Hydrogen Silsesquioxane Research Articles

Quantitative evaluation of residual resist in electron beam lithography based on scanning electron microscopy imaging and thresholding segmentation algorithm

Electron beam lithography is a critical technology for achieving high-precision nanoscale patterning. The presence of resist residues in the structures can significantly affect subsequent processes such as etching and lift-off. However, the evaluation and optimization of resist residues currently relies on qualitative observations like scanning electron microscopy (SEM), necessitating multiple experiments to iteratively optimize exposure parameters, which is not only labor-intensive but also costly. Here, we propose a quantitative method to evaluate resist residues. By processing the obtained SEM images using a threshold segmentation algorithm, we segmented the resist structure region and the residual resist region in the images. The grayscale values of these two regions are identified, and the residues are quantified based on the ratio of these values. Furthermore, a relationship curve between the residue amount and the exposure dose is plotted to predict the optimal exposure dose. To validate this method, we fabricated hydrogen silsesquioxane annular grating structures with 30 nm linewidth and analyzed the residue levels over an exposure dose range of 2000-2500μC cm-2, predicting the optimal dose to be 1800μC cm-2and confirming this through experiments. Additionally, we applied the method to polymethyl methacrylate and ZEP-520A structures, achieving similarly accurate results, further confirming the method's general applicability. This method has the potential to reduce experimental costs and improve yield and production efficiency in nano fabrication.

High-resolution chemical patterns from negative tone resists for the integration of extreme ultraviolet patterns of metal-oxide resists with directed self-assembly of block copolymers

Extreme ultraviolet (EUV) lithography faces significant challenges in designing suitable resist materials that can provide adequate precision, while maintaining economically viable throughput. These challenges in resist materials have led to printing failures and high roughness in EUV patterns, compromising the performance of semiconductor devices. Integrating directed self-assembly (DSA) of block copolymers (BCPs) with EUV lithography offers a promising solution because, while the BCPs register to the EUV-defined chemical guiding pattern, the thermodynamically determined structures of the BCPs automatically rectify defects and roughness in the EUV pattern. Despite the superior resolution of metal-oxide EUV resists (MORs), their application to DSA is limited by the difficulty in converting them into chemical patterns that allow effective transfer of the rectified patterns of DSA films into inorganic materials. To address this challenge, this study introduces a novel strategy for fabricating chemical patterns using hydrogen silsesquioxane (HSQ), a high-resolution negative tone inorganic resist, as a model system for MORs. Initially, a sacrificial Cr pattern is generated from HSQ patterns via reactive ion etching. The sacrificial Cr pattern is converted into a chemical pattern by first grafting a water-soluble polyethylene oxide brush onto the substrate, then wet etching the Cr, and finally grafting nonpolar polystyrene brushes. Assembling polystyrene-block-poly(methyl methacrylate) on these patterns results in structures oriented and registered with the underlying pattern, achieving 24 nm full-pitch resolutions. This approach has the potential to integrate MOR patterns into the DSA process, thereby enabling the generation of high-quality sub-10 nm patterns with high-χ BCPs.

Reliable fabrication of 3D freestanding nanostructures via all dry stacking of incompatible photoresist

Three-dimensional (3D) free-standing nanostructures based on electron-beam lithography (EBL) have potential applications in many fields with extremely high patterning resolution and design flexibility with direct writing. In numerous EBL processes designed for the creation of 3D structures, the multilayer resist system is pivotal due to its adaptability in design. Nevertheless, the compatibility of solvents between different layers of resists often restricts the variety of feasible multilayer combinations. This paper introduces an innovative approach to address the bottleneck issue by presenting a novel concept of multilayer resist dry stacking, which is facilitated by a near-zero adhesion strategy. The poly(methyl methacrylate) (PMMA) film is stacked onto the hydrogen silsesquioxane (HSQ) resist using a dry peel and release technique, effectively circumventing the issue of HSQ solubilization by PMMA solvents typically encountered during conventional spin-coating procedures. Simultaneously, a dry lift-off technique can be implemented by eschewing the use of organic solvents during the wet process. This pioneering method enables the fabrication of high-resolution 3D free-standing plasmonic nanostructures and intricate 3D free-standing nanostructures. Finally, this study presents a compelling proof of concept, showcasing the integration of 3D free-standing nanostructures, fabricated via the described technique, into the realm of Fabry-Perot cavity resonators, thereby highlighting their potential for practical applications. This approach is a promising candidate for arbitrary 3D free-standing nanostructure fabrication, which has potential applications in nanoplasmonics, nanoelectronics, and nanophotonics.

3D Printing of Hierarchical Structures Made of Inorganic Silicon-Rich Glass Featuring Self-Forming Nanogratings.

Hierarchical structures are abundant in nature, such as in the superhydrophobic surfaces of lotus leaves and the structural coloration of butterfly wings. They consist of ordered features across multiple size scales, and their advantageous properties have attracted enormous interest in wide-ranging fields including energy storage, nanofluidics, and nanophotonics. Femtosecond lasers, which are capable of inducing various material modifications, have shown promise for manufacturing tailored hierarchical structures. However, existing methods, such as multiphoton lithography and three-dimensional (3D) printing using nanoparticle-filled inks, typically involve polymers and suffer from high process complexity. Here, we demonstrate the 3D printing of hierarchical structures in inorganic silicon-rich glass featuring self-forming nanogratings. This approach takes advantage of our finding that femtosecond laser pulses can induce simultaneous multiphoton cross-linking and self-formation of nanogratings in hydrogen silsesquioxane. The 3D printing process combines the 3D patterning capability of multiphoton lithography and the efficient generation of periodic structures by the self-formation of nanogratings. We 3D-printed micro-supercapacitors with large surface areas and a high areal capacitance of 1 mF/cm2 at an ultrahigh scan rate of 50 V/s, thereby demonstrating the utility of our 3D printing approach for device applications in emerging fields such as energy storage.

A strategy to fabricate nanostructures with sub-nanometer line edge roughness

Line edge roughness (LER) has been an important issue in the nanofabrication research, especially in integrated circuits. Despite numerous research studies has made efforts on achieving smaller LER value, a strategy to achieve sub-nanometer level LER still remains challenging due to inability to deposit energy with a profile of sub-nanometer LER. In this work, we introduce a strategy to fabricate structures with sub-nanometer LER, specifically, we use scanning helium ion beam to expose hydrogen silsesquioxane (HSQ) resist on thin SiNx membrane (∼20 nm) and present the 0.16 nm spatial imaging resolution based on this suspended membrane geometric construction, which is characterized by scanning transmission electron microscope (STEM). The suspended membrane serves as an energy filter of helium ion beam and due to the elimination of backscattering induced secondary electrons, we can systematically study the factors that influences the LER of the fabricated nanostructures. Furthermore, we explore the parameters including step size, designed exposure linewidth (DEL), delivered dosage and resist thickness and choosing the high contrast developer, the process window allows to fabricate lines with 0.2 nm LER is determined. AFM measurement and simulation work further reveal that at specific beam step size and DEL, the nanostructures with minimum LER can only be fabricated at specific resist thickness and dosage.

(Invited) Synthesis of Ultra-Bright Colloidal Silicon Quantum Dots (PLQY~80%) and Highly Efficient LEDs (EQE>10%)

Silicon is the second most abundant element in the Earth’s crust and could be considered an environmentally benign material. Silicon has been widely used in electronic devices and solar cells, and it has dominated the semiconductor research and development. However, the photoluminescence (PL) of the bulk material shows an invisible NIR wavelength (λ ~ 1100 nm). In addition, the PL quantum yield (PLQY) of bulk crystal Si is ~0.01% owing to the indirect transition nature. In contrast, silicon quantum dots show PL in the entire visible spectral region [1]. Furthermore, colloidal silicon quantum dots demonstrate PLQYs of 60% [2], and thereby they give highly impact as environmentally benign and heavy-metal-free quantum dots (i.e., In, Cd, and Pb free) for displays, lighting, and biomedical imaging via solution processing. Indeed, silicon quantum dot LEDs have recently been produced from a natural substance, by upcycling discarded rice husks [3].Herein, red PL with a PLQY of 60–80% and LEDs with an external quantum efficiency of >10% were obtained at 1/3600th of the cost of existing methods. This was achieved by using trichlorosilane and an organic solvent to prepare a hydrogen silsesquioxane (HSQ) polymer, and by optimizing the LED optoelectric properties. Based on many silicon quantum dots synthesized in our study, each of them enabled us to quantitative the relationships HSQ polymer structure, PLQY, and LED efficiency, exhibiting the critical parameters that governed their performances. Moreover, the simple and cost-effective methods proposed here could prove invaluable for the synthesis and characterization of silicon quantum dots in the near future.

Feasibility study of fabricating 20 nm resolution dielectric Fresnel zone plates with ultrahigh aspect ratio for EUV optics

EUV light optics are either reflective or diffractive due to the substantial absorption characteristics by almost all materials. Despite great successes in manufacturing integrated circuit chips, reflective EUV optics are still unfriendly to small-to-medium enterprise (SME) because of the enormous costs. Recently, diffractive EUV optics has come to the light in hopes to be able to establish manufacturing nanoscale products and inspecting nanoscale structures. Diffractive zone plates with high resolution in EUV wavelengths are urgently needed. This paper reports our latest success in developing 20 nm resolution zone plates for focusing and imaging in the EUV and soft X-ray regions. It firstly discusses the diffraction efficiency of FZPs tailored for 13.5 nm wavelength to decide the essential height of the zone plate. Then, Monte Carlo simulation method was used to figure out the achievable zone plate parameters by high-resolution electron beam lithography (EBL). Finally, this work systematically explored the viability of nanofabricating top-tier 20 nm resolution hydrogen silsesquioxane (HSQ) zone plates with the duty cycle ratio nearing 1:1 and the aspect ratio approaching 13:1 on 50 nm thick Si3N4 membranes.

Blue GaN-based DFB laser diode with sub-MHz linewidth

Distributed feedback laser diodes (DFBs) serve as simple, compact, narrow-band light sources supporting a wide range of photonic applications. Typical linewidths are on the order of sub-MHz for free-running III-V DFBs at infrared wavelengths, but linewidths of short-wavelength GaN-based DFBs are considerably worse or unreported. Here, we present a free-running InGaN DFB operating at 443 nm with an intrinsic linewidth of 685 kHz at a continuous wave output power of 40 mW. This performance is achieved using a first-order embedded hydrogen silsesquioxane (HSQ) surface grating. The frequency noise is measured using a cross-correlated self-heterodyne frequency discriminator, and two estimations of integrated linewidth are evaluated using 1/π integration and β-separation line integration methods.

Multiscale Fabrication Process Optimization of DFB Cavities for Organic Laser Diodes.

In the context of the quest for the Organic Laser Diode, we present the multiscale fabrication process optimization of mixed-order distributed-feedback micro-cavities integrated in nanosecond-short electrical pulse-ready organic light-emitting diodes (OLEDs). We combine ultra-short pulsed electrical excitation and laser micro-cavities. This requires the integration of a highly resolved DFB micro-cavity with an OLED stack and with microwave electrodes. In a second challenge, we tune the cavity resonance precisely to the electroluminescence peak of the organic laser gain medium. This requires precise micro-cavity fabrication performed using e-beam lithography to pattern gratings with a precision in the nanometer scale. Optimal DFB micro-cavities are obtained with 300 nm thick hydrogen silsesquioxane negative-tone e-beam resist on 50 nm thin indium tin oxide anode exposed with a charge quantity per area (i.e., dose) of 620 µC/cm2, developed over 40 min in tetramethylammonium hydroxide diluted in water. We show that the integration of the DFB micro-cavity does not hinder the pulsed electrical operability of the device, which exhibits a peak current density as high as 14 kA/cm2.

Cost-Effective Ultrabright Silicon Quantum Dots and Highly Efficient LEDs from Low-Carbon Hydrogen Silsesquioxane Polymers.

Cost-effective methods of synthesizing bright colloidal silicon quantum dots (SiQDs) for use as heavy-metal-free QDs, which have applications as light sources in biomedicine and displays, are required. We report simple protocols for synthesizing ultrabright colloidal SiQDs and fabricating SiQD LEDs based on hydrogen silsesquioxane (HSQ) polymer synthesis. Red photoluminescence with a quantum yield (PLQY) of 60-80% and LEDs with an external quantum efficiency (EQE) of >10% were obtained at 1/3600th of the cost of existing methods. This was achieved by using HSiCl3 and a low-polarity solvent to prepare the HSQ polymer and by optimizing the LED hole-injection layer thickness. A stochastic analysis of 31 SiQD syntheses revealed that SiQDs with the highest PLQYs were obtained from a hard, low-carbon HSQ polymer precursor containing many Si-H groups and cage structures. Notably, simple FTIR measurements predicted whether a HSQ polymer would yield high-PLQY SiQDs and high-EQE LEDs. These straightforward, cost-effective protocols should lead to advances in SiQD synthesis and LED fabrication methods.

Mitigating challenges in aberration-corrected electron-beam lithography on electron-opaque substrates

Aberration-corrected electron-beam lithography (AC-EBL) using ultra-thin electron transparent membranes has achieved single-digit nanometer resolution in two widely used electron-beam resists: poly (methyl methacrylate) (PMMA) and hydrogen silsesquioxane. On the other hand, AC-EBL implementation on thick, electron-opaque substrates is appealing for conventional top-down fabrication of quantum devices with nanometer-scale features. To investigate the performance of AC-EBL on thick substrates, we measured the lithographic point spread function of a 200 keV aberration-corrected scanning transmission electron microscope by defining both positive and negative patterns in PMMA thin films, spin-cast on thick SiO2/Si substrates. We present the problems encountered during pre-exposure beam focusing and discuss methods to overcome them. In addition, applying some of these methods using commercial 50 nm thick SiN X membranes with thick Si support frames, we printed arrays of holes in PMMA with pitches around 26 nm on SiN X /Si substrates with increasing Si thickness. Our results show that proximity effects from even 50 nm thick SiN X membranes limit hole arrays to 20 nm pitch; however, down to this limit, the effect of the substrate thickness on the pattern quality is minimal. These results highlight the need for novel resists less susceptible to proximity effects, or resists which can be used directly, after development, as the dielectric material in periodic gates in 2D quantum devices.

Improved frequency performance in AlGaN/GaN HEMTs on Si using hydrogen silsesquioxane-assisted gate

AlGaN/GaN HEMTs have been regarded as the most promising option for achieving high-frequency power amplifier in various applications, including wireless communication, aerospace, and radar systems. To enable their use at even higher frequency, we conducted a study to enhance the frequency characteristics of AlGaN/GaN high electron mobility transistors (HEMTs) on a silicon substrate. By employing a hydrogen silsesquioxane (HSQ)-assisted gate, AlGaN/GaN HEMT with an LG of 0.17 μm and LSD of 5 μm exhibited a VTH of 4.5 V, ID.max of 885 mA/mm, and gm.max of 253 mS/mm. The planar-gate without HSQ shows VTH of 4.4 V, ID.max of 876 mA/mm, and gm.max of 258 mS/mm. The DC characteristics are comparable to those observed in planar-gate HEMT with a conventional gate structure. Though the DC characteristics of both devices are similar, the HSQ-assisted gate HEMT exhibits a higher fT/fmax of 55/89 GHz, whereas the planar-gate HEMT yields an fT/fmax of 38/64 GHz. The 32% reduction in the total extrinsic gate capacitance (Cgs + Cgd) is the major contributor to the improved frequency performance of the HSQ-assisted gate AlGaN/GaN HEMT. The adoption of HSQ-assisted gate AlGaN/GaN HEMTs presents itself as a highly advantageous choice for achieving higher-frequency operations. © 2023 Elsevier Inc. All rights reserved.

Understanding the Formation Mechanisms of Silicon Particles from the Thermal Disproportionation of Hydrogen Silsesquioxane.

Crystalline silicon particles sustaining Mie resonances are readily obtained from the thermal processing of hydrogen silsesquioxane (HSQ). Here, the mechanisms involved in silicon particle formation and growth from HSQ are investigated through real-time in situ analysis using an environmental transmission electron microscope and X-ray diffractometer. The nucleation of Si nanodomains is observed starting around 1000 °C. For the first time, a highly mobile intermediate phase is experimentally observed, thus demonstrating a previously unknown growth mechanism. At least two growth processes occur simultaneously: the coalescence of small particles into larger particles and growth mode by particle displacement through the matrix toward the HSQ grain surface. Postsynthetic characterization by scanning electron microscopy further supports the latter growth mechanism. The gaseous environment employed during synthesis impacts particle formation and growth under both in situ and ex situ conditions, impacting the particle yield and structural homogeneity. Understanding the formation mechanisms of particles provides promising pathways for reducing the energy cost of this synthetic route.

Development of EUV interference lithography for 25 nm line/space patterns

In this study, we present the performance of an extreme ultraviolet interference lithography (EUV-IL) setup that was reconstructed at Taiwan Light Source 21B2 EUV beamline in the National Synchrotron Radiation Research Center (NSRRC), Taiwan. An easy-to-perform fabrication method to produce a high-quality transmission grating mask and a simple design of experimental setup for EUV-IL were developed. The current EUV-IL setup is capable of fabricating line/space patterns down to 25 nm half-pitch in hydrogen silsesquioxane (HSQ) resist. Preliminary exposure results revealed that optimized slit width and exposure time significantly improved line/space pattern quality. The current EUV-IL tool at NSRRC can be used for nano-patterning and resist screening to advance the next generation of semiconductor devices.

Electron beam lithography and dimensional metrology for fin and nanowire devices on Ge, SiGe and GeOI substrates

Until now there is no systematic study on the effect of the substrate type on the hydrogen silsesquioxane (HSQ) electron beam lithography (EBL) patterning process. We investigate arrays of line structures with varying width and spacing, starting at 10 nm, exposed at varying dose, and developed by salty NaOH and TMAH developers on group IV semiconductor substrates. We demonstrate that the HSQ EBL process on Ge is much more limited in achieving the smallest obtainable features, having optimal uniformity and fidelity, in comparison to Si. Monte-Carlo simulations of the e-beam/substrate interactions for “pure” Si and Ge substrates, and varying content Ge/Si epitaxial layers on Si, suggest that the limitations seen are directly linked to back-scattered electron (BSE) generation. As predicted by the simulations and shown experimentally, improved fidelity and resolution of the features can be achieved by minimizing the (BSE) generation coming from the Ge contribution in the substartes. Finally, from a metrology perspective, it is demonstrated that although line patterns may appear resolved in SEM images, the variation in the brightness across neighbouring lines is a key parameter in understanding the resist clearance between lines, that will affect the next etching step for pattern transfer onto the underlying substrate. These results are important for patterning high-density line structures and nano-device engineering as required for realising state-of-the art laterally stacked group IV multi-channel field effect transistors (FETs).

GaN and AlGaN/AlN Nanowire Ensembles for Ultraviolet Photodetectors: Effects of Planarization with Hydrogen Silsesquioxane and Nanowire Architecture

GaN and AlGaN/AlN Nanowire Ensembles for Ultraviolet Photodetectors: Effects of Planarization with Hydrogen Silsesquioxane and Nanowire Architecture

Sn-Induced Synthesis of Highly Crystalline and Size-Confined Si Nanorods at Moderately High Temperatures Using Hydrogen Silsesquioxane

Size-confined Si nanorods (NRs) have gained notable interest because of their tunable photophysical properties that make them attractive for optoelectronic, charge storage, and sensor technologies. However, established routes for fabrication of Si NRs use well-defined substrates and/or nanoscopic seeds as promoters that cannot be easily removed, hindering the investigation of their true potential and physical properties. Herein, we report a facile, one-step route for the fabrication of Si NRs via thermal disproportionation of hydrogen silsesquioxane (HSQ) in the presence of a molecular tin precursor (SnCl4) at a substantially lower temperature (450 °C) compared to those used in the synthesis of size-confined Si nanocrystals (>1000 °C). The use of these precursors allows the facile isolation of phase-pure Si NRs via HF etching and subsequent surface passivation with 1-dodecene via hydrosilylation. The diameters (7.7–16.5 nm) of the NRs can be controlled by varying the amount of SnCl4 (0.2–3.0%) introduced during the HSQ synthesis. Physical characterization of the NRs suggests that the diamond cubic structure is not affected by SnCl4, HF etching, and hydrosilylation. Surface analysis of NRs indicates the presence of Si0 and Sin+ species, which can be attributed to core Si and surface Si species bonded to dodecane ligands, respectively, and a systematic variation of the Si0:Si–C ratio with the NR diameter. The NRs show strong size confinement effects with solid-state absorption onsets (2.51–2.80 eV) and solution-state (Tauc) indirect energy gaps (2.54–2.70 eV) that can be tuned by varying the diameter (16.5–7.7 nm). Photoluminescence (PL) and time-resolved PL (TRPL) studies reveal size-dependent emission (1.95–2.20 eV) with short, nanosecond lifetimes across the visible spectrum, which trend closely with absorption trends seen in solid-state absorption data. The facile synthesis developed for size-confined Si NRs with high crystallinity and tunable optical properties will promote their application in optoelectronic, charge storage, and sensing studies.

Three-dimensional printing of silica glass with sub-micrometer resolution

Silica glass is a high-performance material used in many applications such as lenses, glassware, and fibers. However, modern additive manufacturing of micro-scale silica glass structures requires sintering of 3D-printed silica-nanoparticle-loaded composites at ~1200 °C, which causes substantial structural shrinkage and limits the choice of substrate materials. Here, 3D printing of solid silica glass with sub-micrometer resolution is demonstrated without the need of a sintering step. This is achieved by locally crosslinking hydrogen silsesquioxane to silica glass using nonlinear absorption of sub-picosecond laser pulses. The as-printed glass is optically transparent but shows a high ratio of 4-membered silicon-oxygen rings and photoluminescence. Optional annealing at 900 °C makes the glass indistinguishable from fused silica. The utility of the approach is demonstrated by 3D printing an optical microtoroid resonator, a luminescence source, and a suspended plate on an optical-fiber tip. This approach enables promising applications in fields such as photonics, medicine, and quantum-optics.

Atomic layer etching of nanowires using conventional reactive ion etching tool

Innovative material and processing concepts are needed to further enhance the performance of complementary metal-oxide-semiconductor (CMOS) transistors-based circuits as the scaling limits are being reached. To supplement that, we report on the development of an atomic layer etching (ALE) process to fabricate small and smooth nanowires using a conventional dry etching tool. Firstly, a negative tone resist (hydrogen silsesquioxane) is spin-coated on Silicon Germanium-on-insulator (SiGeOI) samples and electron beam lithography is performed to create nanopatterns. These patterns act as an etch mask and are transferred into the SiGeOI layer using an inductively-coupled plasma reactive ion etching (ICP-RIE) process. Subsequently, an SF6 and Ar+ based ALE process is employed to smoothen the nanowires and reduce their widths. SF6 modifies the surface of the samples, while in the next step Ar+ removes the modified surface. To investigate the effect of this process on the nanowire width, several ALE cycles are performed. The etched features are inspected using scanning electron microscopy. With the increasing number of ALE cycles, a reduction in the width is observed. An etch per cycle of 1.1 Å is obtained.

Near-field infrared nanoscopic study of EUV- and e-beam-exposed hydrogen silsesquioxane photoresist

This article presents a technique of scattering-type scanning near-field optical microscopy (s-SNOM) based on scanning probe microscopy as a nanoscale-resolution chemical visualization technique of the structural changes in photoresist thin films. Chemical investigations were conducted in the nanometer regime by highly concentrated near-field infrared on the sharp apex of the metal-coated atomic force microscopy (AFM) tip. When s-SNOM was applied along with Fourier transform infrared spectroscopy to characterize the extreme UV- and electron-beam (e-beam)-exposed hydrogen silsesquioxane films, line and space patterns of half-pitch 100, 200, 300, and 500 nm could be successfully visualized prior to pattern development in the chemical solutions. The linewidth and line edge roughness values of the exposed domains obtained by s-SNOM were comparable to those extracted from the AFM and scanning electron microscopy images after development. The chemical analysis capabilities provided by s-SNOM provide new analytical opportunities that are not possible with traditional e-beam-based photoresist measurement, thus allowing information to be obtained without interference from non-photoreaction processes such as wet development.