Etch Resistance Research Articles

Fabricating 3D Si nanostructure via a novel Ga+ implantation enabled maskless dry etching process

Three-dimensional (3D) nanostructure is the key to the miniaturization of nonlinear photonic and electronic devices. Because of the great demand on the ultra-small nanostructures, the novel nanofabrication technologies with flexible 3D silicon (Si) fabrication capability are of great importance. Herein, by combining Ga+ FIB implantation and ICP dry etching processes, we proposed a novel Ga+ FIB implantation assisted maskless dry etching technology for direct fabrication of 3D Si nanostructures. We found that the implanted Ga+ induced amorphization layer in Si substrate acts as the ‘quasi-mask’ during the ICP dry etching process. The increase of Ga+ concentration in amorphization layer of Si substrate improves the etching resistance of the area. Moreover, enabled by high resolution and flexibility of FIB, the proposed technology is capable of directly fabricating various 3D Si nanostructures in a simple way, such as 3D nanoscale artificial bowtie arrays with sub-10 nm gaps, multi-scale 3D Si nanostructures with arbitrary patterns. More importantly, the proposed technology is compatible to current semiconductor manufacturing process. Benefiting by the advantages of simplicity and high efficiency, the proposed maskless dry etching process promises great application potential in the fields of nonlinear photonics and micro-electronics.

Impact of plasma power on plasma enhanced atomic layer deposited TiO2 as a spacer

As the size of devices is scaled down, micro-patterning technology is increasing in importance. In micro-patterning, spacers require precise thickness and uniform deposition at low temperature. To meet these requirements, atomic layer deposition (ALD), which can be controlled to an accurate thickness, was introduced. Therefore, we investigated plasma-enhanced ALD using radicals for high reactivity. Optical emission spectroscopy and a Langmuir probe were used to evaluate plasma properties such as radical intensity and plasma density at different plasma powers. Regardless of plasma power, growth per cycle and compositions of Ti and O remained constant. X-ray photoelectron spectroscopy showed that application of 500 W decreased the area of Ti2O3 from 20.2 % to 4.5 % compared with 100 W due to the increased amount of oxygen radicals. X-ray reflectivity results showed a 4.09 g/cm3 density of TiO2 film at 100 W, which increased to 4.2 g/cm3 at 500 W, indicating a decrease of Ti2O3. Meanwhile, the wet etch rate of TiO2 film was 1.72 Å/min at 100 W and 0.8 Å/min at 500 W, and the denser film had superior etch resistance. Finally, transmission electron microscopy showed that step coverage of TiO2 films improved from 90.9 % to 99.9 % with increasing power. Thus, application of high power effectively improved the properties of TiO2 films.

Oxygen plasma-assisted magnetron sputtering deposition of non-stoichiometric Y2O3 films: Influence of oxygen vacancies on etching resistance

Yttrium oxide (Y2O3) films are widely used to protect equipment in plasma etching, a crucial technique in semiconductor processing, due to their exceptional resistance to plasma etching. Since oxygen vacancy affects the performance of Y2O3 and may impact physical etching resistance, the internal relationship necessitates further investigation. In this article, Y2O3 films with varying oxygen vacancy concentrations are prepared by reactive magnetron sputtering with the assistance of oxygen plasma. The formation and development of oxygen vacancies in cubic Y2O3 films and their impact on the physical etching resistance were investigated. The experiment results indicate that the accumulation of oxygen vacancies causes non-stoichiometry and the etching rate is significantly reduced. Combined with density-functional theory, it is revealed that oxygen vacancy distorts the lattice, which increases covalent YO bonding and the formation energy of atoms. Moreover, the vacancy line defects resulting from diffusion and aggregation of oxygen vacancies exert a similar influence on the adjacent yttrium and oxygen layers. The enhancement of physical etching resistance is attributed to the strengthened internal YO bonds led by increasing oxygen vacancy concentration in the cubic Y2O3 films without inducing phase transition. The discovery enriches the understanding of how plasma interacts with Y2O3, and the etching mechanism.

Effect of Metal Oxide Deposition on the Sensitivity and Resolution of E-Beam Photoresist.

Organic-inorganic hybrid resists offer a solution to the issue of low sensitivity in organic photoresists like poly(methyl methacrylate) (PMMA). In this study, an organic-inorganic hybrid resist (PMMA-Al2O3) with high sensitivity and resolution was prepared by depositing metal oxides into PMMA using sequential infiltration synthesis (SIS). PMMA-Al2O3 was prepared by precisely controlling the number of SIS cycles (<23) in various atomic layer deposition (ALD) processes to facilitate the growth of metal oxides within PMMA pores. The impact of different metal oxide contents and distributions on the sensitivity and resolution of electron beam exposure was investigated. Numerical simulations of the deposit formation within the PMMA pores were performed by solving the pore-scale ALD governing equations fed by the reactor-scale boundary conditions. The gradual pore constriction with SIS cycles was predicted and validated by the experimental charaterizations. The results demonstrated that PMMA-Al2O3 was prepared using 20 SIS cycles, which corresponds to the numerically predicted occurrence of the pore blockage at the upper region of the PMMA layer, exhibiting optimal electron beam (e-beam) resolution while enabling line exposure with a width of 50 nm. While the corresponding sensitivity was lower than those of the samples prepared using 5 and 10 SIS cycles, the degradation of the PMMA structure was affected under exposure. The pattern transfer results showed that the line width was well retained for 20 cycles of deposition because of the high etching resistance of Al2O3. This research is expected to provide an effective approach to developing next-generation high-performance photoresists.

Single‐Component High‐Resolution Dual‐Tone EUV Photoresists Based on Precision Self‐Immolative Polymers

Electron beam (EB) and extreme ultraviolet (EUV) lithography are advanced techniques capable of achieving sub‐10 nm resolutions, critical for fabricating next‐generation nanostructures and semiconductor devices. However, developing EUV photoresists that meet all demands for resolution, line edge roughness (LER), and sensitivity (RLS) remains a significant challenge. Herein, we introduce high‐performance photoresists based on single‐component self‐immolative polymers (SIPs) with inherent signal amplification via cascade degradation. These SIPs function as dual‐tone photoresists under both EB and EUV lithography, with performance primarily determined by the exposure dose. Lithographic evaluations show that discrete SIPs provide significant improvements over disperse counterparts, achieving higher resolution and reduced LER. Specifically, a discrete SIP with a DP of 12 produces a line‐space pattern with a resolution of approximately 18 nm and an LER of 1.8 nm, compared to 21 nm resolution and 2.5 nm LER for disperse SIPs. Additionally, these SIP‐based photoresists, enriched with aromatic structures, exhibit excellent etch resistance. The single‐component nature and potential to address the RLS trade‐off underscore the promise of discrete SIPs for EUV lithography.

Fabrication, Microstructure and Plasma Resistance Behavior of Y-Al-Si-O (YAS) Glass-Ceramics Coated on Alumina Ceramics.

This study investigates the fabrication, microstructural characteristics and plasma resistance of Y-Al-Si-O (YAS) glass-ceramics coated on alumina ceramics. YAS frits were initially prepared using a melt-quenching method, then homogenously milled and coated onto alumina ceramics. The melt-coating process was conducted at 1650 °C for 1 h. The composition and microstructure of the glass frits and coatings were thoroughly characterized using X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. These analyses revealed a dense microstructure with a polycrystalline structure predominantly composed of Y3Al5O12 (YAG) phase and a minor phase of Y2Si2O7. The YAS coatings on alumina revealed a dense layer with strong adhesion to the substrate. Subsequently, the coatings underwent C4F6/Ar/O2 plasma treatment for 1 h. Plasma exposure tests demonstrated that the YAS-coated alumina exhibited significantly better etching resistance compared to uncoated alumina, with minimal surface damage observed on the YAS coating, confirming its protective properties against plasma. The superior plasma resistance of YAS coatings is attributed to the predominance of its YAG phase. This research offers a more stable and cost-efficient solution for protecting ceramics in demanding plasma environments.

Influence of Chemical Structures on E-Beam Lithography Performance of Polysilsesquioxanes.

Hydrogenated silsesquioxane (HSQ) is a key inorganic electron beam resist, celebrated for its sub-10 nm resolution and etching resistance, but it faces challenges with stability and sensitivity. Our innovative study has comprehensively assessed the lithographic performance of three functionalized polysilsesquioxane (PSQ) resist series─olefins, halogenated alkanes, and alkanes─under electron beam lithography (EBL). We discovered that the addition of olefin groups, such as in the HMP-30 formulation with 30% propyl acrylate, remarkably increased the sensitivity to 0.6 μC/cm2. The inclusion of halogenated aromatic and hydrogen-substituted methyl groups further enhanced sensitivity and contrast, with HClBN-50 achieving a 22.9 nm resolution pattern. At the same time, the storage of PSQ resists was significantly improved compared to commercial HSQ with increasing alkane group content. Crucially, our research has unveiled the lithography reaction mechanism, highlighting how group encapsulation and steric hindrance influence PSQ performance. This insight is groundbreaking, offering a deeper understanding of the molecular structure-performance relationship and laying the groundwork for developing next-generation electron beam resists with superior sensitivity, resolution, and contrast for microelectronics manufacturing.

Microstructure and corrosion resistance of novel rare-earth-zirconia doped Y2O3 plasma-sprayed coating

Y2O3 coatings are widely applied in semiconductor etching machines to protect the inner walls of aluminum alloys. This study reports the preparation of yttria-based coatings on aluminum alloy substrates using atmospheric laminar plasma spraying (ALPS) methods. In this study, four yttria-based coatings were designed and tested for their thermal performance, plasma etching resistance, and resistance to laser ablation. The rare-earth-zirconia (RE-ZrO2) doped Y2O3 coating exhibited the best thermal insulation performance, with a thermal conductivity of approximately 0.6 W m−1 k−1 at 600 °C. Plasma etching experiments demonstrated that more rare-earth fluorides were generated on the surface of the RE-ZrO2 doped Y2O3 coating, which weakened the plasma energy. Finally, the lowest etching rate was achieved. Laser ablation experiments demonstrated that the depth of the ablation pit on the surface of the RE-ZrO2 doped Y2O3 coating was shallow, indicating good laser ablation resistance. These results indicate that rare-earth-doped yttria-based coatings provide excellent corrosion protection against plasma etching and laser ablation.

Plasma etching resistance and mechanical properties of polymorph Gd2O3-MgO nanocomposite with Zr phase stabilizer incorporation

In the semiconductor manufacturing process, including front-end and back-end processes, when conducting plasma etching and plasma dicing of chips, both wafers and the ceramic components comprising the chamber’s interior can be influenced by intense plasma attack. The longer ceramic components are exposed to a strong plasma environment, the more those components will wear away and need to be replaced. In addition, non-volatiles generated by the reaction between the plasma gas and components can rise to the top of the wafer and cause defects. To improve semiconductor production, it is essential to minimize the generation of contaminant particles from ceramics and improve their plasma resistance and mechanical properties. Herein, we synthesized and consolidated Gd2O3-MgO nanocomposite with different incorporations of Zr4+ phase stabilizer. For the first time, we evaluated the plasma etching resistance of these nanocomposites. Compared to those of the Y2O3 reference, the etching rates and surface roughness of these nanocomposites were significantly lower. This research has proposed a variety of candidate materials for ceramic parts in plasma etching equipment; this material is not limited to Y and Al-based materials, and is expected to be applied as a next-generation material to improve the mechanical properties of MgO.

Si-Containing Reverse-Gradient Block Copolymer for Inorganic Pattern Amplification in EUV Lithography.

Although extreme ultraviolet lithography (EUVL) has emerged as a leading technology for achieving high quality sub-10 nm patterns, the insufficient pattern height of photoresist patterns remains a challenge. Directed self-assembly (DSA) of block copolymers (BCPs) is expected to be a complementary technology for EUVL due to its ability to form periodic nanostructures. However, for a combination with EUV patterns, it is essential to develop advanced BCP systems that are suited to inorganic-containing EUV photoresists and offer improved resolution limits, pattern quality, and etch resistance. Here, we report a reverse-gradient BCP system, poly[(styrene-gradient-pentafluorostyrene)-b-4-tert-butyldimetilsiloxystyrene] [P(S-g-PFS)-b-P4BDSS] BCP, which enables universally vertically oriented lamellae even in the absence of a neutral layer, while also containing a Si-containing block with high etch resistance. The gradient block, characterized by a gradual compositional transition from the block junction to the tail, plays a crucial role in creating an adequate surface energy contrast that energetically drives the formation of perpendicular lamellae without neutral layer. When used as a pattern height enhancement layer in EUVL, a high aspect ratio (3.29) of patterns was achieved, thereby offering a supplementary solution for next-generation EUVL.

Aqueous Developable and CO2-Sourced Chemical Amplification Photoresist with High Performance.

Seeking high-performance photoresists is an important item for semiconductor industry due to the continuous miniaturization and intelligentization of integrated circuits. Polymer resin containing carbonate group has many desirable properties, such as high transmittance, acid sensitivity and chemical formulation, thus serving as promising photoresist material. In this work, a series of aqueous developable CO2-sourced polycarbonates (CO2-PCs) were produced via alternating copolymerization of CO2 and epoxides bearing acid-cleavable cyclic acetal groups in the presence of tetranuclear organoborane catalyst. The produced CO2-PCs were investigated as chemical amplification resists in deep ultraviolet (DUV) lithography. Under the catalysis of photogenerated acid, the acetal (ketal) groups in CO2-PC were hydrolysed into two equivalents of hydroxyl groups, which change the exposed area from hydrophobicity to hydrophilicity, thus enabling the exposed area to be developed with water. Through normalized remaining thickness analysis, the optimal CO2-derived resist achieved a remarkable sensitivity of 1.9 mJ/cm2, a contrast of 7.9, a favorable resolution (750 nm, half pitch), and a good etch resistance (38 % higher than poly(tert-butyl acrylate)). Such performances outperform commercial KrF and ArF chemical amplification resists (i.e., polyhydroxystyrene-derived and polymethacrylate-based resists), which endows broad application prospects in the field of DUV (KrF and ArF) and extreme ultraviolet (EUV) lithography for nanomanufacturing.

Aqueous Developable and CO2‐Sourced Chemical Amplification Photoresist with High Performance

AbstractSeeking high‐performance photoresists is an important item for semiconductor industry due to the continuous miniaturization and intelligentization of integrated circuits. Polymer resin containing carbonate group has many desirable properties, such as high transmittance, acid sensitivity and chemical formulation, thus serving as promising photoresist material. In this work, a series of aqueous developable CO2‐sourced polycarbonates (CO2‐PCs) were produced via alternating copolymerization of CO2 and epoxides bearing acid‐cleavable cyclic acetal groups in the presence of tetranuclear organoborane catalyst. The produced CO2‐PCs were investigated as chemical amplification resists in deep ultraviolet (DUV) lithography. Under the catalysis of photogenerated acid, the acetal (ketal) groups in CO2‐PC were hydrolysed into two equivalents of hydroxyl groups, which change the exposed area from hydrophobicity to hydrophilicity, thus enabling the exposed area to be developed with water. Through normalized remaining thickness analysis, the optimal CO2‐derived resist achieved a remarkable sensitivity of 1.9 mJ/cm2, a contrast of 7.9, a favorable resolution (750 nm, half pitch), and a good etch resistance (38 % higher than poly(tert‐butyl acrylate)). Such performances outperform commercial KrF and ArF chemical amplification resists (i.e., polyhydroxystyrene‐derived and polymethacrylate‐based resists), which endows broad application prospects in the field of DUV (KrF and ArF) and extreme ultraviolet (EUV) lithography for nanomanufacturing.

Hybrid Silicon-Organic Methacrylate Monomers and Hyperbranched Polymers that Override the Ohnishi Parameter for Oxygen Plasma Etch Resistance

Hybrid Silicon-Organic Methacrylate Monomers and Hyperbranched Polymers that Override the Ohnishi Parameter for Oxygen Plasma Etch Resistance

Correlative characterization of plasma etching resistance of various aluminum garnets

AbstractPlasma etching is a crucial step in semiconductor manufacturing. High cleanliness and wafer‐to‐wafer reproducibility in the etching chamber are essential in order to successfully achieve nanometer‐sized integrated functions on the wafer. The trend toward the application of more aggressive plasma compositions leads to higher demands on the plasma resistance of the materials used in the etching chamber. Due to its excellent etch resistance, yttrium aluminum garnet Y3Al5O12 (YAG) is starting to replace established materials like SiO2 or Al2O3 in this kind of application. In this study, reactive spark plasma sintering (SPS) was used to manufacture highly dense YAG ceramics from the respective oxides. In addition, yttrium was replaced with heavier lanthanoids (Er, Lu), intending to investigate the role of the A‐site cation in the garnet type structure on the plasma erosion behavior. The produced materials were exposed to fluorine‐based etching plasmas mimicking the conditions in the semiconductor manufacturing apparatus and the erosion behavior was characterized by atomic force microscopy (AFM), secondary ion mass spectrometry (SIMS), transmission electron microscopy (TEM), and profilometry. The induced chemical gradient in the samples is limited to a few nanometers below the surface, which makes its characterization challenging. For advanced analysis, we developed a correlative characterization method combining SIMS and scanning TEM (STEM)–energy‐dispersive spectroscopy (EDS) enabling us to examine the structural and chemical changes in the reaction layer locally resolved. In the case of lanthanoid aluminates, an altered reaction layer and reduced fluorine penetration compared to YAG were found. However, a correlation between the characteristics of the induced chemical gradient and the determined physical erosion rates was not evident.

Plasma enhanced atomic layer deposition of silicon nitride using magnetized very high frequency plasma

To obtain high-quality SiN x films applicable to an extensive range of processes, such as gate spacers in fin field-effect transistors (FinFETs), the self-aligned quadruple patterning process, etc, a study of plasma with higher plasma density and lower plasma damage is crucial in addition to study on novel precursors for SiN x plasma-enhanced atomic layer deposition (PEALD) processes. In this study, a novel magnetized PEALD process was developed for depositing high-quality SiN x films using di(isopropylamino)silane (DIPAS) and magnetized N2 plasma at a low substrate temperature of 200 °C. The properties of the deposited SiN x films were analyzed and compared with those obtained by the PEALD process using a non-magnetized N2 plasma source under the same conditions. The PEALD SiN x film, produced using an external magnetic field (ranging from 0 to 100 G) during the plasma exposure step, exhibited a higher growth rate (∼1 Å/cycle) due to the increased plasma density. Additionally, it showed lower surface roughness, higher film density, and enhanced wet etch resistance compared to films deposited using the PEALD process with non-magnetized plasmas. This improvement can be attributed to the higher ion flux and lower ion energy of the magnetized plasma. The electrical characteristics, such as interface trap density and breakdown voltage, were also enhanced when the magnetized plasma was used for the PEALD process. Furthermore, when SiN x films were deposited on high-aspect-ratio (30:1) trench patterns using the magnetized PEALD process, an improved step coverage of over 98% was achieved, in contrast to the conformality of SiN x deposited using non-magnetized plasma. This enhancement is possibly a result of deeper radical penetration enabled by the magnetized plasma.

Microstructural characterization and inductively coupled plasma-reactive ion etching resistance of Y2O3–Y4Al2O9 composite under CF4/Ar/O2 mixed gas conditions

In the semiconductor manufacturing process, when conducting inductively coupled plasma-reactive ion etching in challenging environments, both wafers and the ceramic components comprising the chamber’s interior can be influenced by plasma attack. When ceramic components are exposed to long-term plasma environments, the eroded components must be replaced. Furthermore, non-volatile reactants can form and settle on semiconductor chips, acting as contaminants and reducing semiconductor production yield. Therefore, for semiconductor processing equipment parts to be utilized, it is necessary that they exhibit minimized generation of contaminant particles and not deviate significantly from the composition of conventionally used Al2O3 and Y2O3; part must also last long in various physicochemical etching environment. Herein, we investigate the plasma etching behavior of Y2O3–Y4Al2O9 (YAM) composites with a variety of mixing ratios under different gas fraction conditions. The investigation revealed that the etching rates and changes in surface roughness for these materials were significantly less than those of Y2O3 materials subjected to both chemical and physical etching. Microstructure analysis was conducted to demonstrate the minimization of crater formation. Mechanical properties of the composite were also analyzed. The results show that the composite can be commercialized as next-generation ceramic component in semiconductor processing equipment applications.

(Invited) Plasma-Enhanced Deposition Mechanism of Hydrogenated Amorphous Carbon Analyzed By Combining Reactive Species Measurement and Machine Learning

Hydrogenated amorphous carbon (a-C:H) thin films synthesized by plasma-enhanced chemical vapor deposition (PECVD)are widely used in various fields of science and technology. For example, they are essential as etching hard masks for the production of 3D-NAND flash memory, because of their high selectivity to Si-based materials and chemical stability. With the demand for higher aspect ratio etching, there is a strong need to improve etching resistance and reduce residual stress of a-C:H masks. They are also widely used in the field of tribology as an important coating for improving friction resistance and slidability. Analyzing the plasma process in which synergistic effects among reactive species and higher-order reactions contribute is generally difficult. Therefore, similar to other process technologies, machine learning-based condition optimization approaches have been actively investigated in recent years. However, machine learning models are generally black boxes, and it is difficult to understand their mechanism of action. Also, the versatility of the learning model is low between different devices. On the other hand, reactive species measurement is effective for understanding the reaction mechanism of the plasma process, but the synergy of multiple reactive species is still extremely complicated. In this study, the contribution of radical species to the etching resistance of a-C:H thin films were quantitatively analyzed using machine learning.The deposition of a-C:H by PECVD using H2/C3H6/CH4 plasma and etching with O2 plasma were alternately repeated at 120 conditions. The radicals generated during the film deposition were measured by a quadrupole mass spectrometer (QMS), and film thickness change during the etching was measured by spectroscopic ellipsometry (SE). A random forest model was learned to predict the etching rate from the mass spectra, and the contribution of each radical to the etching rate was quantitatively evaluated by SHapley additive exPlanation (SHAP).The distribution of SHAP values for the 10 most influential radicals is shown in Figure 1. The positive and negative SHAP values represent the correlation between QMS intensity and SHAP value. The radicals with high hydrogen ratios such as CH~CH4, C2H5, C4H9, C5H9, and C5H11 contributed to the increase of etching rate, while the radicals with low hydrogen ratios such as C3H3 and C5H5 contributed to the decrease of etching rate. The deposition of radicals with low hydrogen ratios and multiple bonds, and the effect of hydrogen extraction in the film are considered to have increased the density of a-C:H and reduced the etching rate. It was found that the control of C/H ratio of radicals as film precursors is important to improve etching resistance. Comparisons with different data set range or other contribution degrees such as LIME enable us to understand the mechanism of action of local active species. By using the contribution analysis methods, it is possible to quantitatively analyze the synergistic effect of reactive species in the process plasma. Figure 1

Enhanced Broadband Light Harvesting in Ultrathin Absorbers Enabled by Epitaxial Stabilization of Silver Thin Film Mirrors.

Silver thin film mirrors are attractive candidates for use as specular back reflectors to enhance broadband light absorption via strong optical interference in ultrathin film semiconductor photoabsorbers. However, deposition of metal-oxide absorbers often requires exposure to high temperature in an oxygen atmosphere, conditions that cause thermal etching and degrade the specular reflectance of silver films. Here, we overcome this challenge and demonstrate that epitaxial growth of silver mitigates thermal etching under the high-temperature oxygen-containing environments that cause polycrystalline films to degrade. The degree of thermal etching resistance is related to the epitaxial film structure, where high-quality films completely prevent thermal etching, allowing for direct deposition of metal-oxide thin film photoabsorbers at elevated temperatures without any degradation of the optical properties of the silver layer. As a proof of concept for device applications, a metal-oxide photoanode for photoelectrochemical water splitting is fabricated by directly growing epitaxial SnO2 and Ti-doped α-Fe2O3 (hematite) thin films onto stabilized silver reflectors by pulsed laser deposition. The photoanode displays enhanced broadband light absorption due to strong interference effects enabled by the highly reflective silver film and demonstrates stable operation in a photoelectrochemical cell under conditions of water photo-oxidation in alkaline electrolyte.

Zinc‐Imidazolate Films as an All‐Dry Resist Technology

AbstractMotivated by the drawbacks of solution phase processing, an all‐dry resist formation process is presented that utilizes amorphous zinc‐imidazolate (aZnMIm) films deposited by atomic/molecular layer deposition (ALD/MLD), patterned with electron beam lithography (EBL), and developed by novel low temperature (120 °C) gas phase etching using 1,1,1,5,5,5‐hexafluoroacetylacetone (hfacH) to achieve well‐resolved 22 nm lines with a pitch of 30 nm. The effects of electron beam irradiation on the chemical structure and hfacH etch resistance of aZnMIm films are investigated, and it is found that electron irradiation degrades the 2‐methylimidazolate ligands and transforms aZnMIm into a more dense material that is resistant to etching by hfacH and has a C:N:Zn ratio effectively identical to that of unmodified aZnMIm. These findings showcase the potential for aZnMIm films to function in a dry resist technology. Sensitivity, contrast, and critical dimensions of the patterns are determined to be 37 mC cm−2, 0.87, and 29 nm, respectively, for aZnMIm deposited on silicon substrates and patterned at 30 keV. This work introduces a new direction for solvent‐free resist processing, offering the prospect of scalable, high‐resolution patterning techniques for advanced semiconductor fabrication processes.

Selective mask deposition using SiCl4 plasma for highly selective etching process

We developed an area-selective deposition process for forming protective layers on top of masks generated using a microwave electron-cyclotron-resonance etching system. A deposition layer is formed only on SiO2 masks without forming an unnecessary deposition layer on the Si surfaces in the etching area, such as the bottoms of the patterns and isolated etching area. The protection layers were selectively formed on a SiO2 mask without forming on a Si etching area by using a SiCl4/H2/Cl2 plasma. The pretreatment to clean the Si and SiO2 surfaces before deposition was important for achieving selective deposition because selectivity appeared by nucleation delay on the cleaned Si surface. On the Si surface, adsorbed SiClx easily desorbed again by reacting with the Cl generated from the plasma. However, adsorbed SiClx on SiO2 was more difficult to desorb by reacting with Cl due to Si–O having a larger binding energy than Si–Si. After the deposition layer was selectively formed on the SiO2 mask, the layer was oxidized by using O2 plasma treatment to improve the etching resistance during the subsequent Si etching. We also investigated a Si etching process using selective deposition during the etching of a 25 nm-pitch line-and-space Si pattern with a SiO2 mask. Extremely highly selective etching was achieved using selective deposition without forming an unnecessary deposition on an isolated Si area.