Katherine E. Roelofs

Interface Engineering in Inorganic-Absorber Nanostructured Solar Cells.

Nanostructured solar cells have the potential to provide a low-cost alternative to more traditional thin film solar cell technologies. Of particular interest are nanostructured solar cells with inorganic semiconductor absorbers, due to their favorable absorption properties. Such devices include quantum-dot-sensitized solar cells (QDSSCs), extremely thin absorber solar cells (ETASCs), and colloidal quantum dot solar cells (CQDSCs). However, these device architectures suffer from high rates of internal recombination and other problems associated with their extensive internal surface areas. Interfacial surface treatments have proven to be a highly effective means to improve the electronic properties of these devices, leading to overall gains in efficiencies. In this Perspective, we focus on three types of interfacial modification: band alignment by molecular dipole layers, improved CQD film mobilities by ligand exchange, and reduced recombination by interfacial inorganic layers. Select examples in each of these categories are highlighted to provide a detailed look at the underlying mechanisms. We believe that surface modification studies in these devices-QDSSCs, ETASCs, and CQDSCs-are of interest not only to these fields, but also to the broader photovoltaics community.

Efficiency enhancement of solid-state PbS quantum dot-sensitized solar cells with Al2O3 barrier layer

Atomic layer deposition (ALD) was used to grow both PbS quantum dots and Al2O3 barrier layers in a solid-state quantum dot-sensitized solar cell (QDSSC). Barrier layers grown prior to quantum dots resulted in a near-doubling of device efficiency (0.30% to 0.57%) whereas barrier layers grown after quantum dots did not improve efficiency, indicating the importance of quantum dots in recombination processes.

Quantifying Geometric Strain at the PbS QD-TiO2 Anode Interface and Its Effect on Electronic Structures

Quantum dots (QDs) show promise as the absorber in nanostructured thin film solar cells, but achieving high device efficiencies requires surface treatments to minimize interfacial recombination. In this work, lead sulfide (PbS) QDs are grown on a mesoporous TiO2 film with a crystalline TiO2 surface, versus one coated with an amorphous TiO2 layer by atomic layer deposition (ALD). These mesoporous TiO2 films sensitized with PbS QDs are characterized by X-ray and electron diffraction, as well as X-ray absorption spectroscopy (XAS) in order to link XAS features with structural distortions in the PbS QDs. The XAS features are further analyzed with quantum simulations to probe the geometric and electronic structure of the PbS QD-TiO2 interface. We show that the anatase TiO2 surface structure induces PbS bond angle distortions, which increases the energy gap of the PbS QDs at the interface.

Tailoring Mixed-Halide, Wide-Gap Perovskites via Multistep Conversion Process

Wide-band-gap mixed-halide CH3NH3PbI3-XBrX-based solar cells have been prepared by means of a sequential spin-coating process. The spin-rate for PbI2 as well as its repetitive deposition are important in determining the cross-sectional shape and surface morphology of perovskite, and, consequently, J-V performance. A perovskite solar cell converted from PbI2 with a dense bottom layer and porous top layer achieved higher device performance than those of analogue cells with a dense PbI2 top layer. This work demonstrates a facile way to control PbI2 film configuration and morphology simply by modification of spin-coating parameters without any additional chemical or thermal post-treatment.

Increased Quantum Dot Loading by pH Control Reduces Interfacial Recombination in Quantum-Dot-Sensitized Solar Cells

The power conversion efficiency of quantum-dot-sensitized solar cells (QDSSCs) hinges on interfacial charge transfer. Increasing quantum dot (QD) loading on the TiO2 anode has been proposed as a means to block recombination of electrons in the TiO2 to the hole transport material; however, it is not known whether a corresponding increase in QD-mediated recombination processes might lead to an overall higher rate of recombination. In this work, a 3-fold increase in PbS QD loading was achieved by the addition of an aqueous base to negatively charge the TiO2 surface during Pb cation deposition. Increased QD loading improved QDSSC device efficiencies through both increased light absorption and an overall reduction in recombination. Unexpectedly, we also found increased QD size had the detrimental effect of increasing recombination. Kinetic modeling of the effect of QD size on interfacial charge transfer processes provided qualitative agreement with the observed variation in recombination lifetimes. These results demonstrate a robust method of improving QD loading, identify the specific mechanisms by which increased QD deposition impacts device performance, and provide a framework for future efforts optimizing the device architecture of QDSSCs.

Role of aluminum in silver paste contact to boron-doped silicon emitters

The addition of aluminum to silver metallization pastes has been found to lower the contact resistivity of a silver metallization on boron-doped silicon emitters for n-type Si solar cells. However, the addition of Al also induces more surface recombination and increases the Ag pattern′s line resistivity, both of which ultimately limit the cell efficiency. There is a need to develop a fundamental understanding of the role that Al plays in reducing the contact resistivity and to explore alternative additives. A fritless silver paste is used to allow direct analysis of the impact of Al on the Ag-Si interfacial microstructure and isolate the influence of Al on the electrical contact from the complicated Ag-Si interfacial glass layer. Electrical analysis shows that in a simplified system, Al decreases the contact resistivity by about three orders of magnitude. Detailed microstructural studies show that in the presence of Al, microscale metallic spikes of Al-Ag alloy and nanoscale metallic spikes of Ag-Si alloy...

Effects of QD surface coverage in solid-state PbS quantum dot-sensitized solar cells

Lead sulfide quantum dots (QDs) were grown in situ on nanoporous TiO2 by successive ion layer adsorption and reaction (SILAR) and by atomic layer deposition (ALD), to fabricate solid-state quantum-dot sensitized solar cells (QDSSCs). With the ultimate goal of increasing QD surface coverage, this work compares the impact of these two synthetic routes on the light absorption and electrical properties of devices. A higher current density was observed in the SILAR-grown QD devices under reverse bias, as compared to ALD-grown QD devices, attributed to injection problems of the lower-band-gap QDs present in the SILAR-grown QD device. To understand the effects of QD surface coverage on device performance, particularly interfacial recombination, electron lifetimes were measured for varying QD deposition cycles. Electron lifetimes were found to decrease with increasing SILAR cycles, indicating that the expected decrease in recombination between electrons in the TiO2 and holes in the hole-transport material, due to increased QD surface coverage, is not the dominant effect of increased deposition cycles.

Recombination barrier layers in solid-state quantum dot-sensitized solar cells

By replacing the dye in the dye-sensitized solar cell design with semiconductor quantum dots as the light-absorbing material, solid-state quantum dot-sensitized solar cells (ss-QDSSCs) were fabricated. Cadmium sulfide quantum dots (QDs) were grown in situ by successive ion layer adsorption and reaction (SILAR). Aluminum oxide recombination barrier layers were deposited by atomic layer deposition (ALD) at the TiO2/hole-conductor interface. For low numbers of ALD cycles, the Al2O3 barrier layer increased open circuit voltage, causing an increase in device efficiency. For thicker Al2O3 barrier layers, photocurrent decreased substantially, leading to a decrease in device efficiency.