Run-Wei Li

Sub-10 nm Fe3O4@Cu2–xS Core–Shell Nanoparticles for Dual-Modal Imaging and Photothermal Therapy

Photothermal nanomaterials have recently attracted significant research interest due to their potential applications in biological imaging and therapeutics. However, the development of small-sized photothermal nanomaterials with high thermal stability remains a formidable challenge. Here, we report the rational design and synthesis of ultrasmall (<10 nm) Fe3O4@Cu2-xS core-shell nanoparticles, which offer both high photothermal stability and superparamagnetic properties. Specifically, these core-shell nanoparticles have proven effective as probes for T2-weighted magnetic resonance imaging and infrared thermal imaging because of their strong absorption at the near-infrared region centered around 960 nm. Importantly, the photothermal effect of the nanoparticles can be precisely controlled by varying the Cu content in the core-shell structure. Furthermore, we demonstrate in vitro and in vivo photothermal ablation of cancer cells using these multifunctional nanoparticles. The results should provide improved understanding of synergistic effect resulting from the integration of magnetism with photothermal phenomenon, important for developing multimode nanoparticle probes for biomedical applications.

Nonvolatile resistive switching in graphene oxide thin films

Reliable and reproducible resistive switching behaviors were observed in graphene oxide (GO) thin films prepared by the vacuum filtration method. The Cu/GO/Pt structure showed an on/off ratio of about 20, a retention time of more than 104 s, and switching threshold voltages of less than 1 V. The switching effect could be understood by considering the desorption/absorption of oxygen-related groups on the GO sheets as well as the diffusion of the top electrodes. Our experiments indicate that GO is potentially useful for future nonvolatile memory applications.

Observation of Conductance Quantization in Oxide‐Based Resistive Switching Memory

Conductance quantization phenomena are observed in oxide-based resistive switching memories. These phenomena can be understood by the formation and disruption of atomic-scale conductive filaments in the insulating oxide matrix. The quantum conductance effect can be artificially modulated by controlling the electrical parameters in Set and Reset processes, and can be used for multi-level data storage and help understand and design one-dimensional structures at atomic scales in various materials systems.

Resistance switching in polycrystalline BiFeO3 thin films

We report resistance switching effects in polycrystalline pure BiFeO3 films prepared by a sol-gel method. By current-voltage and conductive atomic force microscope (c-AFM) measurements, resistance switching effects are observed in BiFeO3 films annealed at and above 650 °C. A fresh sample can be transformed into a low-resistive state by applying a high positive voltage without forming process and then be switched to a high-resistive state by applying a negative voltage. Both c-AFM and retention results suggest that the redistribution of oxygen vacancies in grain boundaries could play a key role on the resistance switching in the polycrystalline pure BiFeO3 films.

Effect of top electrodes on photovoltaic properties of polycrystalline BiFeO3 based thin film capacitors

We investigated capacitors based on polycrystalline narrow-band-gap BiFeO(3) (BFO) thin films with different top electrodes. The photovoltaic response for the capacitor with a Sn-doped In(2)O(3) (ITO) top electrode is about 25 times higher than that with a Au top electrode, which indicates that the electrode plays a key role in determining the photovoltaic response of ferroelectric thin film capacitors, as simulated by Qin et al (2009 Appl. Phys. Lett. 95 22912). The light-to-electricity photovoltaic efficiency for the ITO/polycrystalline BFO/Pt capacitor can reach 0.125%. Furthermore, under incident light of 450 µW cm(-2) and zero bias, the corresponding photocurrent varies from 0.2 to 200 pA, that is, almost a 1000-fold photoconductivity enhancement. Our experiments suggest that polycrystalline BFO films are promising materials for application in photo-sensitive and energy-related devices.

Nonvolatile resistive switching memory based on amorphous carbon

Resistive memory effect has been found in carbon nanostructure-based devices by Standley et al. [Nano Lett. 8, 3345 (2008)]. Compared to nanostructures, hydrogenated amorphous carbon (a-C:H) has much more controllable preparation processes. Study on a-C:H-based memory is of great significance to applications of carbon-based electronic devices. We observed nonvolatile resistance memory behaviors in metal/a-C:H/Pt structures with device yield 90%, ON/OFF ratio >100, and retention time >105 s. Detailed analysis indicates that the resistive switching originates from the formation/rupture of metal filaments due to the diffusion of the top electrodes under a bias voltage.

Pushing extended p-quinodimethanes to the limit: Stable tetracyano-oligo(N-annulated perylene)quinodimethanes with tunable ground states

p-Quinodimethane (p-QDM) is a fundamental building block for the design of π-conjugated systems with low band gap and open-shell biradical character. However, synthesis of extended p-QDMs has usually suffered from their intrinsic high reactivity and poor solubility. In this work, benzannulation together with terminal cyano-substitution was demonstrated to be an efficient approach for the synthesis of a series of soluble and stable tetracyano-oligo(N-annulated perylene)quinodimethanes nPer-CN (n = 1-6), with the longest molecule having 12 para-linked benzenoid rings! The geometry and electronic structures of these oligomers were investigated by steady-state and transient absorption spectroscopy, nuclear magnetic resonance, electron spin resonance, superconducting quantum interference device, and FT Raman spectroscopy assisted by density functional theory calculations. They showed tunable ground states, varying from a closed-shell quinoidal structure for monomer, to a singlet biradical for dimer, trimer, and tetramer, and to a triplet biradical for pentamer and hexamer. Large two-photon absorption cross-section values were observed in the near-infrared range, which also exhibited a clear chain-length dependence.

Dibenzoheptazethrene Isomers with Different Biradical Characters: An Exercise of Clar’s Aromatic Sextet Rule in Singlet Biradicaloids

Clars aromatic sextet rule has been widely used for the prediction of the reactivity and stability of polycyclic aromatic hydrocarbons with a closed-shell electronic configuration. Recent advances in open-shell biradicaloids have shown that the number of aromatic sextet rings plays an important role in determination of their ground states. In order to test the validity of this rule in singlet biradicaloids, the two soluble and stable dibenzoheptazethrene isomers DBHZ1 and DBHZ2 were prepared by different synthetic approaches and isolated in crystalline form. These two molecules have different numbers of aromatic sextet rings in their respective biradical resonance forms and thus are expected to exhibit varied singlet biradical character. This assumption was verified by different experimental methods, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), superconducting quantum interference device (SQUID), steady-state and transient absorption spectroscopy (TA), and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. DBHZ2, with more aromatic sextet rings in the biradical form, was demonstrated to possess greater biradical character than DBHZ1; as a result, DBHZ2 exhibited an intense one-photon absorption (OPA) in the near-infrared region (λabs(max) = 804 nm) and a large two-photon absorption (TPA) cross-section (σ((2))max = 2800 GM at 1600 nm). This investigation together with previous studies indicates that Clars aromatic sextet rule can be further extended to the singlet biradicaloids to predict their ground states and singlet biradical characters.

Mechanism for resistive switching in an oxide-based electrochemical metallization memory

A comparison of the asymmetric OFF-state current-voltage characteristics between Cu/ZnO/Pt and Cu/ZnO/Al-doped ZnO (AZO) electrochemical metallization memory (ECM) cells demonstrates that the Cu filament rupture and rejuvenation occur at the ZnO/Pt (or AZO) interface, i.e., the cathodic interface. Therefore, the filament is most likely to have a conical shape, with wider and narrower diameters formed at the anodic and cathodic interfaces, respectively. It is inferred that the filament growth starts at the anode surface and stops at the cathode surface. Our results indicate that oxide-based ECM cells strongly differ from sulfide- and selenide-based ones in the resistive switching mechanism. VC 2012 American Institute of Physics.

Nonvolatile resistive switching in metal/La-doped BiFeO3/Pt sandwiches

The resistive switching (RS) characteristics of a Bi(0.95)La(0.05)FeO(3) (La-BFO) film sandwiched between a Pt bottom electrode and top electrodes (TEs) made of Al, Ag, Cu, and Au have been studied. Devices with TEs made of Ag and Cu showed stable bipolar RS behaviors, whereas those with TEs made of Al and Au exhibited unstable bipolar RS. The Ag/La-BFO/Pt structure showed an on/off ratio of 10(2), a retention time > 10(5) s, and programming voltages < 1 V. The RS effect can be attributed to the formation/rupture of nanoscale metal filaments due to the diffusion of the TEs under a bias voltage. The maximum current before the reset process (on-to-off switching) was found to increase linearly with the current compliance applied during the set process (off-to-on switching).