Charge Transfer In Blends Research Articles

Size‐Dependent Charge Transfer in Blends of PbS Quantum Dots with a Low‐Gap Silicon‐Bridged Copolymer

AbstractThe photophysics of bulk heterojunctions of a high‐performance, low‐gap silicon‐bridged dithiophene polymer with oleic acid capped PbS quantum dots (QDs) are studied to assess the material potential for light harvesting in the visible‐ and IR‐light ranges. By employing a wide range of nanocrystal sizes, systematic dependences of electron and hole transfer on quantum‐dot size are established for the first time on a low‐gap polymer–dot system. The studied system exhibits type II band offsets for dot sizes up to ca. 4 nm, whch allow fast hole transfer from the quantum dots to the polymer that competes favorably with the intrinsic QD recombination. Electron transfer from the polymer is also observed although it is less competitive with the fast polymer exciton recombination for most QD sizes studied. The incorporation of a fullerene derivative provides efficient electron‐quenching sites that improve interfacial polymer‐exciton dissociation in ternary polymer–fullerene–QD blends. The study indicates that programmable band offsets that allow both electron and hole extraction can be produced for efficient light harvesting based on this low‐gap polymer‐PbS QD composite.

Kinetics of charge transfer processes in organic solar cells: Implications for the design of acceptor molecules

We report the electronic properties of a new class of non-fullerene electron acceptor molecules with electron affinities tunable over an approximately 1eV range. This tunability allows us to vary the thermodynamic driving force for electron transfer (ΔG°) such that it is equal-and-opposite-to the reorganization energy for the ionized states (λ). We utilize this design principle, derived from Marcus–Hush theory, to optimize the rate of charge transfer in blends of these acceptors with poly(3-n-hexylthiophene-2,5-diyl) (P3HT) – a standard organic solar cell donor material. We show that computationally inexpensive calculations can be used to parameterize Marcus–Hush theory so as to correctly predict whether quenching will occur. Arguments based solely on energetics are common in the literature and we show that such theories do not predict the trends observed in our photoluminescence quenching experiments. This is the case whether the energies determined from experiments [cyclic voltammetry (CV) and the optical gap] or calculated from density functional theory for the solid state. We predict essentially barrier-less photoelectron transfer (PET) from P3HT to the acceptor 2-[{7-(9,9-di-n-propyl-9H-fluoren-2-yl)benzo[c] [1,2,5] thiadiazol-4-yl}methylene]malononitrile (or K12), consistent with the experimental photoluminescence quenching efficiencies found for P3HT:K12 blends. Our results clearly show that energetics alone is not sufficient to predict PET between the acceptor–donor pair, and that kinetics are an important determining factor.

Synthesis of lead chalcogenide nanocrystals and study of charge transfer in blends of PbSe nanocrystals and poly(3-hexylthiophene)

Nearly monodisperse lead chalcogenide (PbE, E = S, Se, or Te) semiconductor quantum dots of controllable shape have been produced via a novel synthesis which includes the occurrence of in situ formed Pb(0) particles. Tunable size and shape are achieved through appropriate choice of the precursor type and the stabilizer. As precursor, we use, on the one hand, lead oxide or lead acetate, on the other hand, tellurium, selenium, or sulfur powder dissolved in trioctylphosphine (TOP), tributylphosphine (TBP), or 1-octadecene (ODE). Oleic acid (OA) and various amines, as well as TOP and TBP are used for stabilization. With respect to possible application in hybrid solar cells, the surface of as-synthesized spherical PbSe nanocrystals was investigated by nuclear magnetic resonance (NMR), mass spectrometry (MS) and thermogravimetric analysis (TGA). As an important result, it was found that the surface is not mostly covered by oleic acid after synthesis, but by a phosphorus compound. We also applied a ligand exchange procedure with hexylamine and found evidence for the successful attachment of hexylamine to the nanocrystal surface. Additionally, charge separation between these nanoparticles and the conjugated polymer poly(3-hexylthiophene) (P3HT) is studied by electron spin resonance and photoinduced absorption spectroscopy. The spectra obtained suggest that charges can be produced successfully by photoinduced charge transfer.

Charge transfer in blends of P3HT and colloidally prepared CuInS 2 nanocrystals

CuInS 2 (CIS) is a suitable semiconductor for thin film photovoltaics and also a promising candidate to replace CdSe in hybrid polymer/nanoparticle solar cells, advantages being the lower toxicity and the better absorption properties. In this work, crystalline nanoparticles of CuInS 2 were successfully synthesized with uniform size and shape by means of colloidal chemistry. Photo-induced absorption spectroscopy was used to study charge transfer between poly(3-hexylthiophene) (P3HT) and the CIS nanoparticles. The appearance of signals corresponding to positive polarons provides evidence that charge transfer is possible in the P3HT/CIS system.

Absence of Photoinduced Charge Transfer in Blends of PbSe Quantum Dots and Conjugated Polymers

We use photoluminescence (PL) quenching and photoinduced absorption (PIA) spectroscopy to study charge transfer in bulk heterojunction blends of PbSe quantum dots with the semiconducting polymers poly-3-hexylthiophene (P3HT) and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-para-phenylene vinylene] (MDMO-PPV). PIA spectra from the PbSe blends are compared to spectra from similar blends of the polymers with phenyl-C(61)-butyric acid methyl ester (PCBM) and blends with CdSe quantum dots. We find that the MDMO-PPV PL is quenched, and the PL lifetime is shortened upon addition of PbSe quantum dots, while the PL of the P3HT is unaffected upon blending. However, for PbSe blends with both polymers, the PIA spectra show very little polaronic signal, suggesting that few, if any, long-lived charges are being produced by photoinduced charge transfer.

Energy and charge transfer in blends of dendronized perylenes with polyfluorene

Two generations of polyphenylene dendrimers with a perylene diimide core are compared with a nondendronized tetraphenoxyperylene diimide model compound regarding their application in organic light-emitting diodes (OLEDs). Single layer devices with blends of the first and second generation dendrimers in polyfluorene are investigated as active layers in OLEDs, and the effect of dendronization on the emission color and electroluminescence intensity is studied. In photoluminescence, higher degrees of dendronization lead to a reduction in Forster transfer from the polyfluorene host to the perylene, resulting in a larger contribution of the blue host emission in the photoluminescence spectra. In electroluminescence, the dopants appear to act as active traps for electrons, resulting in a predominant generation of excitons on the dye. This gives rise to a remarkably stronger contribution of red emission in electroluminescence than in photoluminescence where energy is exchanged exclusively via Forster transfer. The pronounced color change from red to blue with higher degrees of dendronization and larger driving voltages is explained by the competition of the recombination of free electrons with holes and trapping of electrons by the emitting guest.

Comparison of blended versus layered structures for poly(p-phenylene vinylene)-based polymer photovoltaics

We characterize and compare blended and bilayered heterojunctions of polymer photovoltaic devices using poly[oxa-1,4-phenylene-1,2-(1-cyano)-ethenylene-2,5-dioctyloxy-1,4-phenylene-1,2-(2-cyano)-ethenylene-1,4-phenylene] (CN-ether-PPV) and poly[2,5-dimethoxy-1,4-phenylene-1,2-ethenylene-2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-1,2-ethenylene] (M3EH-PPV) as electron- and hole-transporting polymers, respectively. We find that both blended and bilayered structures have substantially improved current densities (>3mA∕cm2) and power efficiencies (∼1% under white light) over neat films. Improved exciton dissociation at multiple interfaces and reduced recombination due to energy and charge transfers increases the charge-carrier collection in both types of heterojunction devices, but low electron mobilities in the polymers lead to low fill factors and reduced quantum efficiency (∼20%) that limit the power efficiency. Time-resolved photoluminescence reveals that for blended structures both the hole and electron-transporting polymers undergo efficient quenching with the exciton decay being dominated by the existence of two fast decay channels of 0.12 and 0.78ns that are assigned to interspecies charge transfer and account for the increased short-circuit current observed. For layers, these components are not as prevalent. This result indicates that greater exciton generation at the dissociating interface and more efficient charge collection in the thin layers is primarily responsible for the improved short-circuit current, a conclusion that is further supported by numerical simulations of the exciton generation rate and charge collection. We also report evidence for an intermediate exciplex state in both types of structures with the greatest yield for blends with 50wt% of CN-ether-PPV. Overall, the improved performance is due to different processes in the two structures; efficient bulk exciton quenching and charge transfer in blends and enhanced exciton generation and charge collection in layers. The optimization of each photovoltaic heterostructured device relies on this understanding of the mechanisms by which each material architecture achieves high power efficiencies.

Spectroscopical evidences of photoinduced charge transfer in blends of C 60 and thiophene-based copolymers with a tunable energy gap

We report a study of the photoinduced charge transfer in the blends of buckminsterfullerene (C 60) and thiophene-based copolymers with tunable energy gap. The photoluminescence and steady state photoinduced absorption spectra evidence the electron transfer from the photoexcited copolymer to C 60. The efficiency of the charge transfer depends on the degree of miscibility of the two components which is easily controlled by the copolymer composition. In the blends obtained with a copolymer with an high energy absorption onset, the spectral signatures of the photoinduced hole transfer to the polymer, arising from the selective excitation of the C 60, are also detected.

Efficient charge carrier transfer from m-LPPP to C 60 derivatives

The improvement of dissociation of singlet excitons by electron or hole capturing species like C 60 is essential for efficient photovoltaic cells based on conjugated systems. We investigate the charge transfer in blends of methyl-substituted ladder type poly-(paraphenylene) (m-LPPP) with new well soluble C 60 derivatives, which are characterized by sidegroups of different electronic properties (donor, acceptor nature). It is shown, that the electronic properties of the C 60 sidegroups strongly influence the efficiency of the charge transfer in these blends and hence significant different behaviours in the photocurrent and photoinduced absorption is observed.