Chan Su Jung

Tetragonal phase germanium nanocrystals in lithium ion batteries.

Various germanium-based nanostructures have recently demonstrated outstanding lithium ion storage ability and are being considered as the most promising candidates to substitute current carbonaceous anodes of lithium ion batteries. However, there is limited understanding of their structure and phase evolution during discharge/charge cycles. Furthermore, the theoretical model of lithium insertion still remains a challenging issue. Herein, we performed comparative studies on the cycle-dependent lithiation/delithiation processes of germanium (Ge), germanium sulfide (GeS), and germanium oxide (GeO2) nanocrystals (NCs). We synthesized the NCs using a convenient gas phase laser photolysis reaction and attained an excellent reversible capacity: 1100-1220 mAh/g after 100 cycles. Remarkably, metastable tetragonal (ST12) phase Ge NCs were constantly produced upon lithiation and became the dominant phase after a few cycles, completely replacing the original phase. The crystalline ST12 phase persisted through 100 cycles. First-principles calculations on polymorphic lithium-intercalated structures proposed that the ST12 phase Ge12Lix structures at x ≥ 4 become more thermodynamically stable than the cubic phase Ge8Lix structures with the same stoichiometry. The production and persistence of the ST12 phase can be attributed to a stronger binding interaction of the lithium atoms compared to the cubic phase, which enhanced the cycling performance.

Phase evolution of tin nanocrystals in lithium ion batteries.

Sn-based nanostructures have emerged as promising alternative materials for commercial lithium-graphite anodes in lithium ion batteries (LIBs). However, there is limited information on their phase evolution during the discharge/charge cycles. In the present work, we comparatively investigated how the phases of Sn, tin sulfide (SnS), and tin oxide (SnO2) nanocrystals (NCs) changed during repeated lithiation/delithiation processes. All NCs were synthesized by a convenient gas-phase photolysis of tetramethyl tin. They showed excellent cycling performance with reversible capacities of 700 mAh/g for Sn, 880 mAh/g for SnS, and 540 mAh/g for SnO2 after 70 cycles. Tetragonal-phase Sn (β-Sn) was produced upon lithiation of SnS and SnO2 NCs. Remarkably, a cubic phase of diamond-type Sn (α-Sn) coexisting with β-Sn was produced by lithiation for all NCs. As the cycle number increased, α-Sn became the dominant phase. First-principles calculations of the Li intercalation energy of α-Sn (Sn8) and β-Sn (Sn4) indicate that Sn4Li(x) (x ≤ 3) is thermodynamically more stable than Sn8Li(x) (x ≤ 6) when both have the same composition. α-Sn maintains its crystalline form, while β-Sn becomes amorphous upon lithiation. Based on these results, we suggest that once α-Sn is produced, it can retain its crystallinity over the repeated cycles, contributing to the excellent cycling performance.

CdSSe layer-sensitized TiO2 nanowire arrays as efficient photoelectrodes

Complete composition-tuned CdSxSe1−x alloy layers (avg. thickness = 50 nm) were deposited on pre-grown TiO2 nanowires by the thermal vapor transport of CdS/CdSe powders, producing core–shell nanocable arrays. CdSxSe1−x alloy nanowires were also synthesized with full composition tuning by the same method for comparison. The CdSSe nanowires consisted of Se-rich and S-rich pseudo binary phases, while the nanocable shell consisted of more complex multinary phases including CdSe and CdS. Remarkably, unique CdS–CdSSe–CdSe multishell structures were produced in the Se-rich composition range. The photoelectrochemical (PEC) cells fabricated using the as-grown nanocable arrays show higher solar photocurrents and hydrogen generation rates for the Se-rich shelled TiO2 nanocable arrays. This suggests that the CdS–CdSSe–CdSe multishell structures increase greatly the PEC performance by producing novel band alignment for efficient electron–hole separation following enhanced visible-range photon absorption.

Germanium sulfide(II and IV) nanoparticles for enhanced performance of lithium ion batteries

Germanium sulfide (GeS and GeS2) nanoparticles were synthesized by novel gas-phase laser photolysis and subsequent thermal annealing. They showed excellent cycling performance for lithium ion batteries, with a maximum capacity of 1010 mA h g(-1) after 100 cycles. Metastable tetragonal phase Ge nanoparticles were suggested as active materials for a reversible lithium insertion-extraction process.

Germanium–tin alloy nanocrystals for high-performance lithium ion batteries

Germanium-tin (Ge(1-x)Sn(x)) alloy nanocrystals were synthesized using a gas-phase laser photolysis reaction of tetramethyl germanium and tetramethyl tin. A composition tuning was achieved using the partial pressure of precursors in a closed reactor. For x < 0.1, cubic phase alloy nanocrystals were exclusively produced without separation of the tetragonal phase Sn metal. In the range of x = 0.1-0.4, unique Ge(1-x)Sn(x)-Sn alloy-metal hetero-junction nanocrystals were synthesized, where the Sn metal domain becomes dominant with x. Thin graphitic carbon layers usually sheathed the nanocrystals. We investigated the composition-dependent electrochemical properties of these nanocrystals as anode materials of lithium ion batteries. Incorporation of Sn (x = 0.05) significantly increased the capacities (1010 mA h g(-1) after 50 cycles) and rate capabilities, which promises excellent electrode materials for the development of high-performance lithium batteries.

Red-to-Ultraviolet Emission Tuning of Two-Dimensional Gallium Sulfide/Selenide

Graphene-like two-dimensional (2D) nanostructures have attracted significant attention because of their unique quantum confinement effect at the 2D limit. Multilayer nanosheets of GaS-GaSe alloy are found to have a band gap (Eg) of 2.0-2.5 eV that linearly tunes the emission in red-to-green. However, the epitaxial growth of monolayers produces a drastic increase in this Eg to 3.3-3.4 eV, which blue-shifts the emission to the UV region. First-principles calculations predict that the Eg of these GaS and GaSe monolayers should be 3.325 and 3.001 eV, respectively. As the number of layers is increased to three, both the direct/indirect Eg decrease significantly; the indirect Eg approaches that of the multilayers. Oxygen adsorption can cause the direct/indirect Eg of GaS to converge, resulting in monolayers with a strong emission. This wide Eg tuning over the visible-to-UV range could provide an insight for the realization of full-colored flexible and transparent light emitters and displays.

Zn2GeO4 and Zn2SnO4 nanowires for high-capacity lithium- and sodium-ion batteries

Germanium (Ge) and tin (Sn) are considered to be the most promising alternatives to commercial carbon materials in lithium- and sodium-ion batteries. High-purity zinc germanium oxide (Zn2GeO4) and zinc tin oxide (Zn2SnO4) nanowires were synthesized using a hydrothermal method, and their electrochemical properties as anode materials in lithium- and sodium-ion batteries were comparatively investigated. The nanowires had a uniform morphology and consisted of single-crystalline rhombohedral (Zn2GeO4) and cubic (Zn2SnO4) phases. For lithium ion batteries, Zn2GeO4 and Zn2SnO4 showed an excellent cycling performance, with a capacity of 1220 and 983 mA h g−1 after 100 cycles, respectively. Their high capacities are attributed to a combination of the alloy formation reaction of Zn and Ge (or Sn) with Li, and the conversion reactions: ZnO + 2Li+ + 2e− ↔ Zn + Li2O and GeO2 (or SnO2) + 4Li+ + 4e− ↔ Ge (or Sn) + 2Li2O. For the first time, we examined the cycling performance of Zn2GeO4 and Zn2SnO4 in sodium ion batteries; their capacities were 342 mA h g−1 and 306 mA h g−1 after 100 cycles, respectively. The capacity of Zn2SnO4 is much higher than the theoretical capacity (100 mA h g−1), while that of Zn2SnO4 is close to the theoretical capacity (320 mA h g−1). We suggest a contribution of the conversion reaction in increasing the capacities, which is similar to the case of lithium ion batteries. The present systematic comparison between the lithiation and sodiation will provide valuable information for the development of high-performance lithium- and sodium-ion batteries.

Facile phase and composition tuned synthesis of tin chalcogenide nanocrystals

We synthesized polytypic tin sulfide, SnS, Sn2S3, and SnS2 nanocrystals, by means of novel gas-phase laser photolysis of tetramethyl tin and hydrogen sulfide. A facile composition tuning through the pressure of precursors (addition of dimethyl selenium) yields a series of orthorhombic phase SnX and hexagonal phase SnX2, where X = SxSe1−x with 0 ≤ x ≤ 1. Various polytypic hybrids such as SnS–Sn2S3–SnS2, SnS–SnS2, Sn2S3–SnS2, and SnSe–SnSe2 were synthesized. This resulted in the ability to tune the band gap over a wide range (1.0–2.3 eV). Their photon energy conversion properties were investigated by fabricating photodetector devices using the nanocrystal-reduced graphene oxide nanocomposites. The enhanced photoconversion efficiency was observed from the polytypic hybrid nanostructures. This original synthesis method for tin chalcogenide nanocrystals is expected to help expand applications in high-performance energy conversion systems.

Polymorphism of GeSbTe Superlattice Nanowires

Scaling-down of phase change materials to a nanowire (NW) geometry is critical to a fast switching speed of nonvolatile memory devices. Herein, we report novel composition-phase-tuned GeSbTe NWs, synthesized by a chemical vapor transport method, which guarantees promising applications in the field of nanoscale electric devices. As the Sb content increased, they showed a distinctive rhombohedral-cubic-rhombohedral phase evolution. Remarkable superlattice structures were identified for the Ge(8)Sb(2)Te(11), Ge(3)Sb(2)Te(6), Ge(3)Sb(8)Te(6), and Ge(2)Sb(7)Te(4) NWs. The coexisting cubic-rhombohedral phase Ge(3)Sb(2)Te(6) NWs exhibited an exclusively uniform superlattice structure consisting of 2.2 nm period slabs. The rhombohedral phase Ge(3)Sb(8)Te(6) and Ge(2)Sb(7)Te(4) NWs adopted an innovative structure; 3Sb(2) layers intercalated the Ge(3)Sb(2)Te(6) and Ge(2)Sb(1)Te(4) domains, respectively, producing 3.4 and 2.7 nm period slabs. The current-voltage measurement of the individual NW revealed that the vacancy layers of Ge(8)Sb(2)Te(11) and Ge(3)Sb(2)Te(6) decreased the electrical conductivity.

Zn3P2–Zn3As2 Solid Solution Nanowires

Semiconductor alloy nanowires (NWs) have recently attracted considerable attention for applications in optoelectronic nanodevices because of many notable properties, including band gap tunability. Zinc phosphide (Zn3P2) and zinc arsenide (Zn3As2) belong to a unique pseudocubic tetragonal system, but their solid solution has rarely been studied. Here In this study, we synthesized composition-tuned Zn3(P1-xAsx)2 NWs with different crystal structures by controlling the growth conditions during chemical vapor deposition. A first type of synthesized NWs were single-crystalline and grew uniformly along the [110] direction (in a cubic unit cell) over the entire compositional range (0 ≤ x ≤ 1) explored. The use of an indium source enabled the growth of a second type of NWs, with remarkable cubic-hexagonal polytypic twinned superlattice and bicrystalline structures. The growth direction of the Zn3P2 and Zn3As2 NWs was also switched to [111] and [112], respectively. These structural changes are attributable to the Zn-depleted indium catalytic nanoparticles which favor the growth of hexagonal phases. The formation of a solid solution at all compositions allowed the continuous tuning of the band gap (1.0-1.5 eV). Photocurrent measurements were performed on individual NWs by fabricating photodetector devices; the single-crystalline NWs with [110] growth direction exhibit a higher photoconversion efficiency compared to the twinned crystalline NWs with [111] or [112] growth direction.