx into the PSC device improves its density–voltage (J–V) behavior, giving an enhanced photoconversion efficiency (PCE) of ~12.8% from ~9.8% and ~11.5% when PEDOT:PSS-only and Cu:NiOx-only are fabricated, respectively. The short circuit current density Jsc for the 0.1 M Cu:NiOx and 0.2 M Cu:NiOx-based devices increased by 18% and 9%, respectively, due to the increase in the electrical conductivity of the Cu:NiOx which provides room for more charges to be extracted out of the absorber layer. The increases in the PCEs were due to the copper-doped nickel oxide blend with the PEDOT:PSS which enhanced the exciton density and charge transport efficiency leading to higher electrical conductivity. The results indicate that the devices with the copper-doped nickel oxide hole transport layer (HTL) are slower to degrade compared with the PEDOT:PSS-only-based HTL. The finite element analyses show that the Cu:NiOx layer would not extensively deform the device, leading to improved stability and enhanced performance. The implications of the results are discussed for the design of low-temperature solution-processed PSCs with copper-doped nickel oxide composite HTLs.

The wx-AMPS simulation software is used to model and simulate the Schottky perovskite thin film solar cells. The front and back electrodes with different work functions are applied to the Schottky perovskite solar cells to study the effect of band structure on the performance of solar cells. The results show that in a range from 3.8 to 4.4 eV, as the work function of the front electrode decreases, the conversion efficiency of the Schottky solar cells gradually increases. When the work function of the front electrode is low, the electric field strength is large, which facilitates the transport of carriers in the light-absorbing layer of the perovskite and reduces the carrier recombination rate of the perovskite layer. In addition, the recombination ratio of the light absorbing layer is reduced due to the increase of the electric field strength, and the parallel resistance is increased to a certain extent thereby increasing the FF and improving the output efficiency of the battery. At the same time, when the current electrode work function is maintained at 3.8 eV, in a range from 4.3 to 5.5 eV, the higher the work function of the back electrode, the greater the conversion efficiency of the Schottky solar cell is. This conduces to the band alignment in contact between perovskite and back electrode. Under the premise that the common electrode Au is used as a back electrode, the work function of the front electrode is 3.8 eV and the conversion efficiency of the Schottky perovskite solar cell is 17.93%. In addition, by using the optimized front and rear contact electrodes, the quality of the perovskite layer material, thus the performance of the solar cell can be further improved. Doping till a certain concentration and removing the defects of the perovskite layer, the conversion efficiency of the solar cell with a thickness of 500 nm can be increased from 17.93% to 20.1%. The simulation results show that the Schottky perovskite thin film solar cells can obtain excellent performance with simple device structure and have great potential applications.

Lead-free tin perovskite solar cells

Room-temperature processed plasma activated nickel oxide film for wide-bandgap perovskite solar cells

Enhanced performance of CsPbBr3 perovskite solar cells by reducing the conduction band offsets via a Sr-modified TiO2 layer

The continuing increase of the efficiency of perovskite solar cells has pushed the internal quantum efficiency approaching 100%, which means the light-to-carrier and then the following carrier transportation and extraction are no longer limiting factors in photoelectric conversion efficiency of perovskite solar cells. However, the optimal efficiency is still far lower than the Shockley-Queisser efficiency limit, especially for those inverted perovskite solar cells, indicating that a significant fraction of light does not transmit into the active perovskite layer to be absorbed there. Here, a planar inverted perovskite solar cell (ITO/PTAA/perovskite/PC61BM/bathocuproine (BCP)/Ag) is chosen as an example, and we show that its external quantum efficiency (EQE) can be significantly improved by simply texturing the poly[bis (4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) layer. By washing the film prepared from a mixed polymer solution of PTAA and polystyrene (PS), a textured PTAA/perovskite interface is introduced on the light-input side of perovskite to inhibit internal optical reflection. The reduction of optical loss by this simple texture method increases the EQE and then the photocurrent of the ITO/PTAA/perovskite/PC61BM/BCP/Ag device with the magnitude of about 10%. At the same time, this textured PTAA benefits the band edge absorption in this planar solar cell. The large increase of the short-circuit current together with the increase of fill factor pushes the efficiency of this inverted perovskite solar cell from 18.3% up to an efficiency over 20.8%. By using an antireflection coating on glass to let more light into the device, the efficiency is further improved to 21.6%, further demonstrating the importance of light management in perovskite solar cells.

In recent years, organic-inorganic hybrid perovskite solar cells have aroused the interest of a large number of researchers due to the advantages of large optical absorption coefficient, tunable bandgap and easy fabrication. Recently, the power conversion efficiency of organic-inorganic hybrid perovskite solar cells has been enhanced to more than 23% in laboratory. In solution processed perovskite solar cells, perovskite and charge transport layer are stacked together, due to the different crystallization rates leading to lattice mismatch near the surface region of perovskite film, resulting in a lot of interface defects, especially at the interface between perovskite and charge transport layer. What is more, the photo-induced free carriers must transfer across the interfaces to be collected. But the defects near the interface can trap photogeneration electrons, thus reducing the carrier lifetime and causing the charges to be recombined, which greatly influence the performance and stability of perovskite solar cells. Therefore, reducing and passivating these defects is critical for obtaining the high performance perovskite solar cells. Now, there have been made tremendous efforts devoting to advancing passivation techniques, such as doping and surface modification, for high efficiency perovskite solar cell with improved stability and reduced hysteresis. These approaches also contribute to improving the energy band alignment between carrier transport layers and perovskite absorber improving device performance, or resistance moisture to enhance device stability. In this review we mainly introduce the formation and the effect of defects on perovskite solar cells, analyze the mechanism for passivating the interfacial defects between charge transport layer and perovskite photo absorption layer for different materials, compare the effects of different passivation materials on the photovoltaic performance of perovskite solar cells, and summarize the role of these materials in passivating the defects. Finally we discuss the research trend and development direction of passivation defects in perovskite solar cells.

Enhancing efficiency and stability of inverted structure perovskite solar cells with fullerene C60 doped PC61BM electron transport layer

Organometal hybrid perovskite material has emerged as an attractive competitor in the field of photovoltaics due to its promising potential of low-cost and high-efficiency photovoltaic applications. Although organometal halide perovskite solar cell shows great potential to meet future energy needs, the degradation raises serious questions about its commercialization viability. At present, the stability of perovskite solar cells has been studied in various environmental conditions. Nonetheless, an understanding of the degradation and its performance of CH3NH3PbI3-xClx perovskite solar cell is limited. Herein, we report the mechanical and structural degradation of CH3NH3PbI3-xClx perovskite films at room temperature as a function of time and thermal instability of perovskite solar cells during the heating and cooling processes. For mechanical degradation measurement, we used nanoindentation for CH3NH3PbI3-xClx perovskite films fabricated on FTO/PEDOT:PSS substrate. The hardness and elastic modulus of perovskite films were measured as a function of time. In addition, the mechanical degradation of perovskite thin films was correlated with X-ray diffraction, steady-state and time-resolved photoluminescence (PL). We also investigated the thermal instability of perovskite thin films and the irreversible performance of perovskite solar cells. Particularly, the irreversible performance of CH3NH3PbI3-xClx was analyzed by measuring the development of crystallinity, charge trapping/detrapping, trap depth, and PbI- phase while varying the temperature of perovskite films and solar cells between room temperature and 82 °C. Surprisingly, we found that the degradation of both perovskite films and solar cells occurred at ~70°C. Remarkably, even after the perovskite solar cell temperature cooled down to room temperature, the performance of solar cells continuously degraded. The underlying mechanism of irreversibly degraded performance of perovskite films and solar cells were explained in terms of the development of phase separation, increased trapping rates and deep trap depth of defect states of perovskite films.

Decoupling the effects of defects on efficiency and stability through phosphonates in stable halide perovskite solar cells

Cathode interfacial materials (CIMs) are important to boost the device performance of perovskite solar cells (PVSCs). Herein, we reported two perylenediimide oligomers, PDI-D and PDI-T, which could play the role of an efficient multifunctional cathode interfacial layer (CIL) in the inverted PVSC. With the combinations of good orthogonal solvent solubility, interfacial dipole, self-doping, and interfacial doping in the PDI-T molecule, the contact barrier between the electron-transport layer and the metal cathode is obviously reduced. Adding to the induced good conductivity, the corresponding inverted PVSC with PDI-T as a CIL shows a promising power conversion efficiency (PCE) of 21.06% with simultaneously enhanced open-circuit voltage, current density, and fill factor. Moreover, thickness insensitivity of PDI-T CIL to PCE is also observed. Furthermore, good stability with a PCE loss of only 3.3% after 1032 h is also obtained. As such, it is concluded that the multifunctionalities from a single molecule in the CIM provide a new molecular insight for pursuing high-performance and stable inverted PVSCs.

Two-dimensional Bi2OS2 doping improves the performance and stability of perovskite solar cells

To overcome the fundamental limitation of the low power conversion efficiency (PCE) of perovskite solar cells (PSCs) incorporated with a magnetron sputtered p-type NiOx as a hole transport layer (HTL), the effects of various sputtering conditions of the NiOx layer on MAPbI3 PSC performance are comprehensively investigated. Based on the stoichiometry control of the bulk and surface of the NiOx layer by controlling oxygen partial pressure during the sputtering process, it is found that PSCs with a sputtered NiOx HTL prepared in an Ar atmosphere exhibits higher PCEs than those of devices with an NiOx HTL conventionally grown under Ar/O2 mixed conditions. To elucidate the working principle, influences of defects in the NiOx layer grown under different O2 partial pressure conditions are thoroughly investigated. The sputtered NiOx films under pure Ar conditions with a low Ni3+/Ni2+ ratio show high hole extraction ability due to moderate hole conductivity, high optical transparency, and the improved band alignment with a MAPbI3 perovskite layer. In particular, the NiOx film sputtered in pure Ar ambience results in higher photovoltaic performance with a negligible hysteresis behavior due to excellent crystallinity, the large grain size, and the improved interface morphology of the MAPbI3 layer. In contrast, PSCs incorporated with an NiOx film sputtered under Ar/O2 mixed conditions possess a noncontinuous MAPbI3 perovskite layer having voids and cracks at the interface between MAPbI3/NiOx layer. These results indicate that a sputtered p-type NiOx HTL in Ar ambience can be an alternative route to the conventional solution-processed NiOx HTL for mass production of large-area PSCs.