Despite the central role of light absorption and the subsequent generation of free charge carriers in organic and hybrid organicÀinorganic photovoltaics, the precise process of this initial photoconversion is still debated. We employ a novel broadband (UVÀVisÀNIR) transient absorption spectroscopy setup to probe charge generation and recombination in the thin films of the recently suggested hybrid material combination poly(3-hexylthiophene)/silicon (P3HT/Si) with 40 fs time resolution. Our approach allows for monitoring the time evolution of the relevant transient species under various excitation intensities and excitation wavelengths. Both in regioregular (RR) and regiorandom (RRa) P3HT, we observe an instant (<40 fs) creation of singlet excitons, which subsequently dissociate to form polarons in 140 fs. The quantum yield of polaron formation through dissociation of delocalized excitons is significantly enhanced by adding Si as an electron acceptor, revealing ultrafast electron transfer from P3HT to Si. P3HT/Si films with aggregated RR-P3HT are found to provide free charge carriers in planar as well as in bulk heterojunctions, and losses are due to nongeminate recombination. In contrast for RRa-P3HT/Si, geminate recombination of bound carriers is observed as the dominant loss mechanism. Site-selective excitation by variation of pump wavelength uncovers an energy transfer from P3HT coils to aggregates with a 1/e transfer time of 3 ps and reveals a factor of 2 more efficient polaron formation using aggregated RR-P3HT compared to disordered RRa-P3HT. Therefore, we find that polymer structural order rather than excess energy is the key criterion for free charge generation in hybrid P3HT/Si solar cells.

Freestanding silicon nanocrystals (Si‐ncs) offer unique optical and electronic properties for new photovoltaic, thermoelectric, and other electronic devices. A method to fabricate Si‐ncs which is scalable to industrial usage has been developed in recent years. However, barriers to the widespread utilization of these nanocrystals are the presence of charge‐trapping defects and an oxide shell formed upon ambient atmosphere exposure hindering the charge transport. Here, we exploit low‐cost post‐growth treatment routes based on wet‐etching in hydrofluoric acid plus surface hydrosilylation or annealing enabling a complete native oxide removal and a reduction of the defect density by up to two orders of magnitude. Moreover, when compared with only H‐terminated Si‐ncs we report an enhancement of the conductivity by up to a factor of 400 for films of HF etched and annealed Si‐ncs, which retain a defect density below that of untreated Si‐ncs even after several months of air exposure. Further, we demonstrate that HF etched and hydrosilylated Si‐ncs are extremely stable against oxidation and maintain a very low defect density after a long‐term storage in air, opening the possibility of device processing in ambient atmosphere.

We have produced networks of surface-oxidized and hydrogen-terminated silicon nanocrystals (Si-NCs), both intrinsic and n-type doped, on flexible plastic foil from nanoparticle inks. The charge transport in these networks was comprehensively studied by means of time-dependent conductivity, steady-state current versus voltage characteristics, and steady-state photocurrent measurements as a function of incident light intensity. These measurements were complemented by surface chemistry and structural/morphological analysis from Fourier transform infrared spectroscopy and electron microscopy. Whereas H-terminated Si-NC networks function as semiconductors (both in air and in vacuum), where conductivity enhancement upon impurity doping and photoconductivity were observed, these characteristics are not present in networks of surface-oxidized Si-NCs. For both network types, the observation of a power law behavior for steady-state current versus voltage and a current decaying with time at constant bias indicate that charge transport is controlled by space-charge-limited current (involving trap states) via percolation paths through the networks. We have also monitored the evolution of the networks (photo)conductivity when the internanocrystal separating medium formed by Si–H bonds is progressively replaced by a native oxide upon exposure to air. Although a decrease in the (photo)conductivity is observed, the networks still behave as semiconductors even after a long-term air exposure. From an analysis of all (photo)current data, we deduce that in networks of oxidized Si-NCs inter-NC charge transfer requires the participation of oxide-related electronic states, whereas in H-terminated Si-NC networks direct inter-NC charge transfer plays a major role in the overall long-range conduction process.

Using electron paramagnetic resonance, we find that vacuum annealing at 200 °C leads to a significant reduction in the silicon dangling bond (Si-db) defect density in silicon nanoparticles (Si-NPs). The best improvement of the Si-db density by a factor of 10 is obtained when the vacuum annealing is combined with an etching step in hydrofluoric acid (HF), whereas HF etching alone only removes the Si-dbs at the Si/SiO2 interface. The reduction in the Si-db defect density is confirmed by photothermal deflection spectroscopy and photoconductivity measurements on thin Si-NPs films.

Using current–voltage measurements, photocurrent spectroscopy, and light‐induced electron spin resonance (LESR), we have investigated hybrid solar cells consisting of composites of silicon nanocrystals (Si‐ncs) and poly‐3(hexylthiophene) (P3HT). For a more detailed understanding of the inorganic/organic interface, we have also studied the properties of crystalline silicon (c‐Si)/P3HT heterostructures. Current–voltage characteristics of Si‐ncs/P3HT blends show an open‐circuit voltage of up to 0.76 V. Photocurrent spectroscopy measurements give a strong indication that both, the Si‐ncs and P3HT, contribute to the photo‐induced current. Further, we directly demonstrate a light‐induced charge transfer between the Si‐ncs and P3HT via LESR. Current–voltage measurements of c‐Si/P3HT heterojunctions were performed under illumination with high power light emitting diodes (LEDs) of different wavelengths, which allow a selective excitation of charge carriers in P3HT, silicon, or both materials. We have observed a disadvantageous energy band alignment of the valence band of silicon and the highest occupied molecular orbital (HOMO) level of P3HT which favors the use of small particles with a larger band gap due to quantum confinement.

The future exploitation of the exceptional properties of nanocrystal (NC) thin films deposited from liquid dispersions of nanoparticles relies upon our ability to produce films with improved electrical properties by simple and inexpensive means. Here, we demonstrate that the electronic conduction of solution-processed NC films can be strongly enhanced without the need of postdeposition treatments, via specific molecules adsorbed at the surfaces of adjacent NCs. This effect is demonstrated for Si NC films doped with the strong molecular oxidizing agent tetrafluoro-tetracyanoquinodimethane (F4-TCNQ). Density functional calculations were carried out with molecule-doped superlattice solid models. It is shown that, when populated by electrons, hybrid molecule/NC states edge (and may actually resonate with) the conduction-band states of the NC solid. This provides extra electronic connectivity across the NC network as the molecules effectively flatten the electronic potential barriers for electron transfer across the otherwise vacuum-filled network interstitialcies.

Charge transfer between silicon nanocrystals (Si-nc) and organic semiconductors has been investigated via light-induced electron spin resonance (LESR). Composites of Si-nc with the hole conductor poly(3-hexylthiophene) (P3HT) and with the electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) have been investigated. The LESR measurements allow one to quantify light-induced charge transfer between Si-nc and P3HT, which results in positive P3HT polarons. PCBM, in contrast, acts as an electron acceptor in composites with Si-nc, and after illumination, negative PCBM radicals are created. These results are discussed in terms of light-induced generation and separation of charge carriers in the hybrid composites.

Hybrid organic-inorganic solar cells from poly(3-hexylthiophene) (P3HT) and freestanding silicon nanocrystals (Si-ncs) combine the advantages of siliconbased photovoltaics with the cost-efficient solution processing technique. At present, the microwave-plasma synthesis of Si-ncs that allows for a future upscaling to industrial demands is at the expense of the Si-nc surface quality and the number of charge-trapping defects. Here, we present an enhancement of the solar cell performance by identifying the major factors which are limiting the device efficiency. With the help of low-cost post-growth treatments of the Si-ncs and the optimization of various device parameters, P3HT:Si-ncs bulk heterojunction solar cells with an efficiency up to 1.1 % are achieved. In particular, etching of the Si-ncs with hydrofluoric acid to remove the surface oxide shells and surface defects has a strong impact on the solar cell performance. An intermediate Si weight ratio of around 60 % is found to lead to the highest current densities. For Si-ncs with very small diameters, an additional enhancement of the open circuit voltage was observed. Moreover, we show that the structural order of P3HT has a strong influence on the efficiency, which can be explained by an improved charge carrier separation at the P3HT/Si-ncs interface in combination with an enhanced charge transport in the P3HT phase.