Xinkai Qiu

Enhancing doping efficiency by improving host-dopant miscibility for fullerene-based n-type thermoelectrics

This paper describes a promising n-type doping system with high performance for thermoelectric applications. By introducing the polar triethylene glycol (TEG) side chain onto both fullerene host (PTEG-1) and dopant (TEG-DMBI) materials, the TEG-DMBI doped PTEG-1 films obtained through solution processing provide a better miscibility compared with films doped with commercially available N-DMBI (bearing a dimethylamino group instead of TEG), as determined by phase imaging AFM (atomic force microscopy) measurements and coarse-grain molecular dynamics simulations, leading to high doping efficiency up to 18% at 20 mol% doping concentration and thus high carrier density and mobility, which are critical to the electrical conductivity. Therefore a record power factor of 19.1 μW m−1 K−2 is obtained with an electrical conductivity of 1.81 S cm−1, one of the highest values reported for solution processable fullerene derivatives as n-type organic materials for thermoelectric applications to date.

Conformation-driven quantum interference effects mediated by through-space conjugation in self-assembled monolayers

Tunnelling currents through tunnelling junctions comprising molecules with cross-conjugation are markedly lower than for their linearly conjugated analogues. This effect has been shown experimentally and theoretically to arise from destructive quantum interference, which is understood to be an intrinsic, electronic property of molecules. Here we show experimental evidence of conformation-driven interference effects by examining through-space conjugation in which π-conjugated fragments are arranged face-on or edge-on in sufficiently close proximity to interact through space. Observing these effects in the latter requires trapping molecules in a non-equilibrium conformation closely resembling the X-ray crystal structure, which we accomplish using self-assembled monolayers to construct bottom-up, large-area tunnelling junctions. In contrast, interference effects are completely absent in zero-bias simulations on the equilibrium, gas-phase conformation, establishing through-space conjugation as both of fundamental interest and as a potential tool for tuning tunnelling charge-transport in large-area, solid-state molecular-electronic devices.

Mechanically and Electrically Robust Self-Assembled Monolayers for Large-Area Tunneling Junctions

This paper examines the relationship between mechanical deformation and the electronic properties of self-assembled monolayers (SAMs) of the oligothiophene 4-([2,2′:5′,2″:5″,2‴-quaterthiophen]-5-yl)butane-1-thiol (T4C4) in tunneling junctions using conductive probe atomic force microscopy (CP-AFM) and eutectic Ga–In (EGaIn). We compared shifts in conductivity, transition voltages of T4C4 with increasing AFM tip loading force to alkanethiolates. While these shifts result from an increasing tilt angle from penetration of the SAM by the AFM tip for the latter, we ascribe them to distortions of the π system present in T4C4, which is more mechanically robust than alkanethiolates of comparable length; SAMs comprising T4C4 shows about five times higher Young’s modulus than alkanethiolates. Density functional theory calculations confirm that mechanical deformations shift the barrier height due to changes in the frontier orbitals caused by small rearrangements to the conformation of the quaterthiophene moiety. The mechanical robustness of T4C4 manifests as an increased tolerance to high bias in large-area EGaIn junctions suggesting that electrostatic pressure plays a significant role in the shorting of molecular junctions at high bias.

Tunneling Probability Increases with Distance in Junctions Comprising Self-Assembled Monolayers of Oligothiophenes

Molecular tunneling junctions should enable the tailoring of charge-transport at the quantum level through synthetic chemistry but are hindered by the dominance of the electrodes. We show that the frontier orbitals of molecules can be decoupled from the electrodes, preserving their relative energies in self-assembled monolayers even when a top-contact is applied. This decoupling leads to the remarkable observation of tunneling probabilities that increase with distance in a series of oligothiophenes, which we explain using a two-barrier tunneling model. This model is generalizable to any conjugated oligomers for which the frontier orbital gap can be determined and predicts that the molecular orbitals that dominate tunneling charge-transport can be positioned via molecular design rather than by domination of Fermi-level pinning arising from strong hybridization. The ability to preserve the electronic structure of molecules in tunneling junctions facilitates the application of well-established synthetic design rules to tailor the properties of molecular-electronic devices.

Soft Nondamaging Contacts Formed from Eutectic Ga–In for the Accurate Determination of Dielectric Constants of Organic Materials

A method for accurately measuring the relative dielectric constant (εr) of thin films of soft, organic materials is described. The effects of the bombardment of these materials with hot Al atoms, the most commonly used top electrode, are mitigated by using electrodes fabricated from eutectic gallium–indium (EGaIn). The geometry of the electrode is defined by injection into microchannels to form stable structures that are nondamaging and that conform to the topology of the organic thin film. The εr of a series of references and new organic materials, polymers, and fullerene derivatives was derived from impedance spectroscopy measurements for both Al and EGaIn electrodes showing the specific limitations of Al with soft, organic materials and overcoming them with EGaIn to determine their dielectric properties and provide realistic values of εr.

N‐Type Organic Thermoelectrics of Donor–Acceptor Copolymers: Improved Power Factor by Molecular Tailoring of the Density of States

It is demonstrated that the n-type thermoelectric performance of donor-acceptor (D-A) copolymers can be enhanced by a factor of >1000 by tailoring the density of states (DOS). The DOS distribution is tailored by embedding sp2 -nitrogen atoms into the donor moiety of the D-A backbone. Consequently, an electrical conductivity of 1.8 S cm-1 and a power factor of 4.5 µW m-1 K-2 are achieved. Interestingly, an unusual sign switching (from negative to positive) of the Seebeck coefficient of the unmodified D-A copolymer at moderately high dopant loading is observed. A direct measurement of the DOS shows that the DOS distributions become less broad upon modifying the backbone in both pristine and doped states. Additionally, doping-induced charge transfer complexes (CTC) states, which are energetically located below the neutral band, are observed in DOS of the doped unmodified D-A copolymer. It is proposed that charge transport through these CTC states is responsible for the positive Seebeck coefficients in this n-doped system. This is supported by numerical simulation and temperature dependence of Seebeck coefficient. The work provides a unique insight into the fundamental understanding of molecular doping and sheds light on designing efficient n-type OTE materials from a perspective of tailoring the DOS.

Enhancing the Performance of the Half Tin and Half Lead Perovskite Solar Cells by Suppression of the Bulk and Interfacial Charge Recombination

In this article it is investigated how the hole extraction layer (HEL) influence the charge recombination and performance in half tin and half lead (FASn0.5 Pb0.5 I3 ) based solar cells (HPSCs). FASn0.5 Pb0.5 I3 film grown on PEDOT:PSS displays a large number of pin-holes and open grain boundaries, resulting in a high defect density and shunts in the perovskite film causing significant bulk and interfacial charge recombination in the HPSCs. By contrast, FASn0.5 Pb0.5 I3 films grown on PCP-Na, an anionic conjugated polymer, show compact and pin-hole free morphology over a large area, which effectively eliminates the shunts and trap states. Moreover, PCP-Na is characterized by a higher work function, which determines a favorable energy alignment at the anode interface, enhancing the charge extraction. Consequently, both the interfacial and bulk charge recombination in devices using PCP-Na HEL are considerably reduced giving rise to an overall improvement of all the device parameters. The HPSCs fabricated with this HEL display power conversion efficiency up to 16.27%, which is 40% higher than the efficiency of the control devices using PEDOT:PSS HEL (11.60%). Furthermore, PCP-Na as HEL offers superior performance in larger area devices compared to PEDOT:PSS.

Self-Regenerating Soft Biophotovoltaic Devices

This paper describes the fabrication of soft, stretchable biophotovoltaic devices that generate photocurrent from photosystem I (PSI) complexes that are self-assembled onto Au electrodes with a preferred orientation. Charge is collected by the direct injection of electrons into the Au electrode and the transport of holes through a redox couple to liquid eutectic gallium–indium (EGaIn) electrodes that are confined to microfluidic pseudochannels by arrays of posts. The pseudochannels are defined in a single fabrication step that leverages the non-Newtonian rheology of EGaIn. This strategy is extended to the fabrication of reticulated electrodes that are inherently stretchable. A simple shadow evaporation technique is used to increase the surface area of the Au electrodes by a factor of approximately 106 compared to planar electrodes. The power conversion efficiency of the biophotovoltaic devices decreases over time, presumably as the PSI complexes denature and/or detach from the Au electrodes. However, by circulating a solution of active PSI complexes the devices self-regenerate by mass action/self-assembly. These devices leverage simple fabrication techniques to produce complex function and prove that photovoltaic devices comprising PSI can retain the ability to regenerate, one of the most important functions of photosynthetic organisms.