Control of defect processes in photovoltaic materials is essential for realizing high-efficiency solar cells and related optoelectronic devices. Native defects and extrinsic dopants tune the Fermi level and enable semiconducting p–n junctions; however, fundamental limits to doping exist in many compounds. Optical transitions from defect states can enhance photocurrent generation through sub-bandgap absorption; however, these defect states are also often responsible for carrier trapping and non-radiative recombination events that limit the voltage in operating solar cells. Many classes of materials, including metal oxides, chalcogenides and halides, are being examined for next-generation solar energy applications, and each technology faces distinct challenges that could benefit from point defect engineering. Here, we review the evolution in the understanding of point defect behaviour from Si-based photovoltaics to thin-film CdTe and Cu(In,Ga)Se2 technologies, through to the latest generation of halide perovskite (CH3NH3PbI3) and kesterite (Cu2ZnSnS4) devices. We focus on the chemical bonding that underpins the defect chemistry and the atomistic processes associated with the photophysics of charge-carrier generation, trapping and recombination in solar cells. Finally, we outline general principles to enable defect control in complex semiconducting materials. Point defects have a key role in determining the performance of photovoltaic materials. In this Review, we assess defect processes in a range of photovoltaic materials and outline how point defect engineering could be used to improve the efficiency of solar cells.

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Point defect engineering in thin-film solar cells

In this paper, we present new insight in the degradation and subsequent recovery of charge carrier lifetime upon light soaking at 75 °C observed in float-zone silicon wafers. Variations of doping type, dielectric passivation schemes and thermal treatments after layer deposition were performed. The degradation was only observed for p-type float-zone silicon wafers passivated with passivation schemes involving silicon nitride layers. An influence of thermal treatments after deposition was found. N-type wafers did not degrade independent of their passivation scheme. Room temperature re-passivation experiments showed the degradation to affect the wafer bulk, and photoluminescence studies demonstrated fine lateral striations of effective lifetime. We conclude that the degradation is caused by bulk defects that might be related to hydrogen complexes.

Light-induced activation and deactivation of bulk defects in boron-doped float-zone silicon

The Shockley–Queisser (SQ) limit provides a convenient metric for predicting light-to-electricity conversion efficiency of a solar cell based on the band gap of the light-absorbing layer. In reality, few materials approach this radiative limit. We develop a formalism and computational method to predict the maximum photovoltaic efficiency of imperfect crystals from first principles. The trap-limited conversion efficiency includes equilibrium populations of native defects, their carrier-capture coefficients, and the associated recombination rates. When applied to kesterite solar cells, we reveal an intrinsic limit of 20% for Cu2ZnSnSe4, which falls far below the SQ limit of 32%. The effects of atomic substitution and extrinsic doping are studied, leading to pathways for an enhanced efficiency of 31%. This approach can be applied to support targeted-materials selection for future solar-energy technologies.

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Upper limit to the photovoltaic efficiency of imperfect crystals from first principles

This study aims to better understand the influence of crystallographic structure and impurity decoration on the recombination activity at grain boundaries in multicrystalline silicon. A sample of the upper part of a multicrystalline silicon ingot with intentional addition of iron and copper has been investigated. Correlative electron-beam-induced current, electron backscatter diffraction, and atom probe tomography data for different types of grain boundaries are presented. For a symmetric coherent Σ3 twin boundary, with very low recombination activity, no impurities are detected. In case of a non-coherent (random) high-angle grain boundary and higher order twins with pronounced recombination activity, carbon and oxygen impurities are observed to decorate the interface. Copper contamination is detected for the boundary with the highest recombination activity in this study, a random high-angle grain boundary located in the vicinity of a triple junction. The 3D atom probe tomography study presented here is the first direct atomic scale identification and quantification of impurities decorating grain boundaries in multicrystalline silicon. The observed deviations in chemical decoration and induced current could be directly linked with different crystallographic structures of silicon grain boundaries. Hence, the current work establishes a direct correlation between grain boundary structure, atomic scale segregation information, and electrical activity. It can help to identify interface–property relationships for silicon interfaces that enable grain boundary engineering in multicrystalline silicon. Copyright © 2015 John Wiley & Sons, Ltd.

Grain boundary segregation in multicrystalline silicon: correlative characterization by EBSD, EBIC, and atom probe tomography

This Perspective summarizes recent research into the excited-state dynamics in lead halide perovskites that are of paramount importance for photovoltaic and photocatalytic applications. Nonadiabatic molecular dynamics combined with time-domain ab initio density functional theory allows one to mimic time-resolved spectroscopy experiments at the atomistic level of detail. The focus is placed on realistic aspects of perovskite materials, including point defects, surfaces, grain boundaries, mixed stoichiometries, dopants, and interfaces. The atomistic description of the quantum dynamics of electron and hole trapping and recombination, provided by the time-domain ab initio simulations, generates important insights into the mechanisms of charge and energy losses and guides the development of high-performance perovskite solar cell devices.

Influence of Defects on Excited-State Dynamics in Lead Halide Perovskites: Time-Domain ab Initio Studies

Electronic grade Czochralski and float zone silicon in the as grown state have a very low concentration of recombination generation centers (typically <1010 cm−3). Consequently, in integrated circuit technologies using such material, electrically active inadvertent impurities and structural defects are rarely detectable. The quest for cheap photovoltaic cells has led to the use of less pure silicon, multi-crystalline material, and low cost processing for solar applications. Cells made in this way have significant extrinsic recombination mechanisms. In this paper we review recombination involving defects and impurities in single crystal and in multi-crystalline solar silicon. Our main techniques for this work are recombination lifetime mapping measurements using microwave detected photoconductivity decay and variants of deep level transient spectroscopy (DLTS). In particular, we use Laplace DLTS to distinguish between isolated point defects, small precipitate complexes and decorated extended defects. We compare the behavior of some common metallic contaminants in solar silicon in relation to their effect on carrier lifetime and cell efficiency. Finally, we consider the role of hydrogen passivation in relation to transition metal contaminants, grain boundaries and dislocations. We conclude that recombination via point defects can be significant but in most multi-crystalline material the dominant recombination path is via decorated dislocation clusters within grains with little contribution to the overall recombination from grain boundaries.

E. Don

Papers

Recombination via point defects and their complexes in solar silicon

Back Cover: Recombination via point defects and their complexes in solar silicon (Phys. Status Solidi A 10/2012)