Junghyo Nah

p-Type InP Nanopillar Photocathodes for Efficient Solar-Driven Hydrogen Production†

Water splitting by using sunlight for the production of hydrogen yields a storable product, which can be used as a fuel. There is considerable research into H2 generation, namely the reduction of protons to H2 in aqueous solution using semiconductor photocathodes. To maximize the photoelectrochemical (PEC) performance, the selection of the active materials and device configurations should be carefully considered. First, the short-circuit current density (Jsc) should be maximized by choosing materials with high optical absorption coefficients and low carrier recombination rates, both in the bulk and at the surface. The reflectance should be minimized by using surface nanotexturing to further improve light absorption. The onset potential (Eos) of the PEC device versus the reversible H /H2 redox potential should be maximized. Finally, the surface energy needs to be controlled to minimize the accumulation of gas bubbles on the surface of the photoelectrode. Light absorbers with band gaps in the range of 1.1–1.7 eV provide both a good match to the terrestrial solar spectrum and a significant fraction of the 1.23 eV free energy required to split water. Overpotentials associated with the electron transfer to (solvated) protons in aqueous solution should be minimized by improving carrier transport from semiconductor to electrolyte by decorating the semiconductor with cocatalysts, tuning band edges, and decreasing contact resistance. p-Type Si has been extensively investigated as a photocathode for photochemical hydrogen production. Planar Si has relatively low short-circuit current densities under AM1.5 G illumination, approximately 10 mAcm 2 (reference [9]), compared to what can be achieved in a pn junction solar cell (> 35 mAcm ). Nanostructuring and incorporation of cocatalysts have been used to raise the short-circuit current density to over 30 mAcm . A recent study using np Si radial junction microwires reported an Eos value of 0.54 V and an Jsc value of 15 mA, leading to an overall efficiency near 6%. The onset potential observed to date for p-Si photocathodes is less than half of the value required for overall water splitting (1.23 V). This low onset potential limits the performance of tandem or “Z-scheme” approaches, which would function without external bias, as it limits the potential overlap required for spontaneous water splitting. An ideal photocathode for use in a solar-driven hydrogen production system without bias should have both a high current density and a favorable open-circuit potential versus the reversible H/H2 redox couple. Herein, we employ nanotextured p-InP photocathodes in conjunction with a TiO2 passivation layer and a Ru cocatalyst to increase both Jsc and Eos values under H2 evolution conditions. InP has a number of attractive attributes as a photocathode: 1) Its band gap of 1.3 eV is well-matched to the solar spectrum; InP-based solar cells have achieved AM1.5 G efficiencies of up to 22%. 2) The conduction band edge of InP is slightly above the water reduction potential, thus electron transfer is favorable in this system. 3) The surface-recombination velocity of untreated InP is low (ca. 10 cms 1 for n-type and 10 cms 1 for p-type), which is particularly important for nonplanar devices with high surface areas, such as those explored in this study. For these reasons, InP has been studied previously as a photocathode for both water splitting and CO2 reduction. [18–20] Specifically, Heller and Vadimsky reported attractive PEC performances with current densities up to 28 mAcm 2 and conversion efficiencies of approximately 12% in InP photocathodes. Motivated by these results, we use InP as a model material system to elucidate the role of surface nanotexturing on the PEC device performance. We find that nanotextured InP photocathodes exhibit drastically enhanced performances compared to our planar cells that were processed using identical conditions. We examine the various effects of nanotexturing [*] M. H. Lee, K. Takei, J. Zhang, R. Kapadia, M. Zheng, J. Nah, J. W. Ager, Prof. A. Javey Material Sciences Division, Lawrence Berkeley National Laboratory Berkeley, CA 94720 (USA) E-mail: jwager@lbl.gov ajavey@berkeley.edu M. H. Lee, K. Takei, J. Zhang, R. Kapadia, M. Zheng, J. Nah, Prof. A. Javey Electrical Engineering and Computer Sciences University of California, Berkeley, CA 94720 (USA) M. H. Lee, T. S. Matthews, J. W. Ager, Prof. A. Javey Joint Center for Artificial Photosynthesis Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (USA)

Hemispherically Aggregated BaTiO3 Nanoparticle Composite Thin Film for High-Performance Flexible Piezoelectric Nanogenerator

We report high-performance flexible nanogenerators (NGs) based on a composite thin film, composed of hemispherically aggregated BaTiO3 nanoparticles (NPs) and poly(vinylidene fluoride-co-hexafluoropropene) P(VDF-HFP). The hemispherical BTO-P(VDF-HFP) clusters were realized by a solvent evaporation method, which greatly enhanced piezoelectric power generation. The flexible NGs exhibit high electrical output up to ∼75 V and ∼15 μA at the applied force normal to the surface, indicating the important role of hemispherical BTO clusters. Besides, the durability and reproducibility of the NGs were tested by cyclic measurement under bending stage, generating the output of ∼5 V and ∼750 nA. The approach we introduce here is simple, cost-effective, and well-suited for large-scale high-performance flexible NG fabrication.

Nanoscale InGaSb heterostructure membranes on Si substrates for high hole mobility transistors.

As of yet, III-V p-type field-effect transistors (p-FETs) on Si have not been reported, due partly to materials and processing challenges, presenting an important bottleneck in the development of complementary III-V electronics. Here, we report the first high-mobility III-V p-FET on Si, enabled by the epitaxial layer transfer of InGaSb heterostructures with nanoscale thicknesses. Importantly, the use of ultrathin (thickness, ~2.5 nm) InAs cladding layers results in drastic performance enhancements arising from (i) surface passivation of the InGaSb channel, (ii) mobility enhancement due to the confinement of holes in InGaSb, and (iii) low-resistance, dopant-free contacts due to the type III band alignment of the heterojunction. The fabricated p-FETs display a peak effective mobility of ~820 cm(2)/(V s) for holes with a subthreshold swing of ~130 mV/decade. The results present an important advance in the field of III-V electronics.

III–V Complementary Metal–Oxide–Semiconductor Electronics on Silicon Substrates

One of the major challenges in further advancement of III-V electronics is to integrate high mobility complementary transistors on the same substrate. The difficulty is due to the large lattice mismatch of the optimal p- and n-type III-V semiconductors. In this work, we employ a two-step epitaxial layer transfer process for the heterogeneous assembly of ultrathin membranes of III-V compound semiconductors on Si/SiO(2) substrates. In this III-V-on-insulator (XOI) concept, ultrathin-body InAs (thickness, 13 nm) and InGaSb (thickness, 7 nm) layers are used for enhancement-mode n- and p- MOSFETs, respectively. The peak effective mobilities of the complementary devices are ∼1190 and ∼370 cm(2)/(V s) for electrons and holes, respectively, both of which are higher than the state-of-the-art Si MOSFETs. We demonstrate the first proof-of-concept III-V CMOS logic operation by fabricating NOT and NAND gates, highlighting the utility of the XOI platform.

Self-aligned, extremely high frequency III-V metal-oxide-semiconductor field-effect transistors on rigid and flexible substrates.

This paper reports the radio frequency (RF) performance of InAs nanomembrane transistors on both mechanically rigid and flexible substrates. We have employed a self-aligned device architecture by using a T-shaped gate structure to fabricate high performance InAs metal-oxide-semiconductor field-effect transistors (MOSFETs) with channel lengths down to 75 nm. RF measurements reveal that the InAs devices made on a silicon substrate exhibit a cutoff frequency (f(t)) of ∼165 GHz, which is one of the best results achieved in III-V MOSFETs on silicon. Similarly, the devices fabricated on a bendable polyimide substrate provide a f(t) of ∼105 GHz, representing the best performance achieved for transistors fabricated directly on mechanically flexible substrates. The results demonstrate the potential of III-V-on-insulator platform for extremely high-frequency (EHF) electronics on both conventional silicon and flexible substrates.

High mobility strained germanium quantum well field effect transistor as the p-channel device option for low power (Vcc = 0.5 V) III–V CMOS architecture

In this article we demonstrate a Ge p-channel QWFET with scaled TOXE = 14.5Å and mobility of 770 cm2/V*s at ns =5×1012 cm−2 (charge density in the state-of-the-art Si transistor channel at Vcc = 0.5V). For thin TOXE < 40 Å, this represents the highest hole mobility reported for any Ge device and is 4× higher than state-of-the-art strained silicon. The QWFET architecture achieves high mobility by incorporating biaxial strain and eliminating dopant impurity scattering. The thin TOXE was achieved using a Si cap and a low Dt transistor process, which has a low oxide interface Dit. Parallel conduction in the SiGe buffer was suppressed using a phosphorus junction layer, allowing healthy subthreshold slope in Ge QWFET for the first time. The Ge QWFET achieves an intrinsic Gmsat which is 2× higher than the InSb p-channel QWFET [3]. These results suggest the Ge QWFET is a viable p-channel option for non-silicon CMOS.

Triboelectric Charging Sequence Induced by Surface Functionalization as a Method To Fabricate High Performance Triboelectric Generators

Two different materials, apart from each other in a triboelectric series, are required to fabricate high performance triboelectric generators (TEGs). Thus, it often limits the choices of materials and causes related processing issues for TEGs. To address this issue, we report a simple surface functionalization method that can effectively change the triboelectric charging sequence of the materials, broadening material choices and enhancing the performance of TEGs. Specifically, we functionalized the surfaces of the polyethylene terephthalate (PET) films either with poly-l-lysine solution or trichloro(1H,1H,2H,2H-perfluorooctyl) silane (FOTS). Consequently, the PET surfaces were modified to have different triboelectric polarities in a triboelectric series. The TEGs, fabricated using this approach, demonstrated the maximum Vopen-circuit (Voc) of ∼330 V and Jshort-circuit (Jsc) of ∼270 mA/m(2), respectively, at an applied force of 0.5 MPa. Furthermore, the functionalized surfaces of TEGs demonstrated superior stability during cyclic measurement over 7200 cycles, maintaining the performance even after a month. The approach introduced here is a simple, effective, and cost-competitive way to fabricate TEGs, which can also be easily adopted for various surface patterns and device structures.

Lithium-Doped Zinc Oxide Nanowires–Polymer Composite for High Performance Flexible Piezoelectric Nanogenerator

We present a method to develop high performance flexible piezoelectric nanogenerators (NGs) by employing Li-doped ZnO nanowires (NWs). We synthesized Li-doped ZnO NWs and adopted them to replace intrinsic ZnO NWs with a relatively low piezoelectric coefficient. When we exploited the ferroelectric phase transition induced in Li-doped ZnO NWs, the performance of the NGs was significantly improved and the NG fabrication process was greatly simplified. In addition, our approach can be easily expanded for large-scale NG fabrication. Consequently, the NGs fabricated by our simple method exhibit the excelling output voltage and current, which are stable and reproducible during periodic bending/releasing measurement over extended cycles. In addition, output voltage and current up to ∼ 180 V and ∼ 50 μA, respectively, were obtained in the large-scale NG. The approach introduced here extends the performance limits of ZnO-based NGs and their potentials in practical applications.

Lateral spin injection in germanium nanowires.

Electrical injection of spin-polarized electrons into a semiconductor, large spin diffusion length, and an integration friendly platform are desirable ingredients for spin-based devices. Here we demonstrate lateral spin injection and detection in germanium nanowires, by using ferromagnetic metal contacts and tunnel barriers for contact resistance engineering. Using data measured from over 80 samples, we map out the contact resistance window for which lateral spin transport is observed, manifestly showing the conductivity matching required for spin injection. Our analysis, based on the spin diffusion theory, indicates that the spin diffusion length is larger than 100 mum in germanium nanowires at 4.2 K.

Piezoelectric properties of CH3NH3PbI3 perovskite thin films and their applications in piezoelectric generators

CH3NH3PbI3 (MAPbI3) perovskite thin films were applied to fluorine-doped SnO2 (FTO)/glass and Au/Ti/polyethylene terephthalate (PET) substrates via a two-step process, which involved depositing a CH3NH3I (MAI) solution onto PbI2 films via spin-coating followed by crystallization at temperatures of 100 °C. The 500 nm-thick crystallized MAPbI3 perovskite thin films showed a Curie temperature of ∼328 K, a dielectric permittivity of ∼52, a dielectric loss of ∼0.02 at 1 MHz, and a low leakage current density of ∼10−7 A cm−2 at ±3 V. The polarization–electric field (P–E) hysteresis loop and piezoresponse force microscopy (PFM) results showed that the films had well-developed ferroelectric properties and switchable polarization. Poling at an electrical field of 80 kV cm−1 enhanced the power density of the generator. The values for output voltage and current density of the poled films reached 2.7 V and 140 nA cm−2, respectively, which were 2.7-fold higher than those of the non-poled samples.