Michael A. Filler

Photovoltaic Measurements in Single-Nanowire Silicon Solar Cells

Single-nanowire solar cells were created by forming rectifying junctions in electrically contacted vapor-liquid-solid-grown Si nanowires. The nanowires had diameters in the range of 200 nm to 1.5 microm. Dark and light current-voltage measurements were made under simulated Air Mass 1.5 global illumination. Photovoltaic spectral response measurements were also performed. Scanning photocurrent microscopy indicated that the Si nanowire devices had minority carrier diffusion lengths of approximately 2 microm. Assuming bulk-dominated recombination, this value corresponds to a minimum carrier lifetime of approximately 15 ns, or assuming surface-dominated recombination, to a maximum surface recombination velocity of approximately 1350 cm s(-1). The methods described herein comprise a valuable platform for measuring the properties of semiconductor nanowires, and are expected to be instrumental when designing an efficient macroscopic solar cell based on arrays of such nanostructures.

Growth of vertically aligned Si wire arrays over large areas (>1cm2) with Au and Cu catalysts

Arrays of vertically oriented Si wires with diameters of 1.5 µm and lengths of up to 75 µm were grown over areas >1 cm^2 by photolithographically patterning an oxide buffer layer, followed by vapor-liquid-solid growth with either Au or Cu as the growth catalyst. The pattern fidelity depended critically on the presence of the oxide layer, which prevented migration of the catalyst on the surface during annealing and in the early stages of wire growth. These arrays can be used as the absorber material in novel photovoltaic architectures and potentially in photonic crystals in which large areas are needed.

Secondary ion mass spectrometry of vapor−liquid−solid grown, Au-catalyzed, Si wires

Knowledge of the catalyst concentration within vapor-liquid-solid (VLS) grown semiconductor wires is needed in order to assess potential limits to electrical and optical device performance imposed by the VLS growth mechanism. We report herein the use of secondary ion mass spectrometry to characterize the Au catalyst concentration within individual, VLS-grown, Si wires. For Si wires grown by chemical vapor deposition from SiCl 4 at 1000 degrees C, an upper limit on the bulk Au concentration was observed to be 1.7 x 10(16) atoms/cm(3), similar to the thermodynamic equilibrium concentration at the growth temperature. However, a higher concentration of Au was observed on the sidewalls of the wires.

Chemical control of semiconductor nanowire kinking and superstructure.

We show that methylgermane (GeH(3)CH(3)) can induce a transition from 111 to 110 oriented growth during the vapor-liquid-solid synthesis of Ge nanowires. This hydride-based chemistry is subsequently leveraged to rationally fabricate kinking superstructures based on combinations of 111 and 110 segments. The addition of GeH(3)CH(3) also eliminates sidewall tapering and enables Ge nanowire growth at temperatures exceeding 475 °C, which greatly expands the process window and opens new avenues to create Si/Ge heterostructures.

Controlling Silicon Nanowire Growth Direction via Surface Chemistry

We report on the first in situ chemical investigation of vapor-liquid-solid semiconductor nanowire growth and reveal the important, and previously unrecognized, role of transient surface chemistry near the triple-phase line. Real-time infrared spectroscopy measurements coupled with postgrowth electron microscopy demonstrate that covalently bonded hydrogen atoms are responsible for the (left angle bracket 111 right angle bracket) to (left angle bracket 112 right angle bracket) growth orientation transition commonly observed during Si nanowire growth. Our findings provide insight into the root cause of this well-known nanowire growth phenomenon and open a new route to rationally engineer the crystal structure of these nanoscale semi-conductors.

Single-nanowire Si solar cells

Solar cells based on arrays of CVD-grown Si nano- or micro-wires are being considered as a potentially low-cost route to implementing a vertical multijunction cell design via radial p-n junctions. This geometry has been predicted to enable efficiencies competitive with planar multicrystalline Si designs, while reducing the materials and processing costs of solar cell fabrication [1]. To further assess the potential efficiency of cells based on this design, we present here experimental measurements of minority carrier diffusion lengths and surface recombination rates within nanowires via fabrication and characterization of single-wire solar cell devices. Furthermore, we consider a potential Si wire array-based solar cell design, and present device physics modeling of single-wire photovoltaic efficiency. Based on experimentally observed diffusion lengths within our wires, we model a radial junction wire solar cell capable of 17% photovoltaic energy conversion efficiency.

Surface chemistry controlled diameter-modulated semiconductor nanowire superstructures

The authors demonstrate that semiconductor nanowire diameter can be rationally controlled as a function of axial position during vapor–liquid–solid synthesis. Such nanoscale structural tuning is achieved with a “molecular resist,” specifically tetramethyltin, that adsorbs on the nanowire sidewall and restricts radial deposition without destabilizing the growth front. The temporal modulation of tetramethyltin delivery during Ge nanowire growth yields user-programmable diameter-modulated superstructures with sub-100 nm periodicities. The authors also investigate the effect of Sn accumulation in the growth catalyst and propose a second-order kinetic rate law that accurately predicts changes to nanowire axial growth rate.

Radial PN junction, wire array solar cells

Radial pn junctions are of interest in photovoltaics because of their potential to reduce the materials costs associated with cell fabrication. However, devices fabricated to date based on Au-catalyzed vapor-liquid-solid growth have suffered from low open-circuit voltages (to our knowledge the highest reports are 260 mV in the solid state and 389 mV in solid-liquid junctions). Herein we report on the potential of low-cost catalysts such as Cu and Ni to fabricate Si wire arrays with potentially higher minority-carrier lifetimes than is possible with a Au catalyst, as well as on the use of reactive ion etching to fabricate high-purity analogs to vapor-liquid-solid grown arrays.