Self-assembled block copolymer structures are useful in nanolithography applications, producing patterns with high resolution and throughput. We previously showed control over the direction of in-plane cylindrical microdomains formed by self-assembly of a block copolymer (BCP) using a variety of physical templates made from hydrogen silsesquioxane (HSQ) resist ^{[1] [2]} . The HSQ templates were fabricated by electron-beam lithography and then functionalized with a minority or majority block brush to interact with the BCP and direct the self-assembly (as shown in Figure 1). However, HSQ templates were not easily removed and remained as part of the final pattern. Remaining HSQ caused non-uniform pattern transfer due to dissimilar etch rates between the BCP and HSQ. In this study, we solved this issue by using a removable-resist template coated with an etchable-block brush. We fabricated two- and three-dimensional BCP patterns and then removed the templates. Examples (Figure 2) include three-dimensional bends, junctions and mesh-shaped structures, and the ability to change the BCP morphology through templating.

The negative-tone-post templates were made by electron-beam lithography of poly (methyl methacrylate) (PMMA) resist at high dose (100-600 pC/pixel). After development of patterns using methyl isobutyl ketone (MIBK) and acetone ultrasonication, the surface of the patterns was coated with hydroxyl-terminated polystyrene (PS) brush (1 kg mol^-1). Then poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) BCP (MW=45.5 kg mol^-1, f_PDMS=0.32, period 35 nm) was spun and solvent annealed with a mixture of heptane and toluene. CF₄ and O₂ reactive ion etch (RIE) was used to remove the top PDMS layer and the PS matrix.  The O₂ RIE not only removed not only the PS matrix but also removed the PMMA template in the same step. The final results were in-plane oxidized-PDMS cylindrical microdomain patterns in the form of two- and three-dimensional structures devoid of templates. This study provides a path to complex pattern formation for nanolithography with feature sizes below 20 nm.

1. Yang, J. K. W. et al. Nature Nanotechnology 5, 256-260, 2010.
2. Duan H. et al. Journal of Vacuum Science and Technology B 28 C6C58-C6C62, 2010.

Water oxidation is the thermodynamically demanding step of the water-splitting reaction. Efficient sunlight-driven water splitting into molecular oxygen and hydrogen is a challenging prerequisite for solar-fuels production ^[1] . For this prerequisite to be achieved, two major requirements are necessary: (1) efficient photon-to-charge conversion, with efficient utilization of the solar spectrum, and (2) a lowering of the energetic barriers for the four-proton, four-electron proton-coupled electron transfer (PCET) reaction of water splitting. The first requirement can be addressed by using semiconducting materials that absorb well into the visible range, such as cadmium chalcogenides. However, many of these materials including CdSe are unstable and oxidize rapidly under the aqueous conditions for water oxidation, rendering them unusable for water splitting purposes. The second requirement of lowering energetic barriers to water oxidation has been researched extensively in the last several decades to yield different forms of catalysts. One such catalyst is the cobalt-based water oxidation catalyst (CoPi) ^[2] . CoPi can be formed either via electrochemical deposition from Co²⁺ ions in aqueous solutions containing potassium phosphate (KPi) or by processing of supported thin-film (800 nm thick) cobalt metal anodes in KPi at pH 7 ^[3] .

We demonstrate the dual benefit gained by using thin-film cobalt metal as the precursor in the preparation of CoPi on CdSe photoanodes. First, the cobalt layer protects the underlying semiconductor from oxidation and degradation in the aqueous solution. This process is followed by the advantageous incorporation of the CdSe layer into the CoPi layer during continued processing of the electrode. The resulting hybrid material forms a stable photoactive anode for light-assisted water oxidation. Figure 1 shows the high stability and reproducibility of currents through the hybrid material under demanding conditions. The benefits of the photoactive CdSe component are demonstrated in Figure 2, which presents the shift in catalytic onset under illumination.

1. N. S. Lewis and D. G. Nocera, “Powering the planet: Chemical challenges in solar energy utilization,” Proc. Nat’l. Acad. Sci. USA, , vol. 103, pp. 15729-15735, Oct. 2006.
2. M. W. Kanan and D. G. Nocera, “In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+,” Science, vol. 321, pp. 1072-1075, Aug. 2008.
3. E. R. Young, D. G. Nocera and V. Bulović, “Direct formation of a water oxidation catalyst from thin-film cobalt,” Energy Environ. Sci., vol. 3, pp. 1726-1728, Nov. 2010.

Thin-film solar cells incorporating colloidal quantum dot active layers have recently emerged as a notable third-generation photovoltaic (PV) technology, largely due to the strong absorption, tunable infrared bandgap, and ambient-atmosphere stability of lead sulfide quantum dots (PbS QDs). Photoactive PbS QDs can be solution-deposited on a transparent zinc oxide (ZnO) film to form a depleted np-heterojunction device (Figure 1a,b). However, this standard planar architecture incurs a fundamental trade-off between light absorption and carrier collection: to absorb most incident light, we need a ~1-µm-thick QD film ^[1] , but to collect most photocarriers, we need absorption to occur within a minority carrier diffusion length (~100 nm) of the ~150-nm-thick depletion region ^[2] . By introducing 1-D nanostructures (Figure 1c), we can decouple these parallel requirements and optimize for each independently. A vertical, QD-infiltrated array of ZnO nanowires orthogonalizes the mechanistic length scales of absorption and collection. Absorption is maximized as light traverses a thick QD film in the axial direction, while field-driven carrier collection is retained throughout the film as photogenerated electrons drift to nearby PbS/ZnO interfaces in the radial direction.

Our research demonstrates that moving from a planar ZnO film to a nanowire array can significantly improve QDPV performance, increasing short-circuit current density (J_SC) by ~40% and overall power conversion efficiency by ~15% ^[3] . We confirm the near-complete infiltration of PbS QDs into the ZnO nanowire array via cross-sectional scanning electron microscopy (Figure 1d) and elemental mapping with energy-dispersive x-ray spectroscopy. We further demonstrate a fast solution treatment to assist interfacial charge transfer using a bifunctional linker molecule, 3-mercaptopropionic acid (MPA). A simple MPA treatment increases both J_SC and open-circuit voltage (V_OC) of nanowire-QD devices (see Figure 2). Our work on ZnO nanowire-based QD solar cells—along with the recent demonstration of a 5.6%-efficient TiO₂nanopillar-based QDPV ^[4] —suggests that 1-D nanostructures may be the key to enhancing the efficiency and hence the economic viability of quantum dot photovoltaics.

1. A. G. Pattantyus-Abraham,I. J. Kramer, A. R. Barkhouse,X. Wang, G.Konstantatos, R. Debnath,L. Levina,I. Raabe,M. K. Nazeeruddin, M.Grätzel, and E. H. Sargent, “Depleted-heterojunction colloidal quantum dot solar cells,” ACS Nano, vol. 4, no. 6, pp. 3374-3380, May 2010.
2. K. W. Johnston, A. G. Pattantyus-Abraham, J. P. Clifford, S. H. Myrskog, S. Hoogland, S. Sjoerd, H. Shukla, E. J. D. Klem, L. Levina, and E. H. Sargent, “Efficient Schottky-quantum-dot photovoltaics: The roles of depletion, drift, and diffusion,” Applied Physics Letters, vol. 92, no. 12, pp. 122111, Mar. 2008.
3. P. R. Brown, R. R. Lunt, N. Zhao, T. P. Osedach,D. D. Wanger, L.-Y.Chang, M. G.Bawendi, and V. Bulović, “Improved current extraction from ZnO/PbS quantum dot heterojunction photovoltaics using a MoO₃ interfacial layer,” Nano Letters, vol. 11, no. 7, pp. 2955-2961, June 2011.
4. I. J. Kramer, D. Zhitomirsky, J. D. Bass, P. M. Rice, T. Topuria, L. Krupp, S. M. Thon, A. H. Ip, R. Debnath, H.-C. Kim, and E. H. Sargent, “Ordered nanopillar structured electrodes for depleted bulk heterojunction colloidal quantum dot solar cells,” Advanced Materials, vol. 24, no. 17, pp. 2315-2319, Mar. 2012.

Disordered semiconductors exhibit poor electronic transport properties due to their amorphous nature. Low carrier mobility and lifetime limits the diffusion length to 100 ~ 300 nm. Thus, conventional p-n junction photovoltaic design that is composed of a large quasi-neutral region and a small depletion region (Figure 1a) leads to poor charge extraction. To overcome this material limit, a p-i-n junction has been adopted in amorphous silicon solar cells. The internal electric field extends throughout the intrinsic absorber layer and assists carriers to be efficiently extracted to their respective electrodes (Figure 1b). Films composed of quantum dots (QD) show electronic transport properties similar to disordered semiconductors and may also benefit from the p-i-n “drift” device architecture, which has not been applied to QD solar cells to date.

This project aims to implement two major advantages of the p-i-n heterojunction using the QD as an intrinsic absorber layer. The first goal is to augment the width of the depletion region. This widening enhances the light absorbance of the device, allowing more photogenerated carriers and thereby increasing short-circuit current (J_sc). The second advantage to exploit is the ability to dope n- and p-type layers without having to affect the intrinsic absorber layer. Increasing the Fermi level difference by doping both window layers would increase the build-in electric field, enhancing open-circuit voltage (V_oc). Figure 1c and d show schematic illustrations of the device structure and energy diagram, respectively. Figure 2a and b show the device characteristic studied for each separate junction. Rectifying behavior is observed in both p-i, i-n and p-i-n junctions. Figure 2d and e show the JV curve under illumination with and without the intrinsic QD absorber layer. Future studies will focus on V_oc, J_sc, and fill factor (FF) as a function of p-type and n-type layer doping as well as intrinsic layer thickness.

1. M. Zeman, “Solar Cells,” TU Delft OpenCourseWare, Delft University of Technology, 2011. [Online]. Available: http://ocw.tudelft.nl/courses/microelectronics/solar-cells/readings/

Colloidal lead sulfide quantum dot (PbS QD) solar cells have recently shown attractive improvements in efficiency [1]. PbS QDs have been investigated in various device architectures—including Schottky junction, depleted planar heterojunction, and ordered bulk heterojunction photovoltaic (PV) architectures—with the aim of maximizing light absorption while maintaining efficient charge transport ^[1] . However, the thickness of the PbS QD layer in the aforementioned architectures remains limited by the relatively short exciton diffusion length characteristic of all QD films.  We developed a novel architecture in which PbS QDs and zinc oxide (ZnO) nanoparticles are co-deposited from solution to form a bulk heterojunction (BHJ). Much like a typical polymer BHJ solar cell, these PbS QD PV devices can decouple the light absorption, which is proportional to device thickness, from the exciton diffusion length ^[2] . We fabricated these BHJ PbS QD:ZnO solar cells in solution by layer-by-layer deposition in which each step is followed by ligand exchange as shown in Figure 1a. By conducting preliminary optimization of the processing condition, we obtained the current density as a function of the applied voltage graph shown in Figure 1b. Further studies aim at improving device performance while studying the morphological conformation of PbS and ZnO domains.

Figure 1: a) Schematic of the solution process for fabrication of bulk heterojunction lead sulfide quantum dots (PbS QD) and zinc oxide (ZnO) solar cells. The devices are fabricated by layer-by-layer deposition in which each step is followed by ligand exchange. b) JV characteristics under dark (squares) and AM 1.5 illumination (circles) for planar (control – red) and bulk heterojunction (blue) PbS QD:ZnO devices.

1. J. Tang and E. H. Sargent, “Infrared colloidal quantum dots for photovoltaics: Fundamentals and recent progress,” Advanced Materials, vol. 23, no. 1, pp. 12–29, Jan. 2011.
2. C. J. Brabec, S. Gowrisanker, J. J. M. Halls, D. Laird, S. J. Jia, and S. P. Williams, “Polymer-fullerene bulk-heterojunction solar cells,” Advanced Materials, vol. 22, pp. 3839–3856, Aug. 2010.

Nanostructured solar cells are attracting increasing attention as a promising photovoltaic (PV) technology ^[1] . Generation of free charge carriers in nanostructured PV devices occurs at the electron donor-acceptor interface, analogous to the pn-junction interface in traditional crystalline silicon solar cells. However, recombination at this interface constitutes one of the major charge carrier loss pathways. Thus characterizing and controlling recombination dynamics is critical for informing the design of novel device architectures. Recombination parameters also enable comparisons between different device architectures.

In this work, we employ the transient photovoltage (TPV) technique ^[2] to probe recombination mechanisms under standard operating conditions in three different solar cells, as shown in Figure 1: a poly(3-hexylthiophene) and phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) bulk heterojunction; a chloroaluminium phthalocyanine and fullerene (ClAlPc:C₆₀) planar mixed heterojunction; and a lead sulfide quantum dot and zinc oxide (QD PbS:ZnO) pn-heterojunction. The normalized TPV data acquired at 0.5-sun illumination intensity are shown in Figure 2a, which compares the recombination lifetimes of charge carriers in these devices. The observed differences in carrier lifetimes may arise from variations in the respective interface morphologies: for example, the slower recombination transients observed in the ClAlPc:C₆₀ device may be attributed to the intrinsic planarity of this particular architecture.  We can also measure the charge carrier lifetime as a function of the light intensity, as shown in Figure 2b; this result confirms that recombination dynamics are faster in P3HT:PCBM and QD PbS:ZnO than in ClAlPc:C₆₀ PV devices.

1. Anonymous, “A sunny outlook,” Nature Photonics, vol. 6, no. 3, p. 129, Mar. 2012.
2. C. G. Shuttle, B. O’Regan, A. M. Ballantyne, J. Nelson, D. D. C. Bradley, J. de Mello, and J. R. Durrant, “Experimental determination of the rate law for charge carrier decay in a polythiophene: Fullerene solar cell,” Applied Physics Letters, vol. 92, p. 3, 2008.

As silicon MOSFETs approach the limits of their capabilities, III-V field-effect transistors show promise to replace them. The low-effective mass of various III-V materials such as InGaAs and InAs gives rise to extraordinarily high electron velocities ^[1] . III-V based High-Electron Mobility Transistors (HEMTs) represent a great model system to understand physics of relevance to future III-V MOSFETs. In HEMTs it is known that as the gate length is reduced to the sub-100-nm regime, the device enters the ballistic regime ^[2] . In this project, a comprehensive ballistic transport model is being developed to enable the analysis of nanometer-scale III-V HEMTs and MOSFETs and predict the performance of scaled transistors.

The model uses, at its core, a one-dimensional, self-consistent Poisson-Schrödinger simulation of the heterostructure of the transistor. We then add extrinsic device parameters such as source and drain parasitic resistances (R_S and R_D), as well as appropriate values for the drain-induced barrier lowering (DIBL) and a distribution of interface trap states across the bandgap at the semiconductor surface (D_it). The model uses ballistic transport theory to calculate the current-voltage characteristics of the device. Next, we can display the corresponding transconductance, transfer characteristics, output characteristics, or C-V characteristics. Using an option to graph experimental data on top of simulated data, we can adjust the extrinsic device parameters to fit the simulations to the experiments or to identify discrepancies between the two that indicate where more refined models are needed. In this development phase of the model, we are using HEMTs to calibrate the model’s validity in the various regimes of operation, after which physics of relevance to III-V MOSFETs, such as the effect of D_it and imperfect ballisticity, will be added. Ultimately, our modeling approach will allow us to easily characterize current and future MOSFETs.

1. J. A. del Alamo “Nanometer-scale electronics with III-V compound semiconductors,” Nature, vol. 479, pp. 317-323, Nov. 2011.
2. K. Natori, “Ballistic MOSFET reproduces current-voltage characteristics of an experimental device,” IEEE Electron Device Letters, vol. 23, no. 11, pp. 655-657, Nov. 2002.

Photovoltaics and sustainability have received much attention lately. We seek a tandem photovoltaic device using silicon as both the substrate and lower cell and GaAsP as the upper cell. The ideal band gaps for this two-cell tandem structure with silicon at 1.1eV and GaAsP at 1.75 eV allow access to the highest efficiency possible for a two-cell tandem, 36.5%. The lattice mismatch between GaP and Si is 0.37%; therefore, these two materials constitute a nearly ideal combination for the integration of Si and III–V semiconductor-based technologies. Nevertheless, defect-free heteroepitaxy of GaP on Si has been a major challenge.

One can envision a process in which a Si_1-xGe_x graded buffer is grown on a Si wafer to extend the lattice parameter part of the way to GaAs, at which point a lattice-matched GaAs_yP_1-y is grown on the Si_1-xGe_x surface, followed by tensile grading of the GaAs_yP_1-y until GaP is reached. Identifying the composition where the transition can be made from Si_1-xGe_x to GaAs_yP_1-y depending on the application is an integral objective of this study. This identification will provide the flexibility to engineer the lattice constants from Si to Ge and GaP to GaAs while maintaining low threading dislocation density (TDD) and surface morphology suitable for device processing. This study has achieved the successful growth of high-quality lattice-matched GaAs_yP_1-y on Si_0.5Ge_0.5, Si_0.4Ge_0.6, and Si_0.3Ge_0.7 virtual substrates. Various characterization techniques clearly reveal a high-quality crystalline interface (Figure 1) between Si_1-xGe_x and GaAs_yP_1-y with low TDD suitable for device processing, no rampant dislocation nucleation, anti-phase boundaries, stacking faults or other crystalline defects.  Further work will explore the temperature window for the epitaxial growth of GaAs_yP_1-y on Si_1-xGe_x with higher Si content, as the end goal is to obtain a defect-free GaP film on Si substrate.

Figure 1: Cross-sectionalbright field TEM of GaAsyP1-y on (a) Si0.5Ge0.5 and (b) Si0.4Ge0.6 virtual substrates on 6° offcut towards the nearest {111} plane Si (001) substrate.

Organic/inorganic hybrid solar cells based on the integration of conductive polymers into semiconducting nanowire arrays offer opportunities for the development of hybrid devices with increased power conversion efficiencies due to high charge carrier collection, one-dimensional transport pathways, and large interfacial area ^{[1] [2]} . However, control of the nanowire density and effective infiltration of conductive polymers into nano-sized gaps within semiconducting nanowire arrays have been challenging. Here, an inverted device structure of a hybrid solar cell (Figure 1) has been realized by utilizing ZnO nanowire arrays hydrothermally grown directly on an ITO electrode and by using an effective polymer coating. The hydrothermal growth technique enables realization of highly uniform, vertically-aligned ZnO nanowires over large areas on electrode.

The photovoltaic device performance was investigated by controlling the size and density of ZnO nanowires, the thickness of conductive polymer consistent with carrier diffusion lengths, and the organic interfacial layer ^[3] . The size and density of ZnO nanowires were successfully controlled by the concentration of precursor solution (zinc nitrate hexahydrate, hexamethylenetetramine), growth time, and temperature. Effective infiltration of P3HT was achieved using a vacuum annealing technique which eliminated voids and maximized the interfacial area between ZnO and P3HT. Enhanced P3HT crystallinity was observed through UV-Vis absorption and PL quenching showed effective charge separation in vacuum-annealed samples. Hybrid devices with an interfacial layer, Dibenzo{[f,f′]-4,4′,7,7′-tetraphenyl}diindeno[1,2,3-cd:1′,2′,3′-lm]perylene (DBP), exhibit increased short circuit current (J_sc) and open circuit voltage (V_oc) (Figure 2). The DBP interfacial layer provides cascade charge transfer from P3HT to ZnO nanowires. The highest power conversion efficiency (PCE) has been demonstrated using only ZnO nanowire arrays/organic electron donor materials without any inorganic buffer layer such as TiO₂ or dye modification of ZnO nanowires. The scalable, cost-effective approach to synthesize ZnO nanowire arrays and the effective coating of organic electron donor materials over the arrays are promising for applications in hybrid solar cells device fabrication.

1. S. Ren, N. Zhao, S. C. Crawford, M. Tambe, V. Bulovic, and S. Gradečak, “Heterojunction photovoltaics using GaAs nanowires and conjugated polymers,” Nano Letters, vol. 11, pp. 408–413, Feb. 2011.
2. S. Ren, L.-Y. Chang, S. K. Lim, J. Zhao, M. Smith, N. Zhao, V. Bulovic, M. Bawendi, and S. Gradečak, “Inorganic-organic hybrid solar cell: Bridging quantum dots to conjugated polymer nanowires,” Nano Letters, vol. 11, pp. 3998–4002, Aug. 2011.
3. B. Kannan, K. Castelino, and A. Majumdar, “Design of nanostructured heterojunction polymer photovoltaic devices,” Nano Letters, vol. 3, pp. 1729–1733, Nov. 2003.

Achieving a sharp subthreshold swing is crucial to enable the supply voltage scaling that is necessary to reducing power consumption in logic field-effect transistors. In this research, we are investigating a new approach to accomplish this swing based on nanowire FETs with a band engineered superlattice source (SLS).

A steep-subthreshold swing (S) in an FET requires suppressing the subthreshold regime, which in essence is the injection of relatively high-energy source electrons above the energy barrier with the channel. A way to accomplish this injection is to create a miniband in the source with a minigap above it, where no states are allowed. If appropriately designed, no current is possible until the top of the source miniband lines up with the conduction band edge in the channel.  The transition between the ON state and the OFF state can be quite sharp, and the attainable ON current can reach a value comparable to that of a regular FET. In theoretical calculations performed by Gnani et al ^[1] , they have concluded that a variety of SLs can accomplish these goals: AlGaAs/GaAs, InAlAs/InGaAs, and AlGaN/GaN, among others. These are short period SLs with barriers and wells in the 1-2 nm regime. Furthermore, 7 periods appears to be enough to accomplish the filtering action of the SL. They have shown that values of S in the 10-20 mV/dec are possible (at 300K).

Our goal is to demonstrate a prototype SLS NW-FET in the InAlAs/InGaAs system and to study its suitability for steep-subthreshold and ultra-low voltage operation. The proposed device will be a vertical nanowire transistor with superlattice region incorporated in the source. In order to design a suitable heterostructure and device architecture, we created a simulation environment for the miniband structure of superlattices in various material systems using Nextnano. Based on a built-in 1D ballistic transport model, the local density of states was calculated to show explicitly the miniband position, as in Figure 1. Our calculations indicate that a demanding nanowire diameter of sub-10 nm is needed to achieve single transversal sub-band behavior.

In our quest for nanowire FETs, we are developing a reactive ion etch (RIE) process for InGaAs/InAlAs nanowires. Using HSQ as the hard mask defined by electron beam lithography, we have shown promising etch results using Cl₂ based chemistry, as in Figure 2. This will follow with planarization to provide a contact to the top of the nanowire.

1. E. Gnani, P. Mariorano, S. Reggiani, A. Gnudi, G. Baccarani, “Investigation on superlattice heterostructures for steep-slope nanowire FETs,”, Device Research Conference, 2011, pp. 201-202.