This PDF file contains the front matter associated with SPIE Proceedings Volume 8817, including the Title Page, Copyright Information, Table of Contents, and the Conference Committee listing.

This paper summarizes work in the molecular-level self-assembly of two-dimensional and three-dimensional materials. Synthesis processes are briefly discussed, and examples of multiple properties achievable in two-dimensional and three-dimensional self-assembled materials are given.

The bio-organic thin film transistor (BiOTFT) with the DNA and DNA-surfactant complex as a dielectric layer shows memory function. In order to investigate the effect of surfactant structure on the OTFT memory device performance, different kinds of surfactant were introduced. Cetyltrimethylammonium chloride (CTMA), Lauroylcholine chloride (Lau) or Octadecyltrimethylammonium chloride (OTMA) as the cationic surfactant was mixed with DNA to prepare the DNA complex through the electrostatic interaction. In addition, the different molecular weight DNA also has been studied to analyze the effect of DNA chain length on the performance of the physical property. Many kinds of methods including UV-vis, Circular dichiroism (CD) and I-V characteristic have been applied to analyze the property of DNA complex. In conclusion, all of DNA complex with CTMA, OTMA and Lau were revealed to work as the bio-organic thin film transistor memory, and the device fabricated by Lau has the highest ON current and showed better device performance.

We discuss the increasing effort to adopt biological and biologically inspired concepts to solve problems in photonic materials and devices. This effort ranges from exploiting fundamental material properties, as in fluorescent dyes and DNA-derived polymers, to studying structures that interact strongly with photons, exemplified by butterfly wings. An emerging area of interest is the combination of biological or biologically derived materials with organic or inorganic synthetic materials to achieve material systems with unprecedented performance. We discuss several examples from our recent work including erbium-doped sol-gel/ DNA-CTMA, diatom photonics, and microring resonator based sensing of biological objects.

Interaction of some organic dyes with DNA induces fluorescence enhancement through intercalation or groove binding, stimulating the development of compact tunable thin-film dye lasers. We have demonstrated amplified spontaneous emission (ASE), laser emission and its tuning via distributed feedback (DFB) with a dynamic grating formed in DNA-surfactant complexes doped with cyanine or hemicyanine dyes. The formation of semi-persistent (or quasi-dynamic) grating is more preferable in order to realize stable and easily tunable laser sources, so we fabricated bi-layered devices composed of a DNA-CTMA layer doped with pyridine 1 (Py1) and an PMMA layer including an azo dye, Disperse Red 1 (DR1). Under simultaneous excitation of the azo layer with interfering two beams for grating formation and the emission layer with another beam as pumping, we observed laser emission from the device. The oscillation wavelength was controlled by varying the incident beam angles allowing the fast tuning suitable to applications. Furthermore, monolithic DNA device having two functions of lasing and grating formation would be more promising. DNA-CTMA complex had been considered to be a poor matrix for grating inscription, but we found that doping of an azo-carbazole compound made it possible to inscribe gratings with relatively high diffraction efficiency and with fast response which could be applicable to monolithic tunable laser system.

DNA biopolymer hybrids have been investigated for energy storage applications and also as potential high k gate dielectrics in bioelectronics applications such as BioFETs. DNA-based hybrid films incorporating sol-gel-derived ceramics have shown strong promise as insulating dielectrics for high voltage capacitor applications. Our studies of DNA-CTMA complex/sol-gel hybrid thin film devices have demonstrated reproducibility and stability in temperature-and frequency-dependent dielectric properties as well as reliability in DC voltage breakdown measurements, attaining values consistently in the 300 - 350 V/um range. We have also investigated DNA-inorganic hybrids by ex situ blending of aqueous solutions of DNA with high k ceramics such as BaTiO₃ and TiO₂. These systems are currently being investigated as potential gate dielectrics for BioFETs by virtue of their relatively high dielectric constant, high DC electrical resistivity, and lower leakage currents than pristine DNA. Functionally layered devices have also been designed, fabricated and characterized to determine any added benefit in dielectric applications. The electrical/dielectric characteristics of DNA and DNA-CTMA with sol-gel-derived ceramics, high k ceramic fillers, and in layered devices were examined to determine their effect on vital dielectric parameters for energy storage and bioelectronics applications.

The potential for photonic application of modified deoxyribonucleic acid with cationic surfactant cetyltrimethylammonium chloride, has been shown in many fields. Here we present results of detailed studies on random lasing achieved in a biopolymer based matrix loaded with luminescent dye. The random lasing originates due to the light scattering induced by formation of nanocrystals in the bulk biosystem. We show that lasing parameters for bio-polymeric system can be comparable with similar systems based on standard or π-conjugated polymers and may contribute to commercialization of polymeric lasers.

This study highlights some of the effects of UV crosslinking of DNA-CTMA on its electrical and optical characteristics. The crosslinking of DNA-CTMA occurs via the photodimerization of attached coumarin moieties under UV irradiation. An exposure time of 30 min to UV light with an output power of 166 mW/cm² is needed to complete the crosslinking process. The UV-crosslinked films show a significant increase in the electrical resistivity (decrease in leakage current) and a markedly lower dielectric constant.

This paper, originally published on 1 October 2013, was replaced with a corrected/revised version on 25 October 2013. If you downloaded the original PDF but are unable to access the revision, please contact SPIE Digital Library Customer Service for assistance.

In previous research we have demonstrated improvements in device performance with the incorporation of a deoxyribonucleic acid (DNA)-based biopolymer into organic light emitting diodes, organic thin film transistors and other organic photonic and electronic devices. Here, we investigate nucleobases, nitrogen-containing biological compounds found within DNA, ribonucleic acid (RNA), nucleotides and nucleosides, for use in a few of those previously investigated photonic and electronic devices. Used as an electron blocking layer in OLEDs, a gate insulator for grapheme transistors and as a dielectric in organic-based capacitors, we have produced comparable results to those using DNA-based biopolymers.

Recent experimental results indicate that the inscription of gratings in DR1:DNA-CTMA thin films displays some features of non-exponential grating amplitude growth with time.¹ The origin of this behavior is hypothetically assigned to a complex distribution of local voids in a polymeric matrix^{1, 2} which strongly influences the dynamics of grating inscription modelled using the semi-intercalation hypothesis.^3–7 We discuss critically those topics, review the theoretical methods used for modelling of the grating inscription and point-out a hypothetical relation to complex systems. New experimental results of holographic DTWM recording of the gratings in DNA-CTMA:DR1 and PS:DR1 are presented. The two observed types of dynamics are hypothetically assigned to various distributions of local voids in corresponding polymeric matrices.

The binding of DNA-CTMA (Deoxyribonucleic acid-cetyltrimethylammonium) complex with two tetrameric Copper Phthalocyanine (CuPc) systems, substituted with carboxylic acid (CuPc-COOH) and derivatized further as an imidazolium salt (CuPc-COOR), was investigated in dimethylsulfoxide (DMSO) solutions using UV/Visible Spectroscopy. Absorbance changes at 685 nm (Q band of the CuPc) were monitored as a function of DNA-CTMA added to the dye solution and stock concentrations of DNA-CTMA in DMSO were varied to facilitate observation of the full binding process. Our findings indicated that while binding with DNA-CTMA was more well-defined in the case of CuPc-COOH, the binding profile of the CuPc-COOR showed initial growth followed by decay in its Q-band absorbance which was indicative of a more complex binding mechanism involving the dye and DNA-CTMA. Preliminary findings from photophysical studies involving the CuPc tetramers and DNA-CTMA are also discussed in this paper.

A small, computer-controller drawdown bar device for coating glass-slide size substrates with thin films was designed and constructed. A variety of thin films of DNA-CTMA were fabricated. The results of electrical characterization and micro-Raman spectroscopy studies are reported.

There is considerable research in the area of manipulating light below the diffraction limit, with potential applications ranging from information processing to light-harvesting. In such work, a common problem is a lack of efficiency associated with non-radiative losses, e.g., ohmic loss in plasmonic structures. From this point of view, one attractive method for sub-wavelength light manipulation is to use Förster resonance energy transfer (FRET) between chromophores. Although most current work does not show high efficiency, biology suggests that this approach could achieve very high efficiency. In order to achieve this goal, the geometry and spacing of the chromophores must be optimized. For this, DNA provides an easy means for the self-assembly of these complex structures. With well established ligation chemistries, it is possible to create facile hierarchical assemblies of quantum dots (QDs) and organic dyes using DNA as the platform. These nanostructures range from simple linear wires to complex 3-dimensional structures all of which can be self-assembled around a central QD. The efficiency of the system can then be tuned by changing the spacing between chromophores, changing the DNA geometry such that the donor to acceptor ratio changes, or changing the number of DNA structures that are self-assembled around the central QD. By exploring these variables we have developed a flexible optical system for which the efficiency can be both controlled and optimized.

In this study, we investigate a new technique to fabricate DNA-CTMA films with tunable properties. MAPLE is, for the first time, explored to deposit DNA-CTMA dielectric films on top of epitaxially grown graphene on silicon carbide (SiC) substrate. Silicon dioxide (SiO₂) is commonly used as a gate insulator in graphene based field effect transistors (GFETs) in a top gate configuration. The high temperature deposition of SiO₂ on graphene is known to cause damage to the surface of the graphene leading to poor device operation. We propose an alternative gate insulator based on a bio-organic (DNA-CTMA) material processed and deposited at room temperature (RT) using MAPLE. Hall measurements run before and after DNA-CTMA deposition showed no change in the type of conductivity as well as charge carrier mobility.

The Second Harmonic Generation (SHG) response from Tyrosine-containing peptides at the air-water interface is presented. First, the quadratic hyperpolarizability of the aromatic amino acid Tyrosine obtained by Hyper Rayleigh Scattering is reported, demonstrating its potentiality as an endogenous molecular probe for SHG studies. Then, the single Tyrosine antimicrobial peptide Mycosubtilin is monitored at the air-water interface and compared to another peptide, Surfactin, lacking a Tyrosine residue. Adsorption kinetics and polarization analysis of the SHG intensity for the peptide monolayers clearly demonstrate that the SHG response from Mycosubtilin arises from Tyrosine. Besides, it confirms that indeed Tyrosine can be targeted as an endogenous molecular probe.

Bacteriorhodopsin (bR) is a promising biomaterial for several applications. Optical excitation of bR at an electrode-electrolyte interface generates differential photocurrents while an incident light is turned on and off. This unique functional response is similar to that seen in retinal neurons. The bR-based bipolar photosensor consists of the bR dip-coated thin films patterned on two ITO plates and the electrolyte solution. This bipolar photocell will function as a biomimetic photoreceptor cell. The bipolar structure, due to the photocurrent being generated in alignment with the cathodic direction, makes the excitatory and inhibitory regions possible. This scheme shows our bipolar cell can act as a basic unit of edge detection and forms the artificial visual receptive field.

Luminescent semiconductor nanocrystals or quantum dots (QDs) contain favorable photonic properties (e.g., resistance to photobleaching, size-tunable PL, and large effective Stokes shifts) that make them well-suited for fluorescence (Förster) resonance energy transfer (FRET) based applications including monitoring proteolytic activity, elucidating the effects of nanoparticles-mediated drug delivery, and analyzing the spatial and temporal dynamics of cellular biochemical processes. Herein, we demonstrate how unique considerations of temporal and spatial constraints can be used in conjunction with QD-FRET systems to open up new avenues of scientific discovery in information processing and molecular logic circuitry. For example, by conjugating both long lifetime luminescent terbium(III) complexes (Tb) and fluorescent dyes (A647) to a single QD, we can create multiple FRET lanes that change temporally as the QD acts as both an acceptor and donor at distinct time intervals. Such temporal FRET modulation creates multi-step FRET cascades that produce a wealth of unique photoluminescence (PL) spectra that are well-suited for the construction of a photonic alphabet and photonic logic circuits. These research advances in bio-based molecular logic open the door to future applications including multiplexed biosensing and drug delivery for disease diagnostics and treatment.

Biopolymer-based thin films, such as those composed of CTMA-DNA, can be used as a host material for NLOactive dyes for applications such as electro-optic (EO) switching and second harmonic generation. Previous work by Heckman et al. (Proc. SPIE 6401, 640108-2) has demonstrated functioning DNA-based EO modulators. Improved performance requires optimization of both the first hyperpolarizabilities (β) and degree of acentric ordering exhibited by the chromophores. The cationic dye DANPY-1 (Proc. SPIE 8464, 846409-D) has a high affinity for DNA and a substantial hyperpolarizability; however, its macroscopic ordering has not been previously characterized. We have characterized the acentric ordering of the dye using sum-frequency generation (SFG) vibrational spectroscopy in surface-immobilized DNA and on planar metal and dielectric surfaces.

Dye-sensitized solar cells (DSSCs) rely on a network of titanium dioxide nanoparticles for electron transport and must balance carrier generation and collection. Adding photonic structures may increase light capture without affecting carrier collection. Diatoms are single-celled algae that biologically fabricate silicon dioxide cell walls which resemble photonic crystal slabs. We present a simple fabrication strategy that allows for uniform and controlled placement of biosilica within DSSCs. Integration of biosilica reduces photoanode transmittance to less than 5% prior to dye sensitization at loading levels as low as 6 wt% biosilica. Increased biosilica loading (17 wt%) provides additional enhancements in photocurrent generation. Reflectance measurements suggest that the enhancement results from the combined effects of photonic resonance and Mie scattering. Overall efficiency of these devices is improved by 8% and 14%, respectively.

Protein-hydrogel-based free-form three-dimensional (3D) micro/nano-elements with ‘‘smart’’ stimuli-responsiveness fabricated via femtosecond laser direct writing (FsLDW) have attracted increasing efforts for their wide utilities in many fields, such as bio-micro/nano-machine ^[1], biophotonics ^{[2, 3]}, etc. All processes of this protein-FsLDW are carried out in proteins’ aqueous solutions, as a result of which the approach is noncontact, maskless and biocompatible. So, we applied the promising FsLDW approach, which, in the construction of protein-based 3D optical microdevices, for example, microlenses. In order to meet the requirements of optical applications, FsLDW system and processing parameters were carefully optimized to achieve high-quality surface and 3D morphology. The photo-crosslinked protein microhydrogels showed a rapid and reversible swell-to-shrink behavior once stimulated by chemical signals, by which the protein microdevices can be dynamically tuned. Because of using protein molecules as “building blocks”, protein-based microelements were demonstrated of good biocompatibility. Based on the valuable and unique merits, protein-based optical micro/nano-elements have great potential for micro/nano-bio-optics, bionics, and novel biomedical applications, etc.

The first hyperpolarizability of the aromatic amino acid Tyrosine has been obtained by Hyper Rayleigh Scattering (HRS) in aqueous environment and under non resonant conditions. The rather large value determined is in agreement with previous HRS studies and confirms that Tyrosine can be targeted as an endogenous molecular probe for the second harmonic studies of biological molecules. The same experiment was also performed in an aqueous environment containing 20 nm diameter gold metallic nanoparticles. The resulting first hyperpolarizability measured with the fundamental wavelengths of 815 nm and 1050 nm in these conditions for Tyrosine is reduced as compared to that obtained in absence of metallic nanoparticles.