Hot carrier solar cells and the potential of perovskites for breaking the Shockley-Queisser limit

In this review article, we discuss the working mechanism of hot carrier solar cells (HCSCs), their prerequisites from a material point of view and consider power conversion efficiencies that could reasonably be achieved with these devices. We review phonon decay pathways and proposed design rules for hot carrier absorbers established for classical bulk materials, as well as engineering efforts based on nanostructuring. Our main focus, however, lies on the recently emerged class of metal halide perovskites that not only exhibits tremendous potential in standard solar cells, but also offers highly promising hot carrier lifetimes. We discuss possible origins for this encouraging observation and point out pathways for future research towards HCSCs that break the Shockley-Queisser limit.</p

Cooling, Scattering, and Recombination-The Role of the Material Quality for the Physics of Tin Halide Perovskites

Tin-based perovskites have long remained a side topic in current perovskite optoelectronic research. With the recent efficiency improvement in thin film solar cells and the observation of a long hot carrier cooling time in formamidinium tin iodide (FASnI(3)), a thorough understanding of the material's photophysics becomes a pressing matter. Since pronounced background doping can easily obscure the actual material properties, it is of paramount importance to understand how different processing conditions affect the observed behavior. Using photoluminescence spectroscopy, thin films of FASnI(3) fabricated through different protocols are therefore investigated. It is shown that hot carrier relaxation occurs much faster in highly p-doped films due to carrier-carrier scattering. From high quality thin films, the longitudinal optical phonon energy and the electron-phonon coupling constant are extracted, which are fundamental to understanding carrier cooling. Importantly, high quality films allow for the observation of a previously unreported state of microsecond lifetime at lower energy in FASnI(3), that has important consequences for the discussion of long lived emission in the field of metal halide perovskites

Fundamentals of tin iodide perovskites:A promising route to highly efficient, lead-free solar cells

Hybrid tin-iodide perovskites are investigated as potential lead-free replacement of the lead-iodide perovskites; however, the intrinsic operational limit of these systems has not been described in detail, so far. In this work we combine advanced ab initio calculations with XRD and absorption measurements to lay out the fundamentals of formamidinium (FASnI3) and methylammonium (MASnI3) tin iodide perovskites, in comparison with the lead-halide MAPbI3 prototype. Our theoretical analysis reveals that the tin-based materials display an intrinsic photoconversion efficiency on a par with the lead perovskites, and even superior in the thick-layer limit, where the theoretical PCE reaches 30.5% for lead-halides, and 32.3% for tin-halides under AM1.5G illumination; this is the result of two competing factors: a smaller absorption cross section at the onset for stannates, and their smaller band gap of 1.36 eV, thus very close to the ideal Shockley-Queisser limit. We found the rate of photoluminescence emission extremely sensitive to the absorption spectral weight at the band extrema, resulting in B-factor as different as 7.6 × 10-9 s-1 cm3 for MASnI3 and 0.4 × 10-10 s-1 cm3 for FASnI3. The additional impact of Urbach energy and hole doping, giving rise to large Burstein-Moss effect, is described in detail. This journal i

Extrinsic nature of the broad photoluminescence in lead iodide-based Ruddlesden-Popper perovskites

Two-dimensional metal halide perovskites of Ruddlesden–Popper type have recently moved into the centre of attention of perovskite research due to their potential for light generation and for stabilisation of their 3D counterparts. It has become widespread in the field to attribute broad luminescence with a large Stokes shift to self-trapped excitons, forming due to strong carrier–phonon interactions in these compounds. Contrarily, by investigating the behaviour of two types of lead-iodide based single crystals, we here highlight the extrinsic origin of their broad band emission. As shown by below-gap excitation, in-gap states in the crystal bulk are responsible for the broad emission. With this insight, we further the understanding of the emission properties of low-dimensional perovskites and question the generality of the attribution of broad band emission in metal halide perovskite and related compounds to self-trapped excitons

Influence of morphology on photoluminescence properties of methylammonium lead tribromide films

The morphology of hybrid perovskite thin films plays a crucial role for their photophysical properties. However, the underlying mechanisms are still unclear. To gain further insight into this phenomenon, methylammonium lead tribromide films of different morphology were investigated using photoluminescence spectroscopy. Photostability measurements demonstrate three mechanisms: (A) reversible degradation of the photoluminescence, depending positively on the grain-boundary density, which is presumably caused by photo-induced bromide vacancies, (B) enhancement of the photoluminescence intensity in the presence of oxygen and moisture and (C) destruction of the perovskite after several minutes of ultraviolet illumination with excitation power above 100 W/cm(2). Both the intensity and the lifetime of the photoluminescence were significantly smaller in films with micrometer-sized crystallites compared to granular films. This is ascribed to crystals being partially isolated in the former, causing smaller diffusion lengths, whereas the carriers in the granular films can diffuse from grain to grain resulting in higher photoluminescence lifetime and intensity

Elucidating the Structure and Photophysics of Layered Perovskites through Cation Fluorination

Optoelectronic devices based on layered perovskites containing fluorinated cations display a well-documented improved stability and enhanced performance over non-fluorinated cations. The effect of fluorination on the crystal structure and photophysics, however, has received limited attention up until now. Here, 3-fluorophenethylammonium lead iodide ((3-FPEA)(2)PbI4) single crystals are investigated and their properties to the non-fluorinated ((PEA)(2)PbI4) variant are compared. The bulkier 3-FPEA cation increases the distortion of the inorganic layers, resulting in a blue-shifted absorbance and photoluminescence. Temperature-dependent photoluminescence spectroscopy reveals an intricate exciton substructure in both cases. The fluorinated variant shows hot-exciton resonances separated by 12 to 15 meV, values that are much smaller than the 40 to 46 meV found for (PEA)(2)PbI4. In addition, high-resolution spectra show that the emission at lower energies consists of a substructure, previously thought to be a single line. With the analysis on the resolved photoluminescence, a vibronic progression is excluded as the origin of the emission at lower energies. Instead, part of the excitonic substructure is proposed to originate from bound excitons. This work furthers the understanding of the photophysics of layered perovskites that has been heavily debated lately

Grain-Specific Transitions Determine the Band Edge Luminescence in Dion–Jacobson Type 2D Perovskites

The photophysics of 2D perovskites incorporating 1,4-phenylenedimethanammonium (PDMA) as spacer cations is studied. PDMAPbI4 and PDMASnI4 exhibit absorption and luminescence spectra dominated by excitonic transitions and an emission due to two different states. Low-temperature studies reveal a time-dependent red shift of 12 meV that is correlated with grain-specific luminescence spectra observed in optical micrographs. For the Pb-variant, grains of red-shifted and lower intensity band edge emission simultaneously exhibit a more pronounced luminescence from a broad defect-related band around 2 eV. This suggests the grain-specific emission to be related to local defects. These observations have important consequences for the understanding of luminescence of 2D perovskites, for which peak splitting of the band edge emission is a common, yet not completely resolved observation.</p

Opto-electronics of PbS quantum dot and narrow bandgap polymer blends

Here we report on the interaction between the narrow bandgap polymer [2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta-[2,1-b;3,4-b]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and lead sulphide (PbS) colloidal quantum dots (CQDs) upon photoexcitation. We show that the presence of both materials in a blend leads to a significant reduction of photoluminescence (PL) lifetime of the polymer. This observation is attributed, supported by transient absorption (TA) data, to an efficient electron transfer towards the QDs for excitons generated on the polymer. Furthermore, the ligand capping the QD surface exhibits a great impact on the dynamics of the PL, with the long-chain oleic acid (OA) largely suppressing any kind of interaction. By means of external quantum efficiency (EQE) measurements we find evidence that both components give rise to a contribution to the photocurrent, making this an interesting blend for future applications in hybrid organic-inorganic solar cells.</p

Delocalisation softens polaron electronic transitions and vibrational modes in conjugated polymers

In this work we study the photoinduced signatures of polarons in conjugated polymers and the impact of charge carrier delocalisation on their spectra. The variation of film crystallinity for two prototypical systems - blends of the homopolymer P3HT or the donor-acceptor polymer PCPDTBT with PCBM - allows probing changes of the polaron absorption in the mid infrared spectral region. Increased polaron delocalisation entails a shift of the electronic transition to lower energy in both cases. Also, infrared active vibrations soften due to a higher polymer chain order. Our findings help in providing a more complete understanding of polaron properties in conjugated materials and bring the application of the polaron absorption spectrum as an indicator for the environment on a more thoroughly studied foundation

Electroluminescence Generation in PbS Quantum Dot Light-Emitting Field-Effect Transistors with Solid-State Gating

The application of light-emitting field-effect transistors (LEFET) is an elegant way of combining electrical switching and light emission in a single device architecture instead of two. This allows for a higher degree of miniaturization and integration in future optoelectronic applications. Here, we report on a LEFET based on lead sulfide quantum dots processed from solution. Our device shows state-of-the-art electronic behavior and emits near infrared photons with a quantum yield exceeding 1% when cooled. We furthermore show how LEFETs can be used to simultaneously characterize the optical and electrical material properties on the same device and use this benefit dot film. to investigate the charge transport through the quantum dot film