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1. Effect of water vapor pressure on positive and negative tone electron-beam patterning of poly(methyl methacrylate)

   https://doi.org/10.1116/6.0002118  

   Kumar, Deepak; Chaudhuri, Krishnaroop; Brill, Joseph W.; Pham, Jonathan T.; Hastings, J. Todd (January 2023, Journal of Vacuum Science & Technology B)

   Variable-pressure electron-beam lithography (VP-EBL) employs an ambient gas at subatmospheric pressures to reduce charging during electron-beam lithography. VP-EBL has been previously shown to eliminate pattern distortion and provide improved resolution when patterning poly(methyl methacrylate) (PMMA) on insulating substrates. However, it remains unknown how water vapor affects the contrast and clearing dose nor has the effect of water vapor on the negative-tone behavior of PMMA been studied. In addition, water vapor has recently been shown to alter the radiation chemistry of the VP-EBL process for Teflon AF. Such changes in radiation chemistry have not been explored for PMMA. In this work, VP-EBL was conducted on conductive substrates to study the effect of water vapor on PMMA patterning separately from the effects of charge dissipation. In addition, both positive and negative-tone processes were studied to determine the effect of water vapor on both chain scission and cross-linking. The contrast of PMMA was found to improve significantly with increasing water vapor pressure for both positive and negative-tone patterning. The clearing dose for positive-tone patterning increases moderately with vapor pressure as would be expected for electron scattering in a gas. However, the onset set dose for negative-tone patterning increased dramatically with pressure revealing a more significant change in the exposure mechanism. X-ray photoelectron spectra and infrared transmission spectra indicate that water vapor only slightly alters the composition of exposed PMMA. Also, electron scattering in water vapor yielded a much larger clear region around negative-tone patterns. This effect could be useful for increasing the range of the developed region around cross-linked PMMA beyond the backscattered electron range. Thus, VP-EBL for PMMA introduces a new means of tuning clearing/onset dose and contrast, while allowing additional control over the size of the cleared region around negative-tone patterns. 

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2. Fabrication and Measurement of LT-GaAs Photoconductive THz Broadband Antennas

   Zachary P. Uttley and Magda O. El-Shenawee (July 2022, Digest IEEE Antennas and Propagation Society International Symposium)

   IEEE (Ed.)

   This paper presents fabrication and experimental measurements of broadband terahertz (THz) photoconductive antennas (PCAs), based on the conventional low temperature gallium arsenide (LT-GaAs) material. Various antenna electrode geometries, that were previously designed through computer simulations, are fabricated using the electron beam lithography (EBL). The generated time domain pulse is measured using a time domain spectroscopy system (TDS). The bandwidth of each emitting device is obtained using the fast Fourier transform of the generated electric field pulse. 

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3. Gas assisted electron beam patterning processes

   https://doi.org/10.13023/etd.2024.66  

   Kumar, Deepak (May 2024, University of Kentucky Libraries)

   Radiolysis is a complex phenomenon in which molecules subjected to ionizing radiation form new chemical species. Electron-beam irradiation has proven to be a versatile approach for significantly altering materials’ properties and forms the basis for electron-beam lithography using both organic and inorganic resists. Electron-beam exposure is normally carried out under high vacuum conditions to reduce contamination and allow for unhindered interaction between the electrons and the resist material. Exposure under an ambient gas at sub-atmospheric pressures has been found to provide a distinct mechanism which can be exploited to circumvent some of the challenges associated with material processing and significantly alter or enhance material’s properties. This dissertation discusses the modifications in standard electron beam resist characteristics during gas assisted electron beam pattering. We studied the effect of water vapor pressure on positive and negative tone electron-beam patterning of poly methyl methacrylate (PMMA). For both positive and negative-tone patterning, it was found that increasing the water vapor pressure considerably improved the contrast of PMMA. As expected from electron scattering in a gas, the clearing dosage for positive tone patterning gradually increased with vapor pressure. Also, electron scattering in water vapor yielded a substantially larger clear region around the negative-tone patterns. This effect could be useful for increasing the range of the developed region around cross-linked PMMA far beyond the backscattered electron range. As a result, VP-EBL for PMMA offers a new means of tuning clearing/onset dose and contrast while enabling more control over the size of the cleared region around negative-tone patterns. We provide a novel way to simultaneously tune the emission wavelength and enhance the fluorescence intensity of fluorophores formed by irradiating polystyrene with a focused electron beam under various gaseous environments. We studied the effect of electron dose and gas pressure on the emission spectra and photon yield of irradiated polystyrene film on a variety of substrates. Up to 10x enhancement in fluorescence yield was achieved using water vapor and the peak emission wavelength tuned over a wide wavelength range. Thus, localized electron-beam synthesis of fluorophores in polystyrene can be controlled by both dose and by ambient water-vapor pressure. This technique could enable innovative approaches to photonics where fluorophores with tunable emission properties can be locally introduced by electron-beam patterning. We also studied the effect of ambient gases on contrast and resolution of PMMA on conducting and insulating substrates. E-beam exposures were conducted under vacuum conditions and 1 mbar of water vapor, helium, nitrogen and argon to study their effect on contrast and resolution of PMMA on silicon, fused silica and soda lime glass substrates. On silicon, exposure under water vapor yielded contrast values significantly higher than vacuum exposure, consistent with our previous work. However, exposure under helium yielded slightly improved contrast compared to vacuum exposure. On insulating substrates exposure under helium environment yielded contrast values significantly higher compared to vacuum exposure. The clearing dose was found to increase with the gases’ molecular weight and proton number, consistent with the increase in scattering cross-section. The improved contrast and sensitivity (dose to clear) of PMMA under helium motivated us to study the resolution under various gases. Resolution testing indicated that despite the lower clearing dose, helium still exhibited the best resolution with 25-nm half-pitch dense lines and spaces clearly resolved on soda lime glass. Thus, VP-EBL of PMMA under helium yields higher sensitivity and contrast on insulating substrates without sacrificing resolution. 

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4. Contact engineering for graphene nanoribbon devices

   https://doi.org/10.1063/5.0172432  

   Mutlu, Zafer; Dinh, Christina; Barin, Gabriela Borin; Jacobse, Peter H.; Kumar, Aravindh; Polley, Debanjan; Singh, Hanuman; Wang, Ziyi; Lin, Yuxuan Cosmi; Schwartzberg, Adam; et al (December 2023, Applied Physics Reviews)

   Graphene nanoribbons (GNRs), when synthesized with atomic precision by bottom–up chemical approaches, possess tunable electronic structure, and high theoretical mobility, conductivity, and heat dissipation capabilities, which makes them an excellent candidate for channel material in post-silicon transistors. Despite their immense potential, achieving highly transparent contacts for efficient charge transport—which requires proper contact selection and a deep understanding of the complex one-dimensional GNR channel-three-dimensional metal contact interface—remains a challenge. In this study, we investigated the impact of different electron-beam deposited contact metals—the commonly used palladium (Pd) and softer metal indium (In)—on the structural properties and field-effect transistor performance of semiconducting nine-atom wide armchair GNRs. The performance and integrity of the GNR channel material were studied by means of a comprehensive Raman spectroscopy analysis, scanning tunneling microscopy (STM) imaging, optical absorption calculations, and transport measurements. We found that, compared to Pd, In contacts facilitate favorable Ohmic-like transport because of the reduction of interface defects, while the edge structure quality of GNR channel plays a more dominant role in determining the overall device performance. Our study provides a blueprint for improving device performance through contact engineering and material quality enhancements in emerging GNR-based technology. 

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5. Enhanced electrochemical biosensor and supercapacitor with 3D porous architectured graphene via salt impregnated inkjet maskless lithography

   https://doi.org/10.1039/C8NH00377G  

   Hondred, John A.; Medintz, Igor L.; Claussen, Jonathan C. (April 2019, Nanoscale Horizons)

   Advances in solution-phase graphene patterning has provided a facile route for rapid, low-cost and scalable manufacturing of electrochemical devices, even on flexible substrates. While graphene possesses advantageous electrochemical properties of high surface area and fast heterogenous charge transport, these properties are attributed to the edge planes and defect sites, not the basal plane. Herein, we demonstrate enhancement of the electroactive nature of patterned solution-phase graphene by increasing the porosity and edge planes through the construction of a multidimensional architecture via salt impregnated inkjet maskless lithography (SIIML) and CO 2 laser annealing. Various sized macroscale pores (<25 to ∼250 μm) are patterned directly in the graphene surface by incorporating porogens ( i.e. , salt crystals) in the graphene ink which act as hard templates for pore formation and are later dissolved in water. Subsequently, microsized pores (∼100 nm to 2 μm in width) with edge plane defects are etched in the graphene lattice structure by laser annealing with a CO 2 laser, simultaneously improving electrical conductivity by nearly three orders of magnitude (sheet resistance decreases from >10 000 to ∼50 Ω sq −1 ). We demonstrate that this multidimensional porous graphene fabrication method can improve electrochemical device performance through design and manufacture of an electrochemical organophosphate biosensor that uses the enzyme acetylcholinesterase for detection. This pesticide biosensor exhibits enhanced sensitivity to acetylthiocholine compared to graphene without macropores (28.3 μA nM −1 to 13.3 μA nM −1 ) and when inhibited by organophosphate pesticides (paraoxon) has a wide linear range (10 nM to 500 nM), low limit of detection (0.6 nM), and high sensitivity (12.4 nA nM −1 ). Moreover, this fabrication method is capable of patterning complex geometries [ i.e. interdigitated electrodes (IDEs)] even on flexible surfaces as demonstrated by an IDE supercapacitor made of SIIML graphene on a heat sensitive polymer substrate. The supercapacitor demonstrates a high energy density of 0.25 mW h cm −3 at a power density of 0.3 W cm −3 . These electrochemical devices demonstrate the benefit of using SIIML and CO 2 laser annealing for patterning graphene electrodes with a multidimensional porous surface even on flexible substrates and is therefore a platform technology which could be applied to a variety of different biosensors and other electrochemical devices. 

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