Multi-Benzyl Chloride Based Molecular Resists Enabling 13 nm Half-Pitch Lithography via Self-Crosslinking

Multi-Benzyl Chloride Based Molecular Resists Enabling 13 nm Half-Pitch Lithography via Self-Crosslinking | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 4 July 2025 V1 Latest version Share on Multi-Benzyl Chloride Based Molecular Resists Enabling 13 nm Half-Pitch Lithography via Self-Crosslinking Authors : Zhuoran liu , Jinping Chen 0000-0002-5632-2290 , Tianjun Yu , Yi Zeng 0000-0003-0694-1795 , Xudong Guo , Shuangqing Wang , Rui Hu , … Show All … , Michaela Vockenhuber , Peng Tian , Dimitrios Kazazis 0000-0002-2124-2813 , Yasin Ekinci , Jun Zhao , Yanqin Wu , Guoqiang Yang , and Yi' Li [email protected] Show Fewer Authors Info & Affiliations https://doi.org/10.22541/au.175161979.92720254/v1 302 views 164 downloads Contents Abstract Supplementary Material Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract We developed a novel negative-tone resist platform based on multi-benzyl chloride modified molecular glasses with low molecular weight (< 800 Da) to address the resist challenges of electron beam lithography (EBL) and extreme ultraviolet lithography (EUVL). The molecular glasses with different substitution positions of chloromethyl group (designated as AD4xCl, x = O, M, and P, representing the ortho-, meta-, and para-substitution, respectively) were designed, synthesized, and their resists’ lithographic performance were evaluated. Feature sizes as small as 16 nm half-pitch (HP) were achieved using EBL, and a significant effect of the substitution positions on the resolution and sensitivity was observed. The atomic force microscopy (AFM) measurement confirmed the difference in substituent positions significantly affects the self-crosslinking efficiency and mechanical strength of the resist films, which is the main reason for the differences in sensitivity and resolution limits. The meta-substituted AD4MCl molecule resist exhibited the best performing and was further investigated by EUVL, achieving an impressive 13 nm pattern with a line edge roughness (LER) of 2.6 nm at an exposure of 137.9 mJ cm -2 . Mechanism studies demonstrate EUV-induced self-crosslinking of multi-benzyl radicals among the AD4MCl molecules drives the solubility switch, enabling high-resolution negative-tone patterning. Cite this paper: Chin. J. Chem. 2025 , 43 , XXX—XXX. DOI: 10.1002/cjoc.202500XXX Multi-Benzyl Chloride Based Molecular Resists Enabling 13 nm Half-Pitch Lithography via Self-Crosslinking Zhuoran Liu, a Jinping Chen * , a Tianjun Yu , a Yi Zeng, a Xudong Guo, b Shuangqing Wang, b Rui Hu, b Michaela Vockenhuber, c Peng Tian , c Dimitrios Kazazis , c Yasin Ekinci * , c Jun Zhao , d Yanqing Wu , d Guoqiang Yang * , b and Yi Li* , a a Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, China b Key Laboratory of Photochemistry, Institute of Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, China c Laboratory for X-ray Nanoscience and Technologies, Paul Scherrer Institute, Villigen CH-5232, Switzerland d Shanghai Synchrotron Radiation Facility, Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201204, China Molecular resist | Non-chemically amplified resist | Extreme ultraviolet lithography | Electron beam lithography | Benzyl chloride | Self-crosslinking Comprehensive Summary We developed a novel negative-tone resist platform based on multi-benzyl chloride modified molecular glasses with low molecular weight (< 800 Da) to address the resist challenges of electron beam lithography (EBL) and extreme ultraviolet lithography (EUVL). The molecular glasses with different substitution positions of chloromethyl group (designated as AD4xCl, x = O, M, and P, representing the ortho-, meta-, and para-substitution, respectively) were designed, synthesized, and their resists’ lithographic performance were evaluated. Feature sizes as small as 16 nm half-pitch (HP) were achieved using EBL, and a significant effect of the substitution positions on the resolution and sensitivity was observed. The atomic force microscopy (AFM) measurement confirmed the difference in substituent positions significantly affects the self-crosslinking efficiency and mechanical strength of the resist films, which is the main reason for the differences in sensitivity and resolution limits. The meta-substituted AD4MCl molecule resist exhibited the best performing and was further investigated by EUVL, achieving an impressive 13 nm pattern with a line edge roughness (LER) of 2.6 nm at an exposure of 137.9 mJ cm -2 . Mechanism studies demonstrate EUV-induced self-crosslinking of multi-benzyl radicals among the AD4MCl molecules drives the solubility switch, enabling high-resolution negative-tone patterning. Background and Originality Content Advances in photoresist materials have always been one of the key enablers for progress in lithography in the semiconductor industry, enabling high-throughput and high-resolution patterning down to 3 nm technology node and below. With the introduction of state-of-the-art extreme ultraviolet lithography (EUVL), a wide variety of resists customized for 13.5 nm wavelength radiation have been developed. [1-4] Chemically-amplified resists (CARs) are widely used in high-volume production due to their high sensitivity. [5-6] However, the multi-component characteristic of CARs makes it difficult to overcome the pattern blurring caused by the acid diffusion [7-8] and the shot noise of EUV photons. [9] Although methods such as incorporating acid anion to polymer backbone, [10-11] using photo-acid generator with bulky size, [7] and adding photo-decomposable quencher, [12] were introduced to improve the lithographic performance, it is still difficult to achieve effective enhancement for sub-20 nm patterns with the conventional CARs. In recent years, non-chemically amplified resists (n-CARs) have attracted substantial attention. They rely on the direct reaction of radiation-sensitive groups during exposure and exhibit the potential to form high-resolution and low line edge roughness (LER) patterns. Various ‘chain scission’ type n-CARs, including polymethylmethacrylate, [13-14] polycarbonates, [15-17] and polysulfones. [18-19] have been developed for EUVL and electron beam lithography (EBL). As a typical ‘chain-scission’ n-CAR, PMMA can resolve 50 nm dense line/space (L/S) patterns with an LER of 4.1 nm by EUVL. [14] In recent years, numerous n-CARs based on a decomposable mechanism have emerged with great progress. [20-21] Our research group has reported a series of the sulfonium-modified polymeric or molecular n-CARs, achieving 13 nm half-pitch (HP) patterns with low LER of 1.8-2.8 nm. [22-27] Our recent explorations of molecular resist based on cascade esterification [28] and polystyrene resists functionalized with iodonium salt [29] and oxime ester [30] groups have successfully improved the sensitivity of n-CARs, exhibiting exposure doses below 100 mJ cm -2 . Compared with n-CARs by decomposable mechanisms, n-CARs based on crosslinking mechanisms undergo a self-polymerization to produce solubility switch without significant film thickness loss. Vinyl and benzyl chloride groups have proven to be sensitive to electron beam and EUV radiation. [31-33] For instance, vinyl group is generally introduced as the photosensitive ligand to induce crosslinking in metallic organic resists. [34-38] However, there is a great lack of research on crosslinking triggered molecular resists. Ishida et al. reported a chloromethyl-based calixarene (CMC4) resist, which achieved an isolated 8 nm line pattern by EBL due to its lower molecular weight and excellent solubility switch. [39] Solak et al. further demonstrated that the CMC4 resist could resolve 16 nm features by EUVL. [31] Up to now, studies on self-crosslinking molecular n-CARs are still rare. Recently, Saifullah et al. have conclusively demonstrated that the molecular size of the resist material is one of the most important parameters on determining the resolution limit. [40] Further studies are necessary to explore the relationship between molecular structures and lithographic performance. In this work, a class of muti-benzyl chloride modified molecular glasses with different substitution positions of chloromethyl group (designated as AD4xCl, x = O, M, and P, representing the ortho-, meta-, and para-substitutions, respectively) were designed and prepared, as shown in Figure 1. The correlation between their structures and lithographic performances was extensively investigated by EBL and EUVL. The low molecular weight of AD4xCl (MW < 800 Da) resists is amenable to high resolution patterns. The meta-substituted AD4MCl resist exhibits the highest sensitivity (1800 μC cm -2 and 137.9 mJ cm -2 ), achieving 18 and 13 nm HP patterns by EBL and EUVL, respectively. Figure 1 Structures of muti-benzyl chloride-modified molecular glasses AD4xCl (x = O, M, and P, representing the ortho-, meta-, and para-substitution). Results and Discussion Synthesis and Characterization of AD4xCl The synthesis of the benzyl chloride-modified molecular glasses is outlined in Scheme S1. Suzuki-coupling of 1,3-bis(3,5-dibromophenyl)-adamantane (AD-4Br) and the corresponding hydroxymethylphenylboronic acid in dioxane/H 2 O mixture in the presence of Pd(PPh 3 ) 4 and K 2 CO 3 provided tetrahydroxymethyl-substituted adamantanes (AD4OMeOH, AD4MMeOH, and AD4PMeOH) in high yields. Subsequent treatment of the adamantine derivatives with thionyl chloride afforded the final multi-benzyl chloride modified molecular glasses AD4xCl (x = O, M, and P, representing the ortho-, meta-, and para- substitution, respectively). The detailed synthesis is provided in the Supporting Information. The synthesized compounds were characterized using 1 H NMR and HR-MS spectra. The 1 H NMR spectra of AD4OCl, AD4MCl, and AD4PCl show singlet peaks at 4.57, 4.67, and 4.65 ppm, respectively (Figures S1−S3), confirming the formation of the benzyl chloride group. HR-MS further validated the expected structures (Figures S4-S6), with ion fragment peaks at m/z = 786.2173 (for AD4OCl), 786.2156 (AD4MCl), and 786.2153 (AD4PCl), matching the calculated weight of 786.2168 for [C 50 H 44 Cl 4 ] + cation). These results confirm the successful synthesis and the structural integrity of the AD4xCl compounds. Physical Properties of AD4xCl Figure 2 (a) Thermogravimetric analysis curves and (b) differential scanning calorimetry curves of AD4xCl at a heating rate of 10 °C min -1 under N 2 atmosphere. (c) 2D AFM images (15×15 μm 2 ) of AD4xCl films and their corresponding RMS roughness values. The thermal stability of AD4xCl was investigated through thermal gravimetric analysis (TGA) as shown in Figure 2a. All three molecular compounds exhibit good stability with 2% weight loss at 145, 186, and 282 °C for AD4PCl, AD4MCl, and AD4OCl, respectively. The phase transition behavior of AD4xCl was further investigated by differential scanning calorimetry (DSC) (Figure 2b). No distinct glass transition was observed for the three compounds below 160 °C. A melting point ( T m ) of 141 °C was observed for AD4OCl in the DSC curve, which is consistent with the result given by the melting point apparatus. AD4PCl and AD4MCl both exhibit melting points above 180 °C, which are much higher than that of AD4OCl. It demonstrates that AD4xCl molecules are stable enough for the lithographic baking process. To confirm the film-forming properties of AD4xCl, the morphology of the spin-coated AD4xCl films was evaluated by atomic force microscopy (AFM) as shown in Figure 2c. The films of AD4xCl all exhibit an amorphous film with root-mean-square roughness (RMS) less than 0.6 nm in an area of 15 ×15 µm 2 , indicating excellent film-forming abilities of the molecule glasses. The smooth surfaces of AD4xCl films demonstrated their potential for excellent photolithographic performance. Screening of the Developing Conditions To investigate the suitable developers for AD4xCl resists, a 254 nm light (~2.5 mW cm -2 ) was used to expose the spin-coated films (∼60 nm) for 4 min. Then, the solubility characteristics of the resist films before and after development in different developers were observed by an optical microscope. Table S1 summarizes the solubility characteristics of the resist films before and after exposure in different developers for 60 s. The three resist films exhibit effective switching in many organic solvents from soluble to insoluble after the exposure, indicating the possibility of negative-tone development. As an example, AD4MCl resist can form micron-sized negative-tone patterns (Figure S7) by 254 nm lithography in the commonly used developers of PGME, MIBK, or n-hexane. To further optimize the development conditions, the contrast curves of AD4xCl resists in several representative developers, such as hexane, PGME, and MIBK, were evaluated by electron beam exposures. The normalized remaining thickness (NRT) of resist films after development was plotted against exposure doses as shown in Figure 3. All the resists exhibit high film retention ratios of above 94%. The observed slight thickness reduction is due to the volume shrinkage of the film from the crosslinking reaction during exposure, suggesting high atom economy of the benzyl chloride-modified resists. The sensitivities and contrasts of the resists in different developers were calculated by fitting the plots with a logistic function, with the results summarized in Table 1. Developer choice has a significant impact on the sensitivity and contrast of the resists. The sensitivity of the resist tends to decrease with increasing developer polarity. For example, the sensitivity of AD4OCl resist was calculated to be 2086, 3360, and 4260 µC cm -2 in n-hexane, PGME, and MIBK developers, respectively (Figure 3a, Table 1, entries 1-3). Similar trends were observed for AD4MCl and AD4PCl resists (Figure 3b, Table 1, entries 4-6 and Figure 3c, Table 1, entries 7-9). This trend is attributed to the increasing solubility of unexposed resist films in the order of hexane, PGME, and MIBK developers, which is consistent with our previous calculation of the solubility parameters for AD4xCl molecule in different solvents. [41] Thus, higher exposure doses are required to increase the crosslinking reactions for the formation of negative patterns. We also plotted contrast curves under the same development conditions to evaluate contrasts and sensitivities of the resists (Figures 4d-f). The three resists exhibit distinct contrast behaviors, even in the same developer. Using MIBK or PGME as the developer (Figures 4d and 4e), the sensitivities decrease in the order of AD4PCl, AD4MCl, and AD4OCl. All three molecules have the same benzyl chloride substituent. The different lithographic performance of the resists is attributed to the different substitution positions. It is speculated that the steric effect of the benzyl chloride group at different substitution positions leads to the sensitivity difference. The substitute at ortho-position exhibits obvious steric hindrance for the induced free radical, which results in a low efficiency of self-crosslinking among molecules. Thus, a higher exposure dose is required to facilitate the crosslinking of AD4OCl molecule. Furthermore, the para-substituted AD4PCl resist exhibits the highest sensitivity due to the lowest steric hindrance for the crosslinking. The meta-substituted AD4MCl molecule resist shows a moderate sensitivity when developing in MIBK or PGME, which is consistent with the steric hindrance of the structure. The AD4PCl resist film is partially soluble in n-hexane before exposure, which makes it difficult to apply as a developer for negative-tone lithography. The cyclohexane with higher dispersion interaction [41-42] is used as an alternative for AD4PCl resist (Figures 3c and 3f), resulting in a high sensitivity for AD4PCl resist. The results demonstrate that developers play an important role in the sensitivity and contrast of molecular resists. Considering the sensitivity and contrast of the three resists in different developers, the n-hexane or cyclohexane, both yielding high sensitivity, were selected as the developer for the subsequent high-resolution lithography experiments. Figure 3 Contrast curves of (a) AD4OCl, (b) AD4MCl, and (c) AD4PCl resists developed with different developers. Contrast curves of AD4xCl resists in (d) MIBK, (e) PGME, and (f) hexane (n-hexane or cyclohexane) developers. Table 1 The sensitivity and contrast value of AD4xCl resists by different developers. 1 AD4OCl n-Hexane 2086 2.18 94% 2 PGME 3360 3.76 94% 3 MIBK 4260 4.13 94% 4 AD4MCl n-Hexane 1678 1.47 94% 5 PGME 2750 2.75 95% 6 MIBK 3331 3.88 95% 7 AD4PCl Cyclohexane 1903 2.01 95% 8 PGME 2648 2.27 97% 9 MIBK 3008 3.75 97% High-resolution Lithographic Performance of AD4xCl Resists by EBL To evaluate the resolution performance of the AD4xCl molecules with different substitution positions, their patterning capability was further investigated using EBL. Figure 4 displays the SEM images of 30, 25, 22, 20, 18, 16, and 15 nm HP patterns obtained by these resists with an initial film thickness of ~32 nm. They exhibit different resolution limits because of the slight differences in molecular structure. Under similar film thicknesses and development conditions, AD4OCl, AD4MCl, and AD4PCl resists can resolve the smallest feature sizes of 20, 18, and 16 nm HP patterns, respectively. In addition, the molecular structure also has a significant effect on the exposure dose for patterning. The dose-to-size values for AD4OCl, AD4MCl and AD4PCl resists are 3400, 1800, and 2400 μC cm -2 , respectively, which are consistent with the results from the NRT analysis. To understand the difference in their resolution limits, Young’s moduli of the films before and after exposure were measured by AFM with the peak force quantitative nanomechanical mapping (PF-QNM) mode (Supporting Information S5). The moduli of the unexposed AD4OCl, AD4MCl, and AD4PCl films were measured as 9.6, 11.1, and 15.2 GPa, respectively. After exposure, the moduli changed to 10.0, 13.1, and 20.4 GPa, respectively. The increase of Young’s moduli before and after exposure is in the order of AD4OCl (0.4 GPa) < AD4MCl (2.0 GPa) < AD4PCl (5.2 GPa), which indicates the degree of self-crosslinking of the molecules. The more efficient self-crosslinking in AD4MCl and AD4PCl films by exposure enhances the mechanical strength of the films. For the negative-tone resists, the moduli of the films after exposure are more critical to the resolution of the lithographic pattern. The order of the Young’s moduli after exposure (AD4OCl < AD4MCl < AD4PCl) is exactly as same as that of the resolution limits (i.e., 20, 18, and 16nm HP). It suggests that the molecules with different substituent positions lead to the difference in Young’s modulus of the exposed films. The enhanced moduli by exposure not only indicates the degree of crosslinking but also mitigate pattern collapse, enabling higher resolution in patterning. Figure 4 SEM images for 30, 25, 22, 20, 18, 16, and 15 nm HP patterns of (a)AD4OCl, (b)AD4MCl, and (c) AD4PCl by EBL. (a) and (b) are in n-hexane, and (c) is in cyclohexane developers. (Film thickness: High-resolution Performance of AD4MCl Resist by EUVL Inspired by the sensitivity and resolution of AD4MCl resist by EBL, we further investigated its lithographic performance of using EUVL. Considering the similar mechanism that both electron beam and EUV irradiation generate low-energy secondary electrons to induce chemical reactions, [25, 43] the same process conditions, such as prebake and development conditions in EBL, are also adopted in EUVL. The contrast curve of AD4MCl resist by EUVL was obtained by exposing the resist film over an open frame (0.5×0.5 mm 2 ) upon a series of EUV doses as shown in Figures S14, giving the contrast of 1.66 and sensitivity of 120 mJ cm -2 . To examine the EUV patterning capability of AD4MCl resist in EUVL, the grating mask forming 16, 15, 14, 13, and 12 nm HP patterns on the wafer was performed using the EUV interference lithography at Paul Scherrer Institute (PSI). A thin film of 20 nm thickness was used to prevent the pattern collapse at the potential resolution limit of the AD4MCl resist. The HPs of 16, 15, 14, 13, and 12 nm dense L/S patterns, together with their corresponding doses, line widths (LW), and LERs, are shown in Figure 5. The feature sizes ranging from 16 to 13 nm are successfully resolved without collapse or bridging at exposure doses of 135.6 to 163.5 mJ cm -2 , with low LERs of 2.3-2.7 nm, respectively (Figures 5a-5d, Figures S15−S18). The LW values for the HP 16, 15, 14, and 13 nm L/S patterns are measured to be 16.6, 14.5, 13.2, and 12.4 nm, respectively. They are less than 8% difference compared with the target critical dimensions (CD), suggesting an accurate patterning capability of AD4MCl resist by EUVL. In the case of the smallest feature size of 12 nm HP, the patterns tend to blur and occasionally bridge (Figure 5e), indicating a resolution limit of 13 nm for AD4MCl resist under the used process conditions. The cross-sectional profiles of the HP 15 and 16 nm patterns formed by AD4MCl resist are also measured by SEM, as shown in Figures 5f and 5g. The profiles of the resist patterns exhibit a sine wave shape, which is consistent with the characteristic of interference lithography. [25, 44] Clear trenches without visible residues or footing were observed. In addition, the cross-sections are smooth and homogeneous without obvious top loss, demonstrating the capability of AD4MCl resist for high-resolution patterning and the subsequent etching process. Figure 5 SEM images of AD4MCl resist forming HP (a) 16, (b) 15, (c) 14, (d) 13, (e) 12 nm L/S patterns, and the corresponding cross-sectional profiles of (f) HP 16 and (g) HP 15nm patterns by EUVL. (Development: n-hexane for 60 s). Mechanism Analysis of AD4MCl Resist by EUV To understand the mechanism of pattern formation and chemical reactions in AD4MCl resist films during EUV exposure, an in situ outgassing analysis was performed. An AD4MCl resist film (thickness: 50 nm) spin-coated on a wafer was exposed to EUV radiation over an area of about 0.6 × 0.8 cm 2 . To monitor the fragments released from the EUV exposed films, an in-situ outgassing analysis was conducted using a quadrupole mass spectrum (QMS) during the exposure, and then XPS analysis was performed on the resist film after a 300 s exposure. A small new signal peak at m/z = 36 amu was observed by the QMS (Figure S19) during the exposure. No fragment peak at 71 amu was observed in the mass spectra, suggesting the outgassing of HCl rather than Cl 2 during EUV exposure. Notably, the pressure change in the chamber is almost negligible at 1.73×10 -7 mbar before and after exposure (Figure S20a). Compared with our previous reports, [45-46] the outgassing of AD4MCl resist film by EUV exposure is much lower than that of molecular CARs (Figure S20b), facilitating its potential application in EUVL. [47-49] Figure 6 (a) High-resolution XPS spectra of C 1s, and (b) XPS atomic composition for the unexposed AD4MCl resist film, EUV exposed film and n-hexane developed film. XPS was employed to investigate the chemical composition of the AD4MCl resist film after EUV exposure and development (Figures S21-S23). Figure 6a shows the high-resolution XPS spectrum of C 1s envelope, which is fitted by two peaks as C-Cl and C-C/C=C/C-H at binding energies of 286.40 and 284.80 eV, respectively. The intensity of the C-Cl signal at 286.40 eV was significantly decreased after exposure and was further reduced after development, suggesting the dechlorination of benzyl chloride groups during EUV exposure. The changes of chlorine in the surface chemical composition relative to carbon atoms during processes were shown in Figure 6b. The ratio of chlorine to carbon atoms before exposure was 50:4, which is consistent with the atom composition of the molecular formula of AD4MCl (C 50 H 44 Cl 4 ). The number of chlorine atoms was significantly reduced from 4 to 1.4 after EUV exposure, and further reduced to 0.8 after development. The results are consistent with the outgassing of HCl molecule during EUV exposure. Based on the in situ outgassing, XPS analysis, and previous literatures, [50-52] we propose a mechanism of crosslinking for AD4MCl under EUV irradiation (Figure 7). The C-Cl bond in benzyl chloride group undergoes a homogeneous cleavage to produce a benzyl radical and a Cl • under EUV irradiation (Figure 7a). The crosslinking of multi-benzyl radicals among different AD4MCl molecules yields a polymer and a new Cl • (Figure 7b). The highly reactive Cl • will abstract the hydrogen atom from the phenyl, generating phenyl radical and HCl gas (Figure 7c). The termination process among the free radical species (phenyl and benzyl radicals) by crosslinking results in the polymer with a larger molecular weight. (Figures 7d-7f). Therefore, the exposed resist forms a dense mesh structure and leads to a remarkable solubility switch in the developer, resulting in a negative-tone resist. Figure 7 A postulated mechanism for AD4MCl solubility switching reactions induced by EUV irradiation. Dry Etch Performance of AD4MCl Resist Etch durability is an important parameter for the resist to transfer nanostructure patterns to the substrate. Therefore, the AD4MCl resist film was subjected to a SF 6 /O 2 plasma to test the etch resistance. Figure S23 shows the SEM cross-sectional height of the AD4MCl resist pattern (Figure S24a), the pattern side wall after etching (Figure S24b) and further after resist-stripping (Figure S24c). The remaining resist thickness was measured to be 31 nm after etching, which is the same to the calculated value by comparing the height difference before and after stripping. The etching depth for the silicon and resist are 193 and 10 nm in 10 s, giving etching rates of 19.3 and 1.0 nm s -1 , respectively. The etch selectivity of the AD4MCl resist to the silicon is 19:1, which is almost twice that of the commercial ZEP resist (10:1) under the same etching conditions. [22] The superior dry-etching resistance for AD4MCl resist is attributed to the high carbon content (~98% by XPS analysis in Figure S23) of exposed film. On the other hand, the crosslinked mesh structure of the resist film also ensures a relatively high etch resistance. [53-55] The pattern transfer capability of AD4MCl resist is studied under the same conditions. Figure 8 shows the cross-sectional SEM images of 100 and 50 nm dense L/S patterns, and a 20 nm semi-dense pattern before, after etching, and after resist stripping. The resist patterns can be transferred to the silicon substrate accurately with smooth and vertical sidewalls. Compared with the 100 nm pattern, the etching rate for the 50 nm pattern significantly decreases due to the trenches becoming narrow. [56] The 20 nm semi-dense patterns are successfully transferred into the silicon substrate with a high aspect ratio above 6:1. All results suggest high etch durability and excellent fidelity of pattern transfer by AD4MCl resist. Figure 8 SEM images of 100, 50 nm L/S, and 20 nm L/3S pattern profiles before etching (top), after etching (middle), and after resist stripping (bottom). Conclusions In summary, we report a series of multi-benzyl chloride modified molecules (AD4xCl) with different substitution positions (ortho, meta, or para), leading to low-molecular-weight n-CARs for nanopatterning. We observed that substitution position significantly influences self-crosslinking efficiency and mechanical strength of the resist films. The meta-substituted AD4MCl resist shows the highest sensitivity among the three resists, giving 18 nm L/S patterns at a dose of 1800 μC cm -2 by EBL. Further EUVL performance of AD4MCl resist achieves an impressive pattern with a resolution of 13 nm HP with an LER of 2.6 nm at 137.9 mJ cm -2 . Further process optimization, including developer selection, development time, and pattern collapse mitigation methods, may further enhance the ultimate resolution of this material. The in situ mass spectrometry and XPS analysis demonstrate the self-crosslinking of multi-benzyl radicals among AD4MCl molecules leads to a dense mesh structure and a remarkable solubility switch. This study highlights the advantages of self-crosslinking triggered molecular resists and offers useful insights for the rational design of next-generation patterning materials. Experimental Materials and characteristic instruments All reagents were purchased from InnoChem (Beijing, CN) or Bidepharm (Shanghai, CN) and used as received without further purification. Solvents were purchased from Sinopharm (Shanghai, CN) as analytical reagent-grade. Dichloromethane was dried over activated 3 A˚ molecular sieves. Nuclear magnetic resonance (NMR) spectra were performed by Avance NEO 600 M (Bruker, Germany) by dissolving solid samples in the corresponding deuterated solvents. The 1 H chemical shifts were referenced to the solvent peak CDCl 3 at 7.26 ppm. High-resolution mass spectra (HR-MS) were performed by Solarix 9.4T High-Resolution FT-MS Mass Spectrometer (Bruker, USA). Thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) (PerkinElmer 4000) were performed at a heating rate of 10 ℃ min -1 under nitrogen. Resist films were prepared by spin-coating (CEE200X, Brewer Science CEE, USA). The film thickness was measured by using ES01A (ELLITOP, China). The scanning electron microscopy (SEM) images were captured by SU8230 scanning electron microscope (Hitachi, Japan) at 1.0 kV, 10 μA. AFM images were taken by Dimension FastscanBio system ( Bruker, USA ). X-ray photoelectron spectroscopy (XPS) was performed on ESCALAB 250Xi (ThermoFisher, UK). The LER was measured by analyzing SEM images with commercial ProSEM software. Preparation of resist films AD4xCl were dissolved in propylene glycol monomethyl ether acetate (PGMEA) with a solution strength. After the solution was filtered through a 0.2 µm organic membrane, the resist solution was spin-coated onto the silicon wafer at 1800~5500 rpm for 60 seconds to give film thickness at 20~60 nm. Thereafter, thin films were subjected to a post-application bake (PAB) process at 80 °C for 150 s to evaporate the residual solvent. No post exposure bake was applied, as it was found to be no significant improvement in lithographic performance. Lithographic evaluation Deep-ultraviolet exposures were performed by a mercury lamp with an emission wavelength of 254 nm. Vistec EBPG 5000 plus ES were used to measure the sensitivity and contrast with an acceleration voltage of 100 keV and beam current of 500 pA. The direct EB writing system JBX-6300FS ( JEOL, Japan ) was used to evaluate the nanopattern ability with an acceleration voltage of 100 keV and beam current of 100 pA. The contrast curve by EUVL was obtained at the National Synchrotron Radiation Laboratory at Heifei. The lithographic experiments were performed at the Paul Scherrer Institute (PSI) at the Swiss Light Source (SLS) synchrotron in Switzerland. For mechanism characterization, the in situ EUV outgassing experiments were performed at BL08U1B XIL beamline of Shanghai Synchrotron Radiation Facility (SSRF). Etching resistance Study Etching durability was examined on an Etchlab 200 tool (Sentech, Germany) using a dry plasma etching technique. The plasma conditions were 30 sccm SF 6 gas flow and 15 sccm O 2 gas flow at a pressure of 7 mTorr. The table temperature was set at -110 ℃ for 10 s. The RF forward power is 5 W and a forward inductively coupled plasma (ICP) forward power is 300 W. A plasma cleaner CPC-F (CIF, China) was used to remove the residual resist after etching. The etch rates were evaluated by measuring the depth of the patterns before and after etching. Supporting Information The supporting information for this article is available on the WWW under https://doi.org/10.1002/cjoc.202500xxx. Acknowledgement This work was supported by the National Natural Science Foundation of China (22090012, 22475224). Chinese Academy of Sciences (CAS) is gratefully acknowledged. We thank the National Center for Nanoscience and Technology, and the Institute of Physics, CAS for EBL experiments. The National Synchrotron Radiation Laboratory at Heifei is also thanked for EUV contrast measurement. Part of this work was performed at Swiss Light Source (SLS), Paul Scherrer Institute, Switzerland. References Wang, X.; Tao, P.; Wang, Q.; Zhao, R.; Liu, T.; Hu, Y.; Hu, Z.; Wang, Y.; Wang, J.; Tang, Y.; Xu, H.; He, X. Trends in photoresist materials for extreme ultraviolet lithography: A review. Mater. Today 2023 , 67 , 299-319.Zhang, Y.; Yu, H.; Wang, L.; Wu, X.; He, J.; Huang, W.; Ouyang, C.; Chen, D.; Keshta, B. E. 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Micromachines 2021 , 12 , 542. \tightlist Manuscript received: XXXX, 2025 Manuscript revised: XXXX, 2025 Manuscript accepted: XXXX, 2025 Version of record online: XXXX, 2025 Left to Right: Authors Names You will be invited to submit the most recent photos of all the authors upon acceptance of the manuscript Entry for the Table of Contents Multi-Benzyl Chloride Based Molecular Resists Enabling 13 nm Half-Pitch Lithography via Self-Crosslinking Zhuoran Liu, a Jinping Chen * , a Tianjun Yu , a Yi Zeng, a Xudong Guo, b Shuangqing Wang, b Rui Hu, b Michaela Vockenhuber, c Peng Tian , c Dimitrios Kazazis , c Yasin Ekinci * , c Jun Zhao , d Yanqing Wu , d Guoqiang Yang * , b and Yi Li* , a Chin. J. Chem. 2025 , 43 , XXX—XXX. DOI: 10.1002/cjoc.202500XXX We report a series of nonchemically-amplified resists (n-CARs) based on multi-benzyl chloride modified molecules for nanopatterning. The meta-substituted AD4MCl resist shows the best performance, achieving an impressive 13 nm pattern with an LER of 2.6 nm by EUVL, highlighting the advantages of self-crosslinking triggered low molecular weight resists. Supplementary Material File (image4.emf) Download 148.11 KB Information & Authors Information Version history V1 Version 1 04 July 2025 Copyright This work is licensed under a Non Exclusive No Reuse License. Keywords benzyl chloride electron beam lithography extreme ultraviolet lithography molecular resist non-chemically amplified resist self-crosslinking Authors Affiliations Zhuoran liu Chinese Academy of Sciences Key Laboratory of Photochemical Conversion and Optoelectronic Materials View all articles by this author Jinping Chen 0000-0002-5632-2290 Chinese Academy of Sciences Key Laboratory of Photochemical Conversion and Optoelectronic Materials View all articles by this author Tianjun Yu Chinese Academy of Sciences Key Laboratory of Photochemical Conversion and Optoelectronic Materials View all articles by this author Yi Zeng 0000-0003-0694-1795 Chinese Academy of Sciences Key Laboratory of Photochemical Conversion and Optoelectronic Materials View all articles by this author Xudong Guo Institute of Chemistry Chinese Academy of Sciences View all articles by this author Shuangqing Wang Institute of Chemistry Chinese Academy of Sciences View all articles by this author Rui Hu Institute of Chemistry Chinese Academy of Sciences View all articles by this author Michaela Vockenhuber Paul Scherrer Institute View all articles by this author Peng Tian Paul Scherrer Institute View all articles by this author Dimitrios Kazazis 0000-0002-2124-2813 Paul Scherrer Institute View all articles by this author Yasin Ekinci Paul Scherrer Institute View all articles by this author Jun Zhao Chinese Academy of Sciences Shanghai Advanced Research Institute View all articles by this author Yanqin Wu Chinese Academy of Sciences Shanghai Advanced Research Institute View all articles by this author Guoqiang Yang Institute of Chemistry Chinese Academy of Sciences View all articles by this author Yi' Li [email protected] Chinese Academy of Sciences Key Laboratory of Photochemical Conversion and Optoelectronic Materials View all articles by this author Metrics & Citations Metrics Article Usage 302 views 164 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Zhuoran liu, Jinping Chen, Tianjun Yu, et al. Multi-Benzyl Chloride Based Molecular Resists Enabling 13 nm Half-Pitch Lithography via Self-Crosslinking. Authorea . 04 July 2025. DOI: https://doi.org/10.22541/au.175161979.92720254/v1 If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download. For more information or tips please see 'Downloading to a citation manager' in the Help menu . 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