Jared Crochet

High-efficiency solution-processed perovskite solar cells with millimeter-scale grains

Large-crystal perovskite films The performance of organic-inorganic hybrid perovskite planar solar cells has steadily improved. One outstanding issue is that grain boundaries and defects in polycrystalline films degrade their output. Now, two studies report the growth of millimeter-scale single crystals. Nie et al. grew continuous, pinhole-free, thin iodochloride films with a hot-casting technique and report device efficiencies of 18%. Shi et al. used antisolvent vapor-assisted crystallization to grow millimeter-scale bromide and iodide cubic crystals with charge-carrier diffusion lengths exceeding 10 mm. Science, this issue p. 522, p. 519 Solution processing techniques enable the growth of high-quality, large-area perovskite crystals for solar cells. State-of-the-art photovoltaics use high-purity, large-area, wafer-scale single-crystalline semiconductors grown by sophisticated, high-temperature crystal growth processes. We demonstrate a solution-based hot-casting technique to grow continuous, pinhole-free thin films of organometallic perovskites with millimeter-scale crystalline grains. We fabricated planar solar cells with efficiencies approaching 18%, with little cell-to-cell variability. The devices show hysteresis-free photovoltaic response, which had been a fundamental bottleneck for the stable operation of perovskite devices. Characterization and modeling attribute the improved performance to reduced bulk defects and improved charge carrier mobility in large-grain devices. We anticipate that this technique will lead the field toward synthesis of wafer-scale crystalline perovskites, necessary for the fabrication of high-efficiency solar cells, and will be applicable to several other material systems plagued by polydispersity, defects, and grain boundary recombination in solution-processed thin films.

High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells

Three-dimensional organic–inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley–Queisser limit for a single‐junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden–Popper phases—layered two-dimensional perovskite films—have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.

Light-activated photocurrent degradation and self-healing in perovskite solar cells

Solution-processed organometallic perovskite solar cells have emerged as one of the most promising thin-film photovoltaic technology. However, a key challenge is their lack of stability over prolonged solar irradiation. Few studies have investigated the effect of light soaking on hybrid perovskites and have attributed the degradation in the optoelectronic properties to photochemical or field-assisted ion migration. Here we show that the slow photocurrent degradation in thin-film photovoltaic devices is due to the formation of light-activated meta-stable deep-level trap states. However, the devices can self-heal completely by resting them in the dark for <1 min or the degradation can be completely prevented by operating the devices at 0 °C. We investigate several physical mechanisms to explain the microscopic origin for the formation of these trap states, among which the creation of small polaronic states involving localized cooperative lattice strain and molecular orientations emerges as a credible microscopic mechanism requiring further detailed studies.

Diffusion limited photoluminescence quantum yields in 1-D semiconductors: single-wall carbon nanotubes.

Photoluminescence quantum yields and nonradiative decay of the excitonic S(1) state in length fractionated (6,5) single-wall carbon nanotubes (SWNTs) are studied by continuous wave and time-resolved fluorescence spectroscopy. The experimental data are modeled by diffusion limited contact quenching of excitons at stationary quenching sites including tube ends. A combined analysis of the time-resolved photoluminescence decay and the length dependence of photoluminescence quantum yields (PL QYs) from SWNTs in sodium cholate suspensions allows to determine the exciton diffusion coefficient D = 10.7 ± 0.4 cm(2)s(-1) and lifetime τ(PL) for long tubes of 20 ± 1 ps. PL quantum yields Φ(PL) are found to scale with the inverse diffusion coefficient and the square of the mean quenching site distance, here l(d) = 120 ± 25 nm. The results suggest that low PL QYs of SWNTs are due to the combination of high-diffusive exciton mobility with the presence of only a few quenching sites.

Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials

Solution-processed organometallic perovskites have rapidly developed into a top candidate for the active layer of photovoltaic devices. Despite the remarkable progress associated with perovskite materials, many questions about the fundamental photophysical processes taking place in these devices, remain open. High on the list of unexplained phenomena are very modest mobilities despite low charge carrier effective masses. Moreover, experiments elucidate unique degradation of photocurrent affecting stable operation of perovskite solar cells. These puzzles suggest that, while ionic hybrid perovskite devices may have efficiencies on par with conventional Si and GaAs devices, they exhibit more complicated charge transport phenomena. Here we report the results from an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies using both periodic boundary conditions and isolated structures. Using the hybrid density functional theory, we found that volumetric strain in a CsPbI3 cluster creates a polaron with binding energy of around 300 and 900 meV for holes and electrons, respectively. In the MAPbI3 (MA = CH3NH3) cluster, both volumetric strain and MA reorientation effects lead to larger binding energies at around 600 and 1300 meV for holes and electrons, respectively. Such large reorganization energies suggest appearance of small polarons in organometallic perovskite materials. The fact that both volumetric lattice strain and MA molecular rotational degrees of freedom can cooperate to create and stabilize polarons indicates that in order to mitigate this problem, formamidinium (FA = HC(NH2)2) and cesium (Cs) based crystals and alloys, are potentially better materials for solar cell and other optoelectronic applications.

Photoluminescence imaging of electronic-impurity-induced exciton quenching in single-walled carbon nanotubes

The electronic properties of single-walled carbon nanotubes can be altered by surface adsorption of electronic impurities or dopants. However, fully understanding the influence of these impurities is difficult because of the inherent complexity of the solution-based colloidal chemistry of nanotubes, and because of a lack of techniques for directly imaging dynamic processes involving these impurities. Here, we show that photoluminescence microscopy can be used to image exciton quenching in semiconducting single-walled carbon nanotubes during the early stages of chemical doping with two different species. The addition of AuCl(3) leads to localized exciton-quenching sites, which are attributed to a mid-gap electronic impurity level, and the adsorbed species are also found sometimes to be mobile on the surface of the nanotubes. The addition of H(2)O(2) leads to delocalized exciton-quenching hole states, which are responsible for long-range photoluminescence blinking, and are also mobile.

Ultrafast Excitation Energy Transfer in Small Semiconducting Carbon Nanotube Aggregates

We study excitation energy transfer in small aggregates of chirality enriched carbon nanotubes by transient absorption spectroscopy. Ground state photobleaching is used to monitor exciton population dynamics with sub-10 fs time resolution. Upon resonant excitation of the first exciton transition in (6,5) tubes, we find evidence for energy transfer to (7,5) tubes within our time resolution (<10 fs). Excitation in the visible spectral range, where the second excitonic transitions occur, is followed by fast intratube relaxation and subsequent energy transfer, in particular from the (8,4) tube toward other tubes, the latter process occurring in less than 10 fs.

Disorder Limited Exciton Transport in Colloidal Single-Wall Carbon Nanotubes

We present measurements of S(1) exciton transport in (6,5) carbon nanotubes at room temperature in a colloidal environment. Exciton diffusion lengths associated with end quenching paired with photoluminescence lifetimes provide a direct basis for determining a median diffusion constant of approximately 7.5 cm(2)s(-1). Our experimental results are compared to model diffusion constants calculated using a realistic exciton dispersion accounting for a logarithmic correction due to the exchange self-energy and a nonequilibrium distribution between bright and dark excitons. The intrinsic diffusion constant associated with acoustic phonon scattering is too large to explain the observed diffusion length, and as such, we attribute the observed transport to disorder-limited diffusional transport associated with the dynamics of the colloidal interface. In this model an effective surface potential limits the exciton mean free path to the same size as that of the exciton wave function, defined by the strength of the electron-hole Coulomb interaction.

Electrodynamic and excitonic intertube interactions in semiconducting carbon nanotube aggregates.

The optical properties of selectively aggregated, nearly single chirality single-wall carbon nanotubes were investigated by both continuous-wave and time-resolved spectroscopies. With reduced sample heterogeneities, we have resolved aggregation-dependent reductions of the excitation energy of the S(1) exciton and enhanced electron-hole pair absorption. Photoluminescence spectra revealed a spectral splitting of S(1) and simultaneous reductions of the emission efficiencies and nonradiative decay rates. The observed strong deviations from isolated tube behavior are accounted for by enhanced screening of the intratube Coulomb interactions, intertube exciton tunneling, and diffusion-driven exciton quenching. We also provide evidence that density gradient ultracentrifugation can be used to structurally sort single-wall carbon nanotubes by aggregate size as evident by a monotonic dependence of the aforementioned optical properties on buoyant density.

Intersubband decay of 1-D exciton resonances in carbon nanotubes.

We have studied intersubband decay of E22 excitons in semiconducting carbon nanotubes experimentally and theoretically. Photoluminescence excitation line widths of semiconducting nanotubes with chiral indicess (n,m) can be mapped onto a connectivity grid with curves of constant (n - m) and (2n + m). Moreover, the global behavior of E22 line widths is best characterized by a strong increase with energy irrespective of their (n-m)mod(3) = +/-1 family affiliation. Solution of the Bethe-Salpeter equations shows that the E22 line widths are dominated by phonon assisted coupling to higher momentum states of the E11 and E12 exciton bands. The calculations also suggest that the branching ratio for decay into exciton bands vs free carrier bands, respectively is about 10:1.