Jeremy W. Mares

Surface engineered porous silicon for stable, high performance electrochemical supercapacitors

Silicon materials remain unused for supercapacitors due to extreme reactivity of silicon with electrolytes. However, doped silicon materials boast a low mass density, excellent conductivity, a controllably etched nanoporous structure, and combined earth abundance and technological presence appealing to diverse energy storage frameworks. Here, we demonstrate a universal route to transform porous silicon (P-Si) into stable electrodes for electrochemical devices through growth of an ultra-thin, conformal graphene coating on the P-Si surface. This graphene coating simultaneously passivates surface charge traps and provides an ideal electrode-electrolyte electrochemical interface. This leads to 10–40X improvement in energy density, and a 2X wider electrochemical window compared to identically-structured unpassivated P-Si. This work demonstrates a technique generalizable to mesoporous and nanoporous materials that decouples the engineering of electrode structure and electrochemical surface stability to engineer performance in electrochemical environments. Specifically, we demonstrate P-Si as a promising new platform for grid-scale and integrated electrochemical energy storage.

Biomolecule kinetics measurements in flow cell integrated porous silicon waveguides

A grating-coupled porous silicon (PSi) waveguide with an integrated polydimethylsiloxane (PDMS) flow cell is demonstrated as a platform for near real-time detection of chemical and biological molecules. This sensor platform not only allows for quantification of molecular binding events, but also provides a means to improve understanding of diffusion and binding mechanisms in constricted nanoscale geometries. Molecular binding events in the waveguide are monitored by angle-resolved reflectance measurements. Diffusion coefficients and adsorption and desorption rate constants of different sized chemical linkers and nucleic acid molecules are determined based on the rate of change of the measured resonance angle. Experimental results show that the diffusion coefficient in PSi is smaller than that in free solutions, and the PSi morphology slows the molecular adsorption rate constant by a factor of 102–104 compared to that of flat surface interactions. Calculations based on simplified mass balance equations and COMSOL simulations give good agreement with experimental data.

Porous Silicon and Polymer Nanocomposites for Delivery of Peptide Nucleic Acids as Anti-MicroRNA Therapies

Self-assembled polymer/porous silicon nanocomposites overcome intracellular and systemic barriers for in vivo application of peptide nucleic acid (PNA) anti-microRNA therapeutics. Porous silicon (PSi) is leveraged as a biodegradable scaffold with high drug-cargo-loading capacity. Functionalization with a diblock polymer improves PSi nanoparticle colloidal stability, in vivo pharmacokinetics, and intracellular bioavailability through endosomal escape, enabling PNA to inhibit miR-122 in vivo.

In Situ Synthesis of Peptide Nucleic Acids in Porous Silicon for Drug Delivery and Biosensing

Peptide nucleic acids (PNA) are a unique class of synthetic molecules that have a peptide backbone and can hybridize with nucleic acids. Here, a versatile method has been developed for the automated, in situ synthesis of PNA from a porous silicon (PSi) substrate for applications in gene therapy and biosensing. Nondestructive optical measurements were performed to monitor single base additions of PNA initiated from (3-aminopropyl)triethoxysilane attached to the surface of PSi films, and mass spectrometry was conducted to verify synthesis of the desired sequence. Comparison of in situ synthesis to postsynthesis surface conjugation of the full PNA molecules showed that surface mediated, in situ PNA synthesis increased loading 8-fold. For therapeutic proof-of-concept, controlled PNA release from PSi films was characterized in phosphate buffered saline, and PSi nanoparticles fabricated from PSi films containing in situ grown PNA complementary to micro-RNA (miR) 122 generated significant anti-miR activity in a Huh7 psiCHECK-miR122 cell line. The applicability of this platform for biosensing was also demonstrated using optical measurements that indicated selective hybridization of complementary DNA target molecules to PNA synthesized in situ on PSi films. These collective data confirm that we have established a novel PNA–PSi platform with broad utility in drug delivery and biosensing.

Diffusion dynamics of small molecules from mesoporous silicon films by real-time optical interferometry

Time-dependent laser reflectometry measurements are presented as a means to rigorously characterize analyte diffusion dynamics of small molecules from mesoporous silicon (PSi) films for drug delivery and membrane physics applications. Calculations based on inclusion of a spatially and temporally dependent solute concentration profile in a one-dimensional Fickian diffusion flow model are performed to determine the diffusion coefficients for the selected prototypical polar species, sucrose (340 Da), exiting from PSi films. The diffusion properties of the molecules depend on both PSi pore size and film thickness. For films with average pore diameters between 10-30 nm and film thicknesses between 300-900 nm, the sucrose diffusion coefficient can be tuned between approximately 100 and 550 μm2/s. Extensions of the real-time measurement and modeling approach for determining the diffusivity of small molecules that strongly interact with and corrode the internal surfaces of PSi films are also discussed.

Shape-Engineered multifunctional porous silicon nanoparticles by direct imprinting

A versatile and scalable method for fabricating shape-engineered nano- and micrometer scale particles from mesoporous silicon (PSi) thin films is presented. This approach, based on the direct imprinting of porous substrates (DIPS) technique, facilitates the generation of particles with arbitrary shape, ranging in minimum dimension from approximately 100 nm to several micrometers, by carrying out high-pressure (>200 MPa) direct imprintation, followed by electrochemical etching of a sub-surface perforation layer and ultrasonication. PSi particles (PSPs) with a variety of geometries have been produced in quantities sufficient for biomedical applications (≫10 μg). Because the stamps can be reused over 150 times, this process is substantially more economical and efficient than the use of electron beam lithography and reactive ion etching for the fabrication of nanometer-scale PSPs directly. The versatility of this fabrication method is demonstrated by loading the DIPS-imprinted PSPs with a therapeutic peptide nucleic acid drug molecule, and by vapor deposition of an Au coating to facilitate the use of PSPs as a photothermal contrast agent.

Systematic study and quantification of optical forces on porous silicon nanoparticles

In this work, we report using an optical tweezers system to study the light-matter interaction and gradient optical forces of porous silicon nanoparticles. The particles are fabricated by first electrochemically etching a multi-layer porous film into a silicon wafer and then breaking up the film through ultrasonic fracturing. The particles have average pore diameters ranging from 20-30 nm. The fabricated batches of particles have diameters between approximately 100- 600nm. After fabrication, the particles are size-sorted by centrifugation. A commercially available optical tweezers system is used to systematically study the optical interaction with these nanoparticles. This work opens new strategic approaches to enhance optical forces and optical sensitivity to mechanical motion that can be the basis for future biophotonics applications.

Integrated Nanoscale Porous Silicon Photonic Structures for Molecular Sensing

The application of porous silicon photonic structures for integrated, label-free biosensing is presented. Specifically, on-chip porous silicon waveguides and Bloch surface-wave sensors will be discussed for the real-time detection of DNA and small biological molecules.

Porous materials for optical detection of chemicals, biological molecules, and high-energy radiation

Porous materials offer several advantages for chemical and biomolecular sensing applications. In particular, nanoscale porous materials possess a very large reactive surface area to facilitate the capture of small molecules, and they have the capability to selectively filter out contaminant molecules by size. This paper will provide an overview of the fabrication, functionalization, and application of porous silicon thin films and waveguides, as well as porous gold templates, for the detection of small chemical and biological molecules. Issues of efficient molecule infiltration and capture inside porous materials, binding kinetics in nanoscale pores, the influence of pore size on small molecule detection sensitivity, and the new nanoscale patterning technique of Direct Imprinting of Porous Substrates (DIPS) will be addressed. Additionally, a novel application of porous silicon for detection of x-ray radiation will be introduced.

Integrated Nanoscale Porous Silicon Waveguide for Molecular Sensing Applications

A grating-coupled nanoscale porous silicon waveguide sensor with an integrated microfluidic flow cell is demonstrated for the selective detection of nucleic acid molecules. Diffusion, adsorption, and desorption coefficients of several biomolecules are also presented.