Li-Yong Gan

Atomic-scale observation of lithiation reaction front in nanoscale SnO2 materials.

In the present work, taking advantage of aberration-corrected scanning transmission electron microscopy, we show that the dynamic lithiation process of anode materials can be revealed in an unprecedented resolution. Atomically resolved imaging of the lithiation process in SnO2 nanowires illustrated that the movement, reaction, and generation of b = [1[overline]1[overline]1] mixed dislocations leading the lithiated stripes effectively facilitated lithium-ion insertion into the crystalline interior. The geometric phase analysis and density functional theory simulations indicated that lithium ions initial preference to diffuse along the [001] direction in the {200} planes of SnO2 nanowires introduced the lattice expansion and such dislocation behaviors. At the later stages of lithiation, the Li-induced amorphization of rutile SnO2 and the formation of crystalline Sn and LixSn particles in the Li2O matrix were observed.

Photovoltaic Heterojunctions of Fullerenes with MoS2 and WS2 Monolayers.

First-principles calculations are performed to explore the geometry, bonding, and electronic structures of six ultrathin photovoltaic heterostructures consisting of pristine and B- or N-doped fullerenes and MoS2 or WS2 monolayers. The fullerenes prefer to be attached with a hexagon parallel to the monolayer, where B and N favor proximity to the monolayer. The main electronic properties of the subsystems stay intact, suggesting weak interfacial interaction. Both the C60/MoS2 and C60/WS2 systems show type-II band alignments. However, the built-in potential in the former case is too small to effectively drive electron-hole separation across the interface, whereas the latter system is predicted to show good photovoltaic performance. Unfortunately, B and N doping destroys the type-II band alignment on MoS2 and preserves it only in one spin channel on WS2, which is unsuitable for excitonic solar cells. Our results suggest that the C60/WS2 system is highly promising for excitonic solar cells.

Origin of the Phase Transition in Lithiated Molybdenum Disulfide

Phase transitions and phase engineering in two-dimensional MoS2 are important for applications in electronics and energy storage. By in situ transmission electron microscopy, we find that H-MoS2 transforms to T-LiMoS2 at the early stages of lithiation followed by the formation of Mo and Li2S phases. The transition from H-MoS2 to T-LiMoS2 is explained in terms of electron doping and electron-phonon coupling at the conduction band minima. Both are essential for the development of two-dimensional semiconductor-metal contacts based on MoS2 and the usage of MoS2 as anode material in Li ion batteries.

Twin boundary-assisted lithium ion transport.

With the increased need for high-rate Li-ion batteries, it has become apparent that new electrode materials with enhanced Li-ion transport should be designed. Interfaces, such as twin boundaries (TBs), offer new opportunities to navigate the ionic transport within nanoscale materials. Here, we demonstrate the effects of TBs on the Li-ion transport properties in single crystalline SnO2 nanowires. It is shown that the TB-assisted lithiation pathways are remarkably different from the previously reported lithiation behavior in SnO2 nanowires without TBs. Our in situ transmission electron microscopy study combined with direct atomic-scale imaging of the initial lithiation stage of the TB-SnO2 nanowires prove that the lithium ions prefer to intercalate in the vicinity of the (101̅) TB, which acts as conduit for lithium-ion diffusion inside the nanowires. The density functional theory modeling shows that it is energetically preferred for lithium ions to accumulate near the TB compared to perfect neighboring lattice area. These findings may lead to the design of new electrode materials that incorporate TBs as efficient lithium pathways, and eventually, the development of next generation rechargeable batteries that surpass the rate performance of the current commercial Li-ion batteries.

Order-disorder phase transitions in the two-dimensional semiconducting transition metal dichalcogenide alloys Mo1−xWxX2 (X = S, Se, and Te)

A combination of density functional theory, an empirical model, and Monte Carlo simulations is used to shed light on the evolution of the atomic distribution in the two-dimensional semiconducting transition metal dichalcogenide alloys Mo1−xWxX2 (X = S, Se, and Te) as a function of the W concentration and temperature. Both random and ordered phases are discovered and the origin of the phase transitions is clarified. While the empirical model predicts at x = 1/3 and 2/3 ordered alloys, Monte Carlo simulations suggest that they only exist at low temperature due to a small energetic preference of Mo-X-W over Mo-X-Mo and W-X-W interactions, explaining the experimental observation of random alloy Mo1−xWxS2. Negative formation energies point to a high miscibility. Tunability of the band edges and band gaps by alteration of the W concentration gives rise to a broad range of applications.

Improved charge transfer and photoelectrochemical performance of CuI/Sb2S3/TiO2 heterostructure nanotube arrays.

Charge transfer is important for the performance of a photoelectrochemical cell. Understanding photogenerated charge accumulation and separation is mandatory for the design and optimisation of photoelectrochemical cells. Unique stacked and embedded heterostructure of Sb2S3/TiO2 nanotube arrays (NTAs) was fabricated through anodic oxidation with the hydrothermal method. Surface photovoltage spectroscopy, phase spectra and photoluminescence measurements were performed to explore the mechanism by which the inorganic hole transport material CuI affects the charge transfer and photoelectrochemical properties of Sb2S3/TiO2 heterostructure NTAs. The interfacial separation and transport of photoinduced charge carriers were also examined by applying current-voltage characteristics (J-V), incident-photon-to-current conversion efficiency (IPCE) and Mott-Schottky techniques. Results show that CuI acts not only as a hole-conducting and electron-blocking material but also as a light-absorbing material in the ultraviolet range. Efficient charge transfer processes exist in CuI/Sb2S3/TiO2 heterostructure NTAs. The photoelectrochemical performance of CuI/Sb2S3/TiO2 heterostructure NTAs is dramatically improved. Under AM 1.5G illumination at 100mW/cm(2), the short-circuit current density and open-circuit voltage are 3.51mA/cm(2) and 0.87V, respectively. The photoelectric conversion efficiency of CuI/Sb2S3/TiO2 heterostructure NTAs (0.95%) is 36% higher than that of Sb2S3/TiO2 heterostructure NTAs (0.66%).

Surface structure and phase transition of K adsorption on Au(111): by ab initio atomistic thermodynamics.

We studied the interactions between atomic potassium (K) and Au(111) at a range of coverage (i.e., Θ(K) = 0.11-0.5 monolayer (ML)) by ab initio atomic thermodynamics. For K on-surface adsorption, we found that K energetically favors the three-fold hollow sites (fcc or hcp), while the most significant surface rumpling was obtained at the atop sites. The incorporation of gold atoms in the adsorbate layer gradually becomes energetically favorable with increasing K coverage. We proposed a possible model with a stoichiometry of K(2)Au for the (2 × 2)-0.5 ML phase observed in lower energy electron diffraction (LEED): one K at atop site and the other K as well as one Au adatom at the second-nearest fcc/hcp and hcp/fcc, respectively. Clear theoretical evidences were given for the ionic interaction of K on Au surface. Additionally, phase transitions were predicted based on chemical potential equilibrium of K, largely in line with the earlier reported LEED observations: the clean surface → (√3 × √3)R30° → (2 × 2), and (2 × 2) → (√3 × √3)R30° reversely at an elevated temperature.

A global view of the phase transitions of SnO2 in rechargeable batteries based on results of high throughput calculations

Lithium, sodium and magnesium have attracted wide attention as potential ions for rechargeable batteries. The Materials Project database of high throughput first principles calculations is used to investigate the phase transitions of SnO2 during ion intercalation and extraction. Various intermediate phases are predicted to be formed during the first intercalation, whereas in later cycles other intermediate phases are encountered. The volume expansions after intercalation and extraction are analyzed. We show that different lithium and sodium oxide products found in recent experiments are due to different oxygen chemical potentials.

Exploring molecules beyond CO as tip functionalizations in high-resolution noncontact atomic force microscopy: A first principles approach

Atomic resolution of molecules has been achieved using noncontact atomic force microscopy (AFM) with the key step to functionalize the tip apex by attaching suitable molecules so as to achieve high spatial resolution through a sharper tip. A few molecular terminations have been explored theoretically and experimentally, and they exhibit various imaging behaviors. Here, we explore the influence of the structures and chemical compositions of various molecular candidates as tips on the contrast of AFM images by a first principles approach. Our results reveal that the two end atoms of a linear molecule terminating nearest the sample dominate the imaging behaviors, for example, atomic resolution, sharpness, distortion, and so forth, whereas the symmetry of the termination plays an important role in the distortion of AFM images. These findings suggest that new tip terminations can be engineered by decoupling the three end atoms responsible for imaging behaviors from the tip structure behind them, which is attached to the macro tip apex.

Stacking Modes-Induced Chemical Reactivity Differences on Chemical Vapor Deposition-Grown Trilayer Graphene

Trilayer graphene (TLG) synthesized by chemical vapor deposition (CVD), in particular the twisted TLG, exhibits sophisticated electronic structures that depend on their stacking modes. Here, we computationally and experimentally demonstrate the chemical reactivity differences of CVD-TLG induced by the stacking modes and corroborated by a photoexcited phenyl-grafting reaction. The experimental results show that the ABA stacking TLGs have the most inert chemical property, yet 30°-30° stacking twisted TLGs are the most active. Further, density functional theory calculations have shown that the chemical reactivity difference can be quantitatively explained by the differences in the number of hot electrons generated in their valence band during irradiation. The activity difference is further verified by the calculated adsorption energy of phenyl on the TLGs. Our work provides insight into the chemistry of TLG and addresses the challenges associated with selective functionalization of TLG with phenyl groups. The understandings developed in this project can also guide the future development of TLG-based functional devices.