Thickness-dependent and anisotropic thermal conductivity of black phosphorus nanosheets.

Thickness effects on thermal conductivities of black phosphorus nanosheets, which are anisotropic in the zigzag and armchair planar directions, are experimentally and theoretically investigated in the thickness range of 13 to 48 nm. The thermal conductivities decrease with the thickness, decreasing from 13 to 8 W m-1 K-1 in the zigzag direction and from 10 to 6 W m-1 K-1 in the armchair direction at 300 K, respectively. The anisotropic thermal conductivities, regardless of the thickness, might result from the anisotropic phonon velocity arising from the hinge-like structure. The surface-driven suppression of the thermal conductivities at a nanometer scale is remarkable for a wide temperature range of 100 to 300 K due to phonon-boundary scattering, while the thermal conductivity becomes less dependent on the thickness at higher temperatures above 300 K, owing to the dominant phonon-phonon scattering.

Anomalous thermoelectricity of pure ZnO from 3D continuous ultrathin nanoshell structures.

ZnO is a potential thermoelectric material because of its non-toxicity, high thermal stability, and relatively high Seebeck coefficient (S) of metal oxides. However, the extremely low figure of merit (zT), which comes from a high thermal conductivity (κ) over 40 W m-1 K-1, limits the thermoelectric application of ZnO. In particular, below 500 K, ZnO exhibits a nearly negligible zT (<10-3), unless a dopant is incorporated into the crystal structure. Here, we propose a new strategy for achieving a reduced κ and a correspondingly increased zT of pure ZnO over a wide temperature range from 333 K to 723 K by forming an ∼72 nm thick, 3D continuous ultrathin nanoshell structure. The suppressed κ of the 3D ZnO film is ∼3.6 W m-1 K-1 at 333 K, which is ∼38 times lower than that of the blanket ZnO film (3.2 µm thick), which was set as a reference. The experimental zT of the 3D ZnO film is ∼0.017 at 333 K, which is the highest value among pure ZnO reported to date and is estimated to increase by ∼0.072 at 693 K according to the Debye-Callaway approach. Large-area (∼1 in2) fabrication of the 3D ZnO film with high structural uniformity allows the realization of an integrated thermoelectric device, which generates ∼60 mV at a temperature difference of 40 K along the in-plane direction.

Thermoelectric materials by using two-dimensional materials with negative correlation between electrical and thermal conductivity.

In general, in thermoelectric materials the electrical conductivity σ and thermal conductivity κ are related and thus cannot be controlled independently. Previously, to maximize the thermoelectric figure of merit in state-of-the-art materials, differences in relative scaling between σ and κ as dimensions are reduced to approach the nanoscale were utilized. Here we present an approach to thermoelectric materials using tin disulfide, SnS2, nanosheets that demonstrated a negative correlation between σ and κ. In other words, as the thickness of SnS2 decreased, σ increased whereas κ decreased. This approach leads to a thermoelectric figure of merit increase to 0.13 at 300 K, a factor ∼1,000 times greater than previously reported bulk single-crystal SnS2. The Seebeck coefficient obtained for our two-dimensional SnS2 nanosheets was 34.7 mV K(-1) for 16-nm-thick samples at 300 K.

Structural and electrical properties of catalyst-free Si-doped InAs nanowires formed on Si(111).

We report structural and electrical properties of catalyst-free Si-doped InAs nanowires (NWs) formed on Si(111) substrates. The average diameter of Si-doped InAs NWs was almost similar to that of undoped NWs with a slight increase in height. In the previous works, the shape and size of InAs NWs formed on metallic catalysts or patterned structures were significantly changed by introducing dopants. Even though the external shape and size of the Si-doped NWs in this work were not changed, crystal structures inside the NWs were significantly changed. For the undoped InAs NWs, both zincblende (ZB) and wurzite (WZ) structures were observed in transmission-electron microscope images, where the portion of WZ structure was estimated to be more than 30%. However, only ZB was observed with an increase in stacking fault (SF) for the Si-doped NWs. The undoped and Si-doped InAs NWs were used as channels of four-point electrical measurements with Al/Ni electrodes to investigate electrical properties. The resistivity calculated from the current-voltage curve of a Si-doped InAs NW showed 1.32 × 10(-3) Ωcm, which was dramatically decreased from 10.14 × 10(-3) Ωcm for the undoped InAs NW. A relatively low resistivity of catalyst-free Si-doped InAs NWs was achieved without significant change in structural dimensions.

Effect of the Thermal Conductivity on Resistive Switching in GeTe and Ge2Sb2Te5 Nanowires.

The thermal conduction characteristics of GeTe and Ge2Sb2Te5(GST) nanowires were investigated using an optical method to determine the local temperature by Raman spectroscopy. Since the localization of surface charge in a single-crystalline nanostructure can enhance charge-phonon scattering, the thermal conductivity value (κ) of single crystalline GeTe and GST nanowires was decreased significantly to 1.44 Wm(-1) K(-1) for GeTe and 1.13 Wm(-1) K(-1) for GST, compared to reported values for polycrystalline structures. The SET-to-RESET state in single-crystalline GeTe and GST nanowires are characteristic of a memory device. Unlike previous reports using GeTe and GST nanowires, the SET-to-RESET characteristics showed a bipolar switching shape and no unipolar switching. In addition, after multiple cycles of operation, a significant change in morphology and composition was observed without any structural phase transition, indicating that atoms migrate toward the cathode or anode, depending on their electronegativities. This change caused by a field effect indicates that the structural phase transition does not occur in the case of GeTe and GST nanowires with a significantly lowered thermal conductivity and stable crystalline structure. Finally, the formation of voids and hillocks as the result of the electromigration critically degrades device reliability.

Twin-driven thermoelectric figure-of-merit enhancement of Bi2Te3 nanowires.

Thermoelectric figure-of-merits (ZT) are enhanced or degraded by crystal defects such as twins and excess atoms that are correlated with thermal conductivity (k) and carrier concentration (n). For Bi2Te3, it is unclear whether the crystal defects can enhance ZT without a degradation in the thermopower factor. In the present study, n-type Bi2Te3 nanowires (NWs) are electrochemically synthesized to have twin-free (TF) or twin-containing (TC) microstructures with a ZT of 0.10 and 0.08, respectively, at 300 K. The ZTs of TF and TC NWs remarkably increase up to 0.21 and 0.31, when heat-treatments cause n-reduction and twins induce phonon scattering, as follows: first, the enhancement of the Seebeck coefficient from -70 to -98 µV K(-1) for TF NWs and from -57 to -143 µV K(-1) for TC NWs, by virtue of n-reduction; secondly, twin-driven k-reduction from 1.9 to 1.4 W m(-1) K(-1) of TC NWs, while the k of TF NWs increases from 2.3 to 2.6 W m(-1) K(-1) due to the enhanced carrier mobility. The lattice thermal conductivities of TC NW are lowered from 1.1 to 0.8 W m(-1) K(-1) by phonon scattering at twins. Density functional theory calculations indicate that twins do not significantly influence the Seebeck coefficient of Bi2Te3. It is strongly recommended that twins be incorporated with an optimum carrier concentration to enhance the ZT of Bi2Te3.