Block Copolymer Architectures for Modulating Interactions to Enhance Selectivity and Stability of s-SWCNT Dispersions

Block Copolymer Architectures for Modulating Interactions to Enhance Selectivity and Stability of s-SWCNT Dispersions | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Block Copolymer Architectures for Modulating Interactions to Enhance Selectivity and Stability of s-SWCNT Dispersions Yu-Cheng Chiu, Mei-Nung Chen, Rin Iwasaki, Mayoh Ashiya, Haoyu Zhao, and 9 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5631674/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The challenge of maintaining long-term stability in dispersed nanotube solutions arises in the case of sorting semiconducting single-walled carbon nanotubes (s-SWCNTs) with conjugated homopolymers. A strategic approach that enhances steric hindrance between nanotubes is desirable to inhibit re-aggregation effectively. This study systematically investigates interactions between BCP-SWCNTs, assessing molecular weight and steric factors by introducing a nonpolar poly( ε -caprolactone) (PCL) segment into the lowest-molecular-weight polyfluorene (PF) as a demonstration. Employing a (PCL 6k ) 3 - b -PF 6k miktoarm architecture achieves highly selective dispersions of s-SWCNTs with 1.145 nm diameters, attaining exceptional dispersion stability for over one year without re-aggregation. Thin-film transistors fabricated from these dispersions exhibit hole mobility up to 11.47 cm 2 V − 1 s − 1 without additional washing treatment. This structural design of the soft segment emerges as a powerful strategy to modulate SWCNT-SWCNT interactions, highlighting the significant role of branched, soft segment-based conjugated BCPs in enhancing both sorting selectivity and dispersion stability. Physical sciences/Materials science/Materials for devices/Electronic devices Physical sciences/Nanoscience and technology/Nanoscale materials/Carbon nanotubes and fullerenes Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction Compared to devices based on traditional semiconductors like silicon, those fabricated using semiconducting single-walled carbon nanotubes (s-SWCNTs) offer advantages such as smaller dimensions, lower power consumption, faster switching speeds, and enhanced flexibility, representing the future of electronic technology. 1 Dispersing pristine CNTs from tangled and aggregated bundles into separated states poses a long-standing challenge due to the ultrahigh aspect ratio of CNTs and the strong adsorption between them. 2 Utilizing conjugated polymers as non-covalent surface modifiers presents a straightforward and efficient approach to solubilizing CNTs without compromising their intrinsic characteristics. 3 Conjugated polymer sorting stands as a valuable technique for obtaining s-SCWNTs, which are crucial for various applications, including field-effect transistors (FETs). 4 – 6 Numerous studies have identified factors influencing the selectivity of polymer sorting, with polymer identity being key to obtaining specific chiralities. 7 – 11 Previous research has focused on modifying side chains by leaving the polymer backbone unchanged to enhance the efficiency of conjugated polymers in sorting SWCNTs. Bao et al. investigated rr-P3ATs with varying side-chain lengths, inducting that longer side chains improve the dispersion of s-SWCNTs by facilitating more complete wrapping around nanotubes. 12 Similarly, Loi et al. demonstrated that selective dispersion of SWCNTs could be achieved by tuning the alkyl side-chain length from C 6 to C 18 (PF6 to PF18). 7 The longer side-chain length allowed for more effective coverage of SWCNTs, reducing nanotube re-bundling. Especially, PF12 yielded high-quality SWCNT samples, with long photoluminescence lifetimes and increased photoluminescence yield, indicating enhanced individualization of SWCNTs and minimal defect formation of the nanotubes. In contrast, PF15 and PF18 displayed reduced selectivity for s-SWCNTs of specific chiralities due to the presence of an increased number of SWCNT configurations. Ziegler et al. revealed that elongation of the side chain tends to introduce structural distortions and substantial disorder in the PF backbone, leading to weaker π-π interactions and increased diverse interactions between PF and SWCNT. 13 As mentioned above, polymer-SWCNT interactions have been effectively modulated by tuning the side-chain length of conjugated polymers, where optimal lengths facilitate polymer-SWCNT supramolecular structures, thereby enhancing dispersion efficiency. Beyond side-chain modification, incorporating block segments further improves sorting performance. Our previous studies demonstrated that polyfluorene (PF) with shorter C 8 side chains achieved sorting enhancements by introducing polyisoprene (PI) in block copolymers (BCPs). 14 The addition of PI, with its extended non-polar chains, creates substantial van der Waals forces, effectively preventing nanotube reaggregation and thereby sustaining dispersion stability over extended periods. Even with a relatively low molecular weight for PF (weight-average molecular weight ~ 12 kDa), this BCP significantly enhances sorting efficiency and maintains high dispersion stability with excellent stability for one year in current polymer sorting studies. 9 Furthermore, coil-conjugated-coil triblock copolymers comprising oligomeric PF ( M n ~ 6 kDa) and polystyrene coils exhibited even higher selectivity than conventional homopolymers. 15 From the above reports, introducing non-polar segments significantly bolsters sorting capabilities and long-term stability. Hence, systematic investigation into interactions contributed by non-polar segments remains necessary to clarify their influence on both stability and sorting efficiency throughout the entire sorting process. In this work, block copolymers (BCPs) based on polyfluorene (PF) with varied soft segment architectures, including linear diblock and miktoarm configurations, were investigated and illustrated in Fig. 1 . Specifically, the miktoarm configuration is thought to incorporate steric hindrance elements that modify nanotube-nanotube interactions, thereby reducing reaggregation tendencies. In contrast to previous studies that relied on step-growth polycondensation for PF-based polymer synthesis aimed at SWCNT sorting, 7 , 15 this study employed the Suzuki-Miyaura catalyst transfer polycondensation (SCTP) method using a triolborate-type fluorene monomer. 16 This approach carries out the precise synthesis of end-functionalized PF-based BCPs with narrow dispersity to effectively control the SWCNT sorting results. 17 Poly( ε -caprolactone) (PCL) is selected as a promising soft segment candidate for studying the SWCNTs sorting due to van der Waals interactions among polymer chains, 18 which supports the PF wrapping process on SWCNTs during sorting, resulting in stable dispersion and enhanced sorting performance. Furthermore, PCL of linear diblock copolymers and miktoarm star polymers can be precisely synthesized via living ring-opening polymerization. 19 Hence, the influence of PCL-based BCPs on SWCNT sorting was thoroughly investigated by evaluating the sorting efficacy of various molecular weights and architectures of PCL- b -PF and PCL 3 - b -PF. Among these polymers, PCL 17k - b -PF 6k (linear BCPs) and (PCL 6k ) 3 - b -PF 6k (branched BCPs) demonstrated optimal dispersion yield and selectivity, with (PCL 6k ) 3 - b -PF 6k exhibiting exceptional stability over 1 year which is the longest duration observed without aggregate formation. These polymers effectively disperse s-SWCNTs, primarily around 1.145 nm in diameter, resulting in high performance in thin-film transistor devices based on sorted s-SWCNT random networks. Atomic force microscopy-based infrared spectroscopy (AFM-IR) cPRICE Results Synthesis of PF-based block copolymer. Figure 1 a presents a synthetic schematic for the PF-containing block copolymers (BCPs) with poly( ε -caprolactone) (PCL) as the soft segment. The BCP synthesis involves the preparation of hydroxy-terminated PF via Suzuki-Miyaura catalyst transfer polycondensation (SCTP) of a triolborate-type fluorene monomer (M3) followed by ring-opening polymerization (ROP) of ε-caprolactone. Here, the SCTP of M3 monomer, as previously reported by the group, offers an efficient and versatile strategy for synthesizing end-functionalized PFs with relatively narrow dispersity. 17 Supplementary Scheme 1 outlines the detailed synthetic route for M3. To investigate the influence of BCP molecular parameters on the sorting ability of SWCNT, both the linear AB diblock copolymer with different PF and PCL length (PF- b -PCL) and the A 3 B-type miktoarm star polymers ((PCL) 3 - b -PF) were synthesized. For synthesizing the PF- b -PCL and (PCL) 3 - b -PF, the PFs with one and three hydroxyl groups at the terminal (HO-PF and (HO) 3 -PF, respectively) were first prepared via the SCTP using different initiators ( Supplementary Schemes 2 and 5 ). To identify the end-group structure of the obtained HO-PF and (HO) 3 -PF, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) measurements were conducted, revealing periodic molecular ion peaks ranging from approximately 1,000 to 5,000 Da ( Supplementary Fig. 1a ). The peak spacing of 332 Da for both products matched well with the theoretical molecular weight of a PF monomer unit (332.25 Da), indicating that the product consisted of repeating units of dihexyl fluorene. The peaks at m / z of 1770.95 and 1849.91, are assignable to the desired HO-PF with the ω -chain end structures of H or Br, respectively. Similarly, the peaks at m / z of 1889.13 and 1929.21 observed in the MALDI-TOF MS of (HO) 3 -PF are assignable to the desired (HO) 3 -PF with the ω-chain end structures of H or Br, respectively ( Supplementary Fig. 1b ). The number-averaged molecular weight calculated from the 1 H NMR spectrums ( M n,NMR ) of HO-PFs is 9100 Da and 5800 Da; (HO) 3 -PF is 6200 Da, which exhibited relatively narrower dispersity ( Ð ) values ( Supplementary Table 1 ) of 1.74, 1.59, and 1.64, respectively. Since the terminal hydroxyl group serves as the initiating point for ROP, the subsequent ROP of ε -caprolactone from HO-PF and (HO) 3 -PF give rise PF- b -PCL and (PCL) 3 - b -PF, respectively ( Supplementary Schemes 3 and 6 ). Figure 2 d displays the size-exclusion chromatography (SEC) traces of the obtained PF- b -PCL and (PCL) 3 - b -PF from HO-PF and (HO) 3 -PF after the ROP steps. Shifting towards the higher molecular weight region compared to the elution peak of the PF macroiniaitors confirmed the successful chain extension of PCL segment from the terminal hydroxyl groups. The Ð M values estimated from the SEC measurement (Table 1 ) indicate relatively narrow (1.36–1.48) for the BCPs. The 1 H NMR signals from the benzyl group (Aromatic, 7.68–7.86 ppm; 5.19 ppm), PF backbone (Aromatic, 7.68–7.86 ppm; a, 0.76–1.26 ppm; b, 2.13 ppm), and PCL backbone (d, 2.31 ppm; e, 1.26–1.68 ppm; f, 4.06 ppm; g, 3.65 ppm) were observed in the 1 H NMR spectrum (Fig. 2 a), with each signal appropriately attributed to the structure of the target PF- b -PCL and (PCL) 3 - b -PF. Molecular weight and Ð of the PF and PF-containing BCPs used in this study are summarized in Table 1 and Supplementary Table 1 . In addition to the BCP comprising PF and PCL, a series of BCP with different soft segments were also synthesized. To investigate the influence of soft segment structure, three monomers with six-membered cyclic structures, poly( δ -valerolactone) (PVL), polylactide (PLA), and poly(trimethylene carbonate) (PTMC), were utilized for the ROP using HO-PF 6k macroinitiator. 20 Thease monomers vary in their in-ring functionalities: ester for δ -valerolactone ( δ VL), diester for lactide (LA), and carbonate for trimethylene carbonate (TMC), as illustrated in Supplementary Schemes 7, 8, and 9 , respectively, giving the soft segments with varied chemical characteristics. 21 The NMR spectra and SEC traces of BCPs are shown in Supplementary Fig. 2. Polymer Characterization. First, to elucidate how the BCP molecular weight and architecture affect the fundamental polymer characteristics, PF, PCL- b -PF, and (PCL) 3 - b -PF polymers were subjected to the UV-visible absorption and photoluminescence (PL) spectral measurements, as well as thermogravimetric and differential scanning calorimetry (DSC) analyses (Fig. 2 c and S3). As the molecular weight of PF increases, a red-shifted absorption peak occurs, shifting from 381 nm for PF 6k to 382 nm for PF 9k , attributed to the increased backbone length. 22 Similarly, higher molecular weight results in red-shifted PL peaks, transitioning from 418 to 421 nm due to increased aggregation of PF. Moreover, the absorption and emission results of the PF- b -PCL copolymer show negligible differences compared to those of the PF homopolymer, suggesting that the incorporation of the PCL block has a negligible effect on the optical properties and formation of the PF. The thermal behavior of the BCPs was examined through TGA traces recorded from 20 to 550°C under a nitrogen atmosphere ( Supplementary Fig. 3b ). The HO-PF 6k and HO-PF 9k polymers demonstrate the 5% weight loss temperature ( T d, 5% ) at approximately 377°C and 411°C, respectively. The BCPs display T d, 5% ranging from 363 to 378°C, indicating their overall high thermal stability. The thermal properties of films comprising PCL-blocked BCPs were assessed using DSC, as depicted in Supplementary Fig. 3c . A summary of all thermal transitions and the corresponding PCL crystallinity ( X PCL ) values is provided in Supplementary Table 2 . It was observed that as the molecular weight of the PCL increased, the corresponding increase in the melting temperature and X PCL was evident in the PCL segment. The melting enthalpies and crystallization of branched architectures are lower than linear ones, attributed to the constrained mobility of densely packed monomers near the branch points. 23 In addition, wide-angle X-ray scattering (WAXS) analysis ( Supplementary Fig. 3d ) also exhibits a slight enhancement in the crystallinity of PCL, particularly evident in the (110), (111), and (200) planes, with increasing molecular weight of the PCL block. 24 Table 1 Synthesis of PF-based BCP a Sample Macroinitiator [monomer] 0 /[initiator] 0 conv. (%) M n,NMR b (g mol − 1 ) M n,SEC c (g mol − 1 ) Ð c Yield (%) PCL 6k -b -PF 9k HO-PF 9k 60/1 88.6 15,000 25,500 1.40 83.2 PCL 12k -b -PF 9k 120/1 95.1 21,600 33,600 1.45 88.2 PCL 6k -b -PF 6k HO-PF 6k 60/1 93.3 11,400 21,500 1.36 65.1 PCL 12k -b -PF 6k 120/1 87.1 17,600 26,800 1.36 74.8 PCL 17k -b -PF 6k 180/1 84.0 22,800 32,900 1.48 88.4 (PCL 4k ) 3 -b - PF 6k (HO) 3 -PF 6k 120/1 78.6 17,300 31,300 1.48 63.3 (PCL 6k ) 3 -b - PF 6k 180/1 94.5 22,300 43,800 1.43 72.3 a Polymerization conditions: temperature, r.t.-90°C; atmosphere, Ar; [Macroinitiator] 0 /[TBD] = 1/1. b Determined by 1 H NMR spectrum in CDCl 3 . c Determined by SEC in THF using PSt standards. Sorting of SWCNTs by conjugated polymers. In our previous studies, we demonstrated the successful sorting of SWCNTs using polyfluorene (PF) copolymers with low weight-average molecular weight ( M w ≤ 12 kDa). 10 , 14 Low molecular weight conjugated polymers offer several advantages during synthesis, including easier control of polymerization, reduced synthesis time and cost, and enhanced purity of polymer. However, excessively short polymers fail to provide sufficient interaction with SWCNTs, leading to low dispersion and reaggregate during centrifugation. Despite these challenges, our previous work showed that PF copolymers with low M w could still successfully sort SWCNTs, attributed to the ability of longer PI segments to create non-polar van der Waals interactions between the nanotubes. Therefore, the interaction contributed from the soft segment is crucial to study the sorting ability of polymers with different weight-average molecular weights. In this investigation, we intentionally designed PF BCPs with different soft segment structures to explore their sorting capabilities and the interaction between the hybrids. SWCNTs of diameter ranging from 0.89 to 2.04 nm, synthesized via the chemical vapor deposition (CVD) method as previously reported, 25 were dispersed in toluene using the PF-based BCPs. The sorting steps followed a similar procedure for PF-based polymer dispersions in previous work. 14 After sonication and ultracentrifugation, the supernatant portion was extracted for optical investigations. Photoluminescence excitation (PLE) measurements provide evidence regarding the chirality and diameters of individual s-SWCNTs among the sorted nanotubes. This method excludes metal SWCNTs due to their lack of fluorescence and eliminates the bundles of aggregation since they quench luminescence and broaden optical transitions. 26 , 27 The positions of SWCNT resonances were plotted using the scheme proposed by Weisman and Bachilo. 28 As Fig. 3 a illustrates, PLE measurements indicate minimal sorting by HO-PF 9k , a relatively short homopolymer, as its π-π interactions with SWCNTs remain insufficient to counteract competing interactions between polymer-wrapped SWCNTs or between polymers. 29 In sharp contrast, incorporating PCL 6k or PCL 12k segments into the short PF polymers significantly enhances the signal intensity, particularly for species (10,9) and (15,1) (Fig. 3 b and 3 c), suggesting that PCL strongly augments favorable polymer-SWCNT interactions. To further substantiate that the polymer-SWCNT interaction serves as a key factor by PCL segment, PF 6k diblock copolymers with shorter PF segments were designed. The HO-PF 6k homopolymer also lacks effective sorting as illustrated in Supplementary Fig. 4 . The synthesis of PCL 6k - b -PF 6k and PCL 12k - b -PF 6k exhibit significant emission peaks from s-SWCNTs (Fig. 3 d and 3 e), with selectivity for major semiconducting species (15,1) and (12,4), indicating a marked enhancement in sorting efficiency through PCL segment. Hence, to achieve effective sorting, the role of non-conjugated coil interactions introduced by the PCL segments predominantly governs the interactions between the BCP and SWCNT, while the π-π interactions from the polymer backbone remain limited. Supplementary Fig. 5a shows that the hydrodynamic radius ( R h ) of PCL 6k - b -PF 9k is larger than that of PCL 6k - b -PF 6k in solutions assessed by dynamic light scattering (DLS), indicating that longer conjugated-segment in BCPs may facilitate aggregation. 30 According to the above sorting performance, the two types of copolymers with PF 9k and PF 6k exhibit minor differences. Therefore, PF 6k is selected as the conjugated segment to further investigate the effect of the soft segment. The extended coil segment length of PCL 17k in PF 6k was specifically designed to strengthen interactions with the nanotube surface, as illustrated in Fig. 3 f. This configuration results in a remarkably concentrated sorting with a narrower chirality distribution, prominently for (12,4) SWCNTs with a diameter of 1.145 nm. To our knowledge, this represents the shortest PF segment demonstrating high sorting efficiency, attributed to the enhanced polymer-SWCNT interaction through non-covalent interactions. Increasing coil segment length in short PF-based BCPs reduces the attractive forces between conjugated polymer-wrapped SWCNTs, mitigating reaggregation and thereby enhancing sorting efficiency. Further exploration of interaction effects between polymer-wrapped SWCNTs by the introduction of branched PCL in BCPs creates steric hindrance to reduce π-π interactions and stabilize polymer-wrapped SWCNTs. Results confirm that branched PCL chains improve selective interactions with specific nanotube chiralities, even where π-π stacking provides weak contributions, as seen in Fig. 3 g and 3 h. Compared to linear PCL 6k - b -PF 6k and PCL 12k - b -PF 6k , the branched (PCL 4k ) 3 - b -PF 6k with shorter PCL segments per branch shows more selective PLE spectrum demonstrates the enrichment of the major semiconducting species (12,4) SWCNTs sorted by the branched BCPs. Additionally, (PCL 6k ) 3 - b -PF 6k also achieves significant enrichment of SWCNTs with (12,4) chirality, further validating the effectiveness of the branched PCL approach. Figure 3 i displays the names of the seven polymers employed and a chirality map of the SWCNTs, covering a diameter range of approximately 0.9–1.2 nm, as determined from optical measurements. In this map, pale-yellow hexagons represent successfully selected SWCNT species, with the colors of the rhombuses inside indicating which BCPs can selectively sort the specific tubes. Figure 3 j depicts a schematic illustration of the sorting process mechanism using the designed BCPs in toluene. Toluene enhances the selective dispersal of individual SWCNTs and promotes the propensity of PF to adopt a helical structure in this solvent. 31 , 32 Within the suspension, π-π stacking interaction between the PF backbone and the SWCNT surface dominates the binding energy between the PF and nanotubes, facilitating the adsorption of polymers onto the SWCNTs. 31 The PCL segment provides abundant physical interactions, primarily van der Waals forces, 18 to enhance sorting results and acts as a barrier among nanotubes to prevent the reaggregation of sorted SWCNTs. The absorption ratios between the first (M 11 ) interband transition of metallic tubes, and the second (S 22 ) and third (S 33 ) interband transitions of semiconducting tubes provide a qualitative measure of the proportion of metallic SWCNTs remaining in the sorted tubes. 33 , 34 Fig. 3 k illustrates the absorption spectrum of sorted SWCNTs exhibiting these three bands. Both PCL 17k - b -PF 6k and (PCL 6k ) 3 - b -PF 6k -wrapped SWCNTs exhibit the absence of the metallic absorption band, while the intensity of the semiconducting absorption bands is notably pronounced. Furthermore, the separated semiconducting SWCNTs, enriched to approximately 90% purity as assessed using Supplementary Eq. 1 (refer to Supplementary Table 3 ), 35 , 36 , 37 were sorted by these two BCPs. This indicates their potential as candidates for achieving higher yields and purer s-SWCNTs and paves the way for subsequent investigation into the stability and application of SWCNTs wrapped with different BCP architectures. Long-term stability of dispersion is crucial for maintaining consistent s-SWCNT performance in electronic applications. Figure 3 l and 3 m illustrate the impact of BCP architecture on dispersion stability, evaluated through UV-Vis absorption spectroscopy. Over one year, the linear BCP, PCL 17k - b -PF 6k , maintained 76% of its initial S 22 peak intensity (as calculated by Supplementary Eq. 2 ), with the decrease attributed to gradual reaggregation and sedimentation. 9 Furthermore, it is particularly noteworthy that the absorption intensity of the branched BCP-wrapped tubes, (PCL 6k ) 3 - b -PF 6k , remained consistent with the initial profile after one year (stability ratio ~ 95%) at room temperature, exhibiting the ultrahigh stability of branched BCP-wrapped SWCNT hybrids in solution within current polymer sorting studies. The improvement in long-term stability achieved by (PCL 6k ) 3 - b -PF 6k is attributed to the inherent steric hindrance provided by the branched PCL segments, which act as barriers between conjugated block-wrapped SWCNTs. This strategy increases free volume and van der Waals interactions, creating additional unoccupied space that reduces reaggregation tendencies. 8 , 38 , 39 DLS data ( Supplementary Fig. 5b ) indicates that BCPs with a branched PCL moiety exhibit a smaller radius compared to a linear PCL block, providing advantages in maintaining polymer-SWCNT hybrid stability without significant impact from the polymer in suspension. The stability of both linear and branched polymer-wrapped SWCNT solutions is further supported by PLE mapping ( Supplementary Fig. 6 ), where a narrow chirality distribution persists even after one year. Demonstration of the molecular weight and architecture of the model coil segments, PCL, do significantly influence the properties and stability of the sorted SWCNTs, emphasizing the importance of designing the soft segment interactions within the sorting system. To extend the concept of soft segments playing a critical role in SWCNT sorting to various chemical structures, PVL, PLA, and PTMC with varying degrees of polarity were introduced into PF-based BCPs and assessed through optical absorption spectra, as shown in Supplementary Fig. 7a and 7b . Dispersions of metallic and semiconducting SWCNTs were quantified by calculating the area under the absorption spectra ( Supplementary Table 4 ). Among these studied BCPs, PCL 6k - b -PF 6k reveals the highest purity of semiconducting SWCNTs, while PTMC 6k - b -PF 6k results in almost absent in absorption intensity. This trend correlates with the polarity order of the soft segments (CL < VL < LA < TMC), 21,40,41 suggesting that lower polarity enhances efficiency and selectivity in the toluene solution system. The stronger affinity between more polar segments and metallic SWCNTs reduces the purity of SWCNTs. 42 Moreover, the PCL with better solubility in toluene improves the dispersion of nanotubes within the polymer matrix, which is crucial for achieving a uniform distribution of SWCNTs. These effects lead to a higher sorting yield and improved purity in PCL-based systems, highlighting the potential of the PCL segment for efficient SWCNT separation. The PLE results also unveiled the selective ability of different soft segment polymers, even when transitioning to the polar LA units, which retained their selectivity despite having a shorter molecular weight. The PLE maps ( Supplementary Fig. 7c-f ) also illustrate the increasing broad emission and decreasing selectivity of SWCNTs solutions sorted by relative polar BCPs, highlighting the potential effectiveness of PCL in sorting SWCNTs. Application in Transistors using Sorted SWCNTs. To further confirm the enrichment of s-SWCNT through the BCPs sorting method, Raman spectra were measured under various excitation wavelengths. Under 532 nm excitation (Fig. 4 a), the metallic radial breathing mode (RBM) peaks disappeared post-sorting, while the broad semiconducting RBM peaks persisted, indicating the removal of most metallic species. 8 , 43 Upon 633 nm laser excitation (Fig. 4 b), a stronger RBM peak at 200 cm⁻¹, characteristic of metallic tubes, was observed in pristine SWCNTs but significantly reduced in sorted SWCNTs. 8 Additionally, the G band Raman spectra of metallic and semiconducting nanotubes show differences under 633 nm excitation (Fig. 4 c). 44 The broad G⁻ peak, which indicates metallic nanotubes, was significantly decreased in the sorted SWCNTs compared to the pristine SWCNTs. These results demonstrate that metallic tubes were effectively removed after sorting with PCL 17k - b -PF 6k and (PCL 6k ) 3 - b -PF 6k . This sorting method offers a pathway to produce enriched s-SWCNT materials, which have promising potential for testing in semiconductor-based electronics. Therefore, the bottom-gate top-contact device configuration was employed to construct random SWCNT networks on SiO 2 (300 nm)/Si wafers using a simple solution coating method, as illustrated in Fig. 4 d. The transfer curve and atomic force microscopy (AFM) height image of a typical TFT device are shown in Fig. 4 e. The hole charge carrier mobility was observed across 10 fabricated devices ranging from 3.29 to 4.84 cm 2 V − 1 s − 1 (average: 4.02 cm 2 V − 1 s − 1 ) for PCL 17k - b -PF 6k and from 9.26 to 13.00 cm 2 V − 1 s − 1 (average: 11.47 cm 2 V − 1 s − 1 ) for (PCL 6k ) 3 - b -PF 6k . Detailed electrical characteristics, including hysteresis sweeps and the square root of the source-drain current, are presented in Supplementary Fig. 8 and Supplementary Table 5 . As shown in Supplementary Fig. 8a and 8b , the dual sweeps of the sorted SWCNT devices exhibit a noticeable hysteresis loop, attributed to the PF with excellent hole-trapping ability. 45 , 46 The square root of the source-drain current and the output curve of transistors fabricated with sorted SWCNTs are presented in Supplementary Fig. 8e and 8f . The most promising transistor achieved a high mobility of 19.68 cm 2 V − 1 s − 1 and an on/off ratio of 2.6 \(\:\times\:\) 10 3 ( Supplementary Fig. 9 ). In addition, SWCNTs sorted with PCL 17k - b -PF 6k and (PCL 6k ) 3 - b -PF 6k solutions, stored for one year, were fabricated devices to evaluate performance ( Supplementary Fig. 10 ). The average hole charge carrier mobilities reached 3.71 and 9.42 cm 2 V − 1 s − 1 , respectively, both exhibiting excellent electrical properties. These results demonstrate that even after one year in solution, the polymer-SWCNT hybrids maintained uniform dispersion and retained electrical characteristics. The strong interaction between polymers and SWCNTs complicates the removal of polymer wrapping, which may reduce charge transport between s-SWCNTs due to potential charge-trapping effects. Nevertheless, electrical performance remains exceptional, revealing the viability of s-SWCNTs sorted by PCL 17k - b -PF 6k and (PCL 6k ) 3 - b -PF 6k for semiconductor applications requiring long-term stability. Topology and Mechanical Properties of Sorted SWCNTs. To verify the presence of BCPs wrapped around the surface of SWCNTs, AFM-based infrared spectroscopy (AFM-IR) was employed to gain critical insights into the distribution of polymer components within thin films on the SiO 2 /Si substrate, as depicted in Fig. 5 a-d. 47 The FTIR spectra ( Supplementary Fig. 11 ) reveal a significantly stronger absorbance signal at 1726 cm − 1 in the BCPs compared to SWCNTs. This peak corresponds to the C = O stretching vibration, indicating the presence of the PCL molecule within the BCPs. 48 Hence, the IR laser was tuned to 1726 cm − 1 to excite the PCL phase for AFM-IR map measurement. The height image obtained from AFM (Fig. 5 a and 5 d) provides insight into the morphology of the tubes, while the corresponding AFM-IR absorption map (Fig. 5 b and 5 e) highlights regions of higher amplitude (depicted in red) where the tubes are situated. These red regions signify areas of higher polymer concentration, suggesting effective wrapping of the CNT tube surfaces by the polymer. The intensity of amplitude at points 1 and 2 for SWCNTs sorted by PCL 17k - b -PF 6k , and at points 3 and 4 for SWCNTs sorted by (PCL 6k ) 3 - b -PF 6k , is illustrated in Fig. 5 c and 5 f, which evidences that the intensity of points 1 and 3 (tubes) is stronger than that of points 2 and 4 (wafer), confirming the successful wrapping of the SWCNTs surfaces by the BCPs. The discrepancy in surface mechanical properties, including Derjaguin-Muller-Toporov (DMT) modulus, dissipation, and adhesion, between thin films of (PCL 6k ) 3 - b -PF 6k , SWCNTs, and their hybrid materials was investigated using PeakForce Quantitative Nanomechanical Mapping (QNM) AFM, as illustrated in Fig. 6 . The pure BCP sample (Fig. 6 a) exhibits evident phase separation, the characteristic also observed in PF- block -poly( δ -decanolactone) (PF- b -PDL) films, which contributes to the tight packing of PF blocks promoted by intermolecular π-π interactions, while the softer PCL blocks with lower modulus form an amorphous matrix around the PF fibers. 49 , 50 , 51 This phase separation is further elucidated by the mechanical properties analysis (Fig. 6 m) exhibited through line profiles obtained at specific locations (indicated by arrows) in the AFM images in Fig. 6 b-d, which reveal higher modulus, and lower dissipation and adhesion in the PF domain region than PCL domain region. Figure 6 e depicts the morphology of pure SWCNTs fabricated without polymer sorting, exhibiting significant aggregation for larger tube sizes (> 40 nm height) compared to sorted SWCNTs (Fig. 6 i). The surface mechanical properties of pure SWCNTs are exhibited in Fig. 6 f-h and Fig. 6 n. AFM-IR verification confirms polymer coating on the surfaces of sorted SWCNT, leading to lower modulus but higher dissipation and adhesion compared to pure SWCNTs, as illustrated in Fig. 6 j-l and Fig. 6 o. Notably, the adhesion image and adhesion line profile of SWCNTs sorted by the BCPs were significantly observed in the increased adhesion force at the tube edges, indicating the presence of polymer on the exterior of the tubes. Force-displacement (F-δ) curves (Fig. 6 p) obtained at specific locations (indicated by arrows) over particles in the AFM images also provide mechanical properties of different materials. The energy dissipation (ED) is measured from the area hysteresis between the approach and withdrawal curves. 52 The larger area between the curves for BCPs compared to tubes indicates lower stiffness and higher viscosity. Moreover, the slope of the F-δ curve in the repulsive force (RF) region directly reflects polymer stiffness, which is softer compared to pure nanotubes. 53 This observation is consistent with the smaller slope of repulsive forces observed in sorted SWCNTs compared to pure tubes, indicating the softer and less viscous behavior of the sorted SWCNTs. Despite the soft polymer wrapping the SWCNT surface, the conductivity of the SWCNTs within the polymer matrix is evident through current measurements using tunneling AFM (TUNA) mode, as depicted in Supplementary Fig. 12 . The brighter areas in Supplementary Fig. 12b correspond to the nanotube material, demonstrating a noticeable current flow, which confirms the efficient charge transport ability of SWCNTs within the BCPs matrix. Discussion In summary, the critical role of block copolymer architecture is in achieving both high selectivity and long-term stability in semiconducting single-walled carbon nanotube (s-SWCNT) dispersions. The introduction of a PCL segment into PF-based BCPs not only modulates SWCNT sorting but also enhances dispersion stability by providing steric hindrance and additional van der Waals interactions. The linear PF- b -PCL copolymers with longer PCL segments demonstrated increased selectivity of sorted nanotubes demonstrated. Moreover, the branched (PCL 6k ) 3 - b -PF 6k architecture exhibited superior performance, maintaining exceptional dispersion stability for over one year, attributed to the enhanced steric hindrance introduced by the branched structure, which prevents reaggregation and stabilizes polymer-wrapped SWCNT hybrids in solution. Both linear and branched block copolymers achieved narrow distributions of SWCNT chirality around 1.145 nm in diameter and purity of approximately 90% semiconducting nanotubes. Investigation with alternative soft segments of varying polarity further demonstrated that lower polarity enhances sorting selectivity in the toluene system, suggesting the dominant influence of van der Waals interactions between the nanotubes. The AFM-based analyses, including Nano-IR and QNM measurements, provided direct evidence of polymer wrapping and the mechanical influence on SWCNT hybrids in the thin film state. Thin-film transistors fabricated from branched BCP-wrapped nanotubes exhibited high performance with hole mobilities reaching 11.47 cm² V⁻¹ s⁻¹. Therefore, this study provides a valuable strategy for adjusting both polymer-nanotube and nanotube-nanotube interactions by designing block copolymer architectures to improve SWCNT sorting efficiency and dispersion stability. Methods Synthesis of PF- b -PCL. Tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct Pd 2 (dba) 3 •CHCl 3 . 54 1,8-Diazabicyclo[5.4.0]-undec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 4-iodobenzyl alcohol, 4-iodobenzyl bromide, ε -caprolactone ( ε -CL), rac -lactide ( rac -LA), sodium hydride (NaH; 60% dispersion in paraffin liquid), tetrabutylammonium iodide (TBAI), trans -2-[3-(4- tert- butylphenyl)-2-methyl-2-propylidene]malononitrile, and 2,2-bis(hydroxymethyl)-1,3-propanediol were purchased from Tokyo Chemical Industry Co., Ltd. (TCI) and used as received. Dry-dichloromethane (CH 2 Cl 2 ), dry-dimethylformamide (DMF), dry-tetrahydrofuran (THF), and dry-toluene were purchased from Kanto Chemical Co., Inc. and used as received. 1,1,1-Tris(hydroxymethyl)ethane, tri( tert -butyl)phosphine ( t -Bu 3 P), and tripotassium phosphate (K 3 PO 4 ) were purchased from Fujifilm Wako Pure Chemical Co. and used as received. rac -Lactide (> 98.0%) was purified by recrystallization (twice) from dry toluene and stored in a glovebox. DBU (> 98.0%) and ε -CL (> 99.0%) were purified by distillation over CaH 2 under reduced pressure and stored in a glovebox. Dry-CH 2 Cl 2 (> 99.5%; water content, 99.5%; water content, 99.5%; water content, < 0.001%) were further purified using an MBRAUN MB-SPS Compact solvent purification system equipped with a MB-KOL-C column and MB-KOL-A column (for dry-toluene), a MB-KOL-A column and a MB-KOL-A column (for dry-CH 2 Cl 2 ), or a MB-KOL-A column and a MB-KOL-M Type 1 column (for dry-THF), which were then directly used for the polymerizations. Preparation of SWCNT/PF- b -PCL dispersions. Single-walled carbon nanotubes (SWCNTs; d ≤ 2.0 nm) were prepared according to the reported methods. 25 For all SWCNT dispersions, a mixture consisting of 0.15 mg mL - 1 of SWCNTs and 0.00009 mmol mL - 1 of polymer was added to 10 mL of toluene. The mixture was sonicated for 1.5 h in the cup horn of a high-power sonicator (Qsonica) used at 490 W. The temperature of the sample was kept constant at 4°C in the cooling bath during sonication. Immediately after sonication, the dispersion was centrifuged at 48000 g for 3 h (Beckman Avanti J-26 Hitachi) for samples used to fabricate field effect transistors. The upper supernatant was taken and used for further measurements. The pure SWCNTs (1.7mg) were dispersed in 10 mL of n-methyl pyrrolidinone (NMP). This solution was sonicated at an amplitude level of 490 W for 30 min in the cooling bath. Then, the centrifuge at 6,000 rpm for 30 min to dissociate the undispersed CNT. The upper supernatant was taken and used for further measurements. Thin film and device fabrication. Thin films of pure polymer dissolved in toluene (5 mg mL - 1 ) were spin-cast on SiO 2 /Si substrates at a spinning rate of 1000 rpm for 60 s. Subsequently, the films underwent thermal annealing at 170 ℃ for 20 min. The supernatant solution of pure CNT was slowly spray-coated on a Si wafer at 200 ℃ to form a thin film. Field-effect transistor (FET) devices were fabricated on highly doped n-type Si (100) wafers with a 300 nm SiO 2 layer. The semiconducting layer was spin-coated onto SiO 2 /Si substrates at 1000 rpm for 60 s from a prepared polymer-SWCNT suspension at room temperature and in ambient conditions. Devices were thermally annealed at 120°C for 1 h to remove residual solvent. Top-contact gold electrodes (50 nm) were deposited by evaporation through a shadow mask, defining the channel length (L) and width (W) as 50 µm and 1000 µm, respectively. Transistor measurements were carried out using a Keithley 4200 semiconductor parameter analyzer (Keithley Instruments Inc., Cleveland, OH, USA). Analytical measurements. Glovebox. The polymerization was carried out in an MBRAUN stainless steel glovebox equipped with a gas purification system (molecular sieves and copper catalyst) and a dry Ar atmosphere (H 2 O, O 2 < 1 ppm). The moisture and oxygen contents in the glovebox were monitored by an MB-MO-SE 1 moisture sensor and an MB-OX-SE 1 oxygen sensor, respectively. Nuclear magnetic resonance (NMR). The 1 H NMR (400 MHz) and 13 C NMR (100 MHz) spectra were obtained by a JEOL JNM-ECS400 instrument or a JEOL JNM-ECX400P instrument at 25 ºC. Size exclusion chromatography (SEC). The size exclusion chromatography (SEC) was performed at 40°C in THF (flow rate, 1.0 mL min − 1 ) using a Shodex GPC-101 gel permeation chromatography system (Shodex DU-2130 dual pump, Shodex RI-71-S reflective index detector, and Shodex ERC-3125SN degasser) equipped with a Shodex KF-G guard column (4.6 mm × 10 mm; particle size, 8 µm) and two Shodex KF-804L columns (linear, 8 mm × 300 mm). The number-average molecular weight ( M n,SEC ) and the dispersity ( Ð ) of the polymers were calculated based on polystyrene calibrations. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). MALDI-TOF MS measurement of the polymer was carried out in the reflector mode using an ABSCIEX TOF/TOF/5800 equipped with a 337 nm nitrogen laser (3 ns pulse width). The MALDI-TOF MS samples were prepared by depositing a mixture of the polymer and matrix in THF onto a sample plate. A 1:80 (v/v) ratio of [PF (1.0 g L − 1 in THF)]/[ trans -2-[3-(4- tert -butylphenyl)-2-methyl-2-propylidene]malononitrile (10 g L − 1 in THF)] was used. Thermogravimetric analysis (TGA). The TGA experiments were performed using a Hitachi High-Tech Science STA200RV under nitrogen atmosphere. The obtained block copolymers were heated from 30 ºC to 550 ºC at the heating rate of 10 ºC min − 1 . Differential scanning calorimetry (DSC). The thermal properties of the samples were measured by a Hitachi High-Tech Science DSC7000X differential scanning calorimeter (DSC) under a nitrogen atmosphere. The obtained block copolymers were heated from 30°C to 270 ºC at a rate of 30 ºC min − 1 , staying at 270 ºC for 5 min to erase thermal history. Then the sample was cooled to -70 ºC at a rate of 20 ºC min − 1 , keeping at -70 ºC for 5 min. Finally, the sample was heated to 270 ºC at a rate of 10 ºC min − 1 . Wide-angle X-ray scattering (WAXS). The WAXS measurements of the obtained polymers were performed at the BL-6A beamline of the Photon Factory in the High Energy Accelerator Research Organization (KEK, Tsukuba, Japan) using X-ray beams with λ = 0.150 nm at room temperature. The scattering data were collected by a 2D detector (PILATUS3 100K (Dectris Ltd.)), where the samples-to-detector distance was set to be around 25 cm for WAXS measurement. The scattering angle ( θ ) was calibrated using silver behenate (Nagara Science Co., Ltd) as the standard and derived the scattering vector ( q ) from Bragg’s equation (| q | =(4 π / λ )sin( θ /2)). The polymer solids or powders were sandwiched by two pieces of Kapton tapes with a spacer of a stainless washer, which were applied for the measurement. Ultraviolet-visible-near infrared (UV-Vis-NIR) absorption spectroscopy. The absorption spectra measurements were performed using a UV-Vis/NIR spectrophotometer (model V-676 JASCO) at a wavelength range of 500–1500 cm − 1 . Photoluminescence excitation (PLE) measurement. The measurements of photoluminescence excitation (PLE) spectra were performed using a fluorescence spectrophotometer (model Fluorolog 3, HORIBA Scientific Japan) at an excitation wavelength range of 400–1000 nm and an emission wavelength range of 1000–1600 nm. Dynamic Light Scattering (DLS). DLS measurements were carried out using a Zetasizer Nano ZS instrument (He-Ne laser, 633 nm, max 4 mW, Malvern Panalytical Ltd). A micro quartz cuvette (ZEN2112, Hellma Analytics) was used. Measurements were carried out at 25°C with a 60 s equilibration time. A cumulant analysis performed using the inbuilt software of the instrument was used to determine the z-average radius. Raman spectroscopy. Raman spectral measurements were conducted by using a JASCO 5100 spectrometer (JASCO, Japan) under green laser excitation (λ = 532 nm) and red laser excitation (λ = 633 nm). Electrical parameter analyzer. The electrical properties of OFET were measured by Keithley 4200-SCS semiconductor parameter analyzer at room temperature in a completely dark and inert N 2 -filled glove box. Attenuated Total Reflectance-Fourier transform infrared spectroscopic (ATR-FTIR). IR spectra were tested using ATR-FTIR (PerkinElmer, USA). Atomic force microscope (AFM). The morphology of thin films was measured by tapping mode AFM from Bruker Dimension ICON. The mechanical properties were measured by quantitative nanomechanical mapping (QNM) from Bruker Dimension Icon. The probe used a model of RTESPA-150 with a nominal spring constant (k) 6.0 N/m and a resonant frequency (f 0 ) of 150 Hz. Tunneling-AFM (TUNA) is a method for measuring ultra-low currents on low-conductive samples. A DC bias is applied between the sample and the conductive tip as the tip scans the sample in contact mode. A PtIr-coated tip with 0.01–0.025 Ωcm Antimony (n) doped Si was used. Atomic force microscopy with nanoscale infrared spectroscopy (Nano-IR AFM). The device surface morphology was measured using a nanoIR3 AFM-IR from Anasys Instruments (Santa Barbara, CA) coupled to a MIRcat-QT quantum cascade mid-infrared laser operating at 1470 kHz in ranges 917–1700 and 1900–2230 cm - 1 . AFM-IR data were collected in tapping mode using a gold-coated AFM probe [spring constant ( k ) = 40 N m - 1 and resonant frequency (f o ) = 300 kHz]. Declarations Acknowledgments The authors thankfully acknowledge the financial support from the National Science and Technology Council in Taiwan (NSTC 111-2628-E-011-008-MY3, 113-2811-E-011-008-MY2, and 113-2124-M-011-002) and JSPS Fund for the Promotion of Joint International Research (No. 21KK0096). The authors also appreciate the financial support provided by “the Sustainable Electrochemical Energy Development Center (SEED Center)” from The Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education of Taiwan. The WAXS study was approved by the Photon Factory Program Advisory Committee (Proposal No. 2023G574). T.S. thanks the funding support from the Frontier Chemistry Center (Hokkaido University), the Photo-Excitonic Project (Hokkaido University), the Creative Research Institution (CRIS, Hokkaido University), and the List Sustainable Digital Transformation Catalyst Collaboration Research Platform (List-PF, Hokkaido University). H.Z. amd X.G. thanks the funding support from Office of Naval Research (ONR) under the contract number N00014-23-1-2063 to enable the AFM-IR meausrments. Author Contributions M.-N.C. and Y.-C.C. conceived the idea and designed the experiments. I.T. and S.T. designed the studied conjugated block polymers. A.M. and I.R. synthesized the conjugated block polymers and characterized their properties using NMR, SEC, MALDI-TOF MS, TGA, DSC, and WAXS. M.-N.C. conducted the fabrication of SWCNT sorting and thin-film transistors and characterized them by UV-Vis-NIR, PLE, DLS, Raman, electrical measurements, ATR-FTIR, and AFM analyses. 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Mississippi","correspondingAuthor":false,"prefix":"","firstName":"Xiaodan","middleName":"","lastName":"Gu","suffix":""},{"id":393840636,"identity":"a80f472b-147c-478c-a2e0-64f2110b736b","order_by":11,"name":"Wei-Hung Chiang","email":"","orcid":"https://orcid.org/0000-0002-6350-6696","institution":"National Taiwan University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Wei-Hung","middleName":"","lastName":"Chiang","suffix":""},{"id":393840637,"identity":"d70ba910-e64a-4c64-af76-8bfd6d2ad17c","order_by":12,"name":"Takuya Isono","email":"","orcid":"https://orcid.org/0000-0003-3746-2084","institution":"Hokkaido University","correspondingAuthor":false,"prefix":"","firstName":"Takuya","middleName":"","lastName":"Isono","suffix":""},{"id":393840638,"identity":"9511011a-2c87-4f21-a0a3-5e95a78e1fce","order_by":13,"name":"Toshifumi Satoh","email":"","orcid":"https://orcid.org/0000-0001-5449-9642","institution":"Hokkaido University","correspondingAuthor":false,"prefix":"","firstName":"Toshifumi","middleName":"","lastName":"Satoh","suffix":""}],"badges":[],"createdAt":"2024-12-12 12:40:38","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5631674/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5631674/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":78884669,"identity":"e6407c97-2bda-4e5a-ac98-3e35e51cb76b","added_by":"auto","created_at":"2025-03-20 09:23:46","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":95738,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSynthetic schemes of PF-based block copolymers incorporating PCL segments. \u003c/strong\u003eSchematic for the synthesis of the PF‐containing and PCL-containing block copolymers.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-5631674/v1/850e99e1c1a68cba1e6e7139.png"},{"id":78884692,"identity":"3225167f-a10c-4a3f-87cd-4c66d39af6f4","added_by":"auto","created_at":"2025-03-20 09:23:47","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":362547,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCharacterization of block copolymer structures by SEC, NMR, and spectroscopic analysis. a\u003c/strong\u003e ¹H NMR spectra of BCPs (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e). \u003cstrong\u003eb\u003c/strong\u003e SEC traces of BCPs (detected by RI detector; eluent, THF; flow rate, 1.0 mL min\u003csup\u003e-1\u003c/sup\u003e). \u003cstrong\u003ec\u003c/strong\u003e The UV-Vis and PL spectra of PF and BCPs.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-5631674/v1/d63feae8ac52e93f3c076d69.png"},{"id":78884693,"identity":"68a38284-1bdd-4caf-9bc1-79c3433c74d1","added_by":"auto","created_at":"2025-03-20 09:23:47","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":910262,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSelective sorting of s-SWCNTs by linear and branched block copolymers. a-h \u003c/strong\u003e2D PLE maps of sorted SWCNTs by different polymers dispersed in aqueous toluene solution.\u003cstrong\u003e i\u003c/strong\u003e Chirality map of SWCNTs selected by different BCPs sorting. The major (yellow background with black border) and minor (faint yellow background) chirality of SWCNTs; the color of the diamonds inside the hexagons indicates which of the BCPs majorly derivative (color code used for the chemical structures) could select the nanotubes. \u003cstrong\u003ej\u003c/strong\u003e Schematic illustration of the mechanism of the sorting process using the designed BCPs in toluene. \u003cstrong\u003ek \u003c/strong\u003eAbsorption spectra of the polymers-SWCNTs suspensions. The stability of suspensions of \u003cstrong\u003el\u003c/strong\u003e PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e and \u003cstrong\u003em \u003c/strong\u003e(PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e sorting SWCNTs for one-year measurement.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-5631674/v1/c8913a3807ab58e2699af10a.png"},{"id":78884695,"identity":"9d5be85b-551e-4ad2-baa1-3653c8f672e6","added_by":"auto","created_at":"2025-03-20 09:23:48","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":423912,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eElectronic performance of thin-film transistors fabricated with sorted s-SWCNTs. \u003c/strong\u003eThe laser Raman spectra of RBM bands from the SWCNT with excitation laser wavelengths of \u003cstrong\u003ea\u003c/strong\u003e 532 nm, and \u003cstrong\u003eb\u003c/strong\u003e 633 nm; \u003cstrong\u003ec\u003c/strong\u003e G band excited with a 633 nm laser. \u003cstrong\u003ed\u003c/strong\u003e Schematic illustration of TFT devices with SWCNTs sorted by BCPs as the semiconductor layer. The transfer curves of TFTs of SWCNTs are sorted by \u003cstrong\u003ee\u003c/strong\u003e PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e (right) and (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e (left) under V\u003csub\u003e\u003cem\u003eDS\u003c/em\u003e\u003c/sub\u003e= -60 V. Inset in each transfer curves image is atomic force microscope (AFM) topography image of SWCNTs sorted by BCPs. The scanning size was 55 μm\u003csup\u003e2\u003c/sup\u003e at the digital resolution of 256256 pixels.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-5631674/v1/c97d7e87ae49df0d63003e5c.png"},{"id":78884699,"identity":"e803eec8-914a-48ad-b0b4-177deec568dc","added_by":"auto","created_at":"2025-03-20 09:23:49","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":939329,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAFM-IR mapping and spectroscopic confirmation of polymer wrapping on SWCNTs.\u003c/strong\u003e AFM topographic image, AFM-IR absorption map, and absorption spectra obtained at locations indicated in AFM-IR absorption map at 1726 cm\u003csup\u003e-1\u003c/sup\u003e of thin film with SWCNTs sorted by \u003cstrong\u003ea, b, c\u003c/strong\u003e PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e\u003cstrong\u003e, \u003c/strong\u003eand \u003cstrong\u003ed, e, f\u003c/strong\u003e (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e. The scanning size was 22 μm\u003csup\u003e2\u003c/sup\u003e at the digital resolution of 256256 pixels.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-5631674/v1/bce0b44f47e3f410a3a3c1cc.png"},{"id":78885170,"identity":"fb4bbc15-63c0-4ab0-85e7-5e2bc1b42f9f","added_by":"auto","created_at":"2025-03-20 09:31:50","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":1652516,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eMechanical properties of sorted SWCNT hybrids assessed by AFM-QNM. \u003c/strong\u003eThe images of AFM topographic, quantitative nano-mechanical (QNM) properties of materials, such as DMT modulus, dissipation energy, and adhesion force of the thin film with \u003cstrong\u003ea-d\u003c/strong\u003e (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e,\u003cstrong\u003e e-h\u003c/strong\u003e pure SWCNT,\u003csub\u003e \u003c/sub\u003eand \u003cstrong\u003ei-l\u003c/strong\u003e SWCNT sorted by (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e. The scanning size was 11 μm\u003csup\u003e2\u003c/sup\u003e at the digital resolution of 256256 pixels. \u003cstrong\u003em-o\u003c/strong\u003e Height, modulus, dissipation energy, and adhesion force of locations indicated in the red arrow direction in AFM-QNM images. \u003cstrong\u003ep\u003c/strong\u003e Force-displacement (F-δ) curves of the pure (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e, pure SWCNT, and sorted SWCNT obtained at the location indicated by the arrow in AFM image. The negative values of F-δ curves indicate attractive forces (AF), while positive values signify repulsive forces (RF). All the force constant of the cantilever is k=6 N/m.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-5631674/v1/4965920526830a088ae03dab.png"},{"id":78886237,"identity":"357fe8ae-fb4a-42db-9388-ce76a241c5a0","added_by":"auto","created_at":"2025-03-20 09:39:51","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5477900,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5631674/v1/f81d5063-e910-41fc-9334-7a1841992d94.pdf"},{"id":78884700,"identity":"50f7d2eb-b192-4684-b3cd-e012f9f1eaec","added_by":"auto","created_at":"2025-03-20 09:23:50","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2731046,"visible":true,"origin":"","legend":"Supplementary information","description":"","filename":"NatureComsupplementaryvictoria1212.docx","url":"https://assets-eu.researchsquare.com/files/rs-5631674/v1/2a5b2331fb1f0da57443d888.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Block Copolymer Architectures for Modulating Interactions to Enhance Selectivity and Stability of s-SWCNT Dispersions","fulltext":[{"header":"Introduction","content":"\u003cp\u003eCompared to devices based on traditional semiconductors like silicon, those fabricated using semiconducting single-walled carbon nanotubes (s-SWCNTs) offer advantages such as smaller dimensions, lower power consumption, faster switching speeds, and enhanced flexibility, representing the future of electronic technology.\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e Dispersing pristine CNTs from tangled and aggregated bundles into separated states poses a long-standing challenge due to the ultrahigh aspect ratio of CNTs and the strong adsorption between them.\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e Utilizing conjugated polymers as non-covalent surface modifiers presents a straightforward and efficient approach to solubilizing CNTs without compromising their intrinsic characteristics.\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e Conjugated polymer sorting stands as a valuable technique for obtaining s-SCWNTs, which are crucial for various applications, including field-effect transistors (FETs).\u003csup\u003e\u003cspan additionalcitationids=\"CR5\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e Numerous studies have identified factors influencing the selectivity of polymer sorting, with polymer identity being key to obtaining specific chiralities.\u003csup\u003e\u003cspan additionalcitationids=\"CR8 CR9 CR10\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003ePrevious research has focused on modifying side chains by leaving the polymer backbone unchanged to enhance the efficiency of conjugated polymers in sorting SWCNTs. Bao et al. investigated rr-P3ATs with varying side-chain lengths, inducting that longer side chains improve the dispersion of s-SWCNTs by facilitating more complete wrapping around nanotubes.\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e Similarly, Loi et al. demonstrated that selective dispersion of SWCNTs could be achieved by tuning the alkyl side-chain length from C\u003csub\u003e6\u003c/sub\u003e to C\u003csub\u003e18\u003c/sub\u003e (PF6 to PF18).\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e The longer side-chain length allowed for more effective coverage of SWCNTs, reducing nanotube re-bundling. Especially, PF12 yielded high-quality SWCNT samples, with long photoluminescence lifetimes and increased photoluminescence yield, indicating enhanced individualization of SWCNTs and minimal defect formation of the nanotubes. In contrast, PF15 and PF18 displayed reduced selectivity for s-SWCNTs of specific chiralities due to the presence of an increased number of SWCNT configurations. Ziegler et al. revealed that elongation of the side chain tends to introduce structural distortions and substantial disorder in the PF backbone, leading to weaker π-π interactions and increased diverse interactions between PF and SWCNT.\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eAs mentioned above, polymer-SWCNT interactions have been effectively modulated by tuning the side-chain length of conjugated polymers, where optimal lengths facilitate polymer-SWCNT supramolecular structures, thereby enhancing dispersion efficiency. Beyond side-chain modification, incorporating block segments further improves sorting performance. Our previous studies demonstrated that polyfluorene (PF) with shorter C\u003csub\u003e8\u003c/sub\u003e side chains achieved sorting enhancements by introducing polyisoprene (PI) in block copolymers (BCPs).\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e The addition of PI, with its extended non-polar chains, creates substantial van der Waals forces, effectively preventing nanotube reaggregation and thereby sustaining dispersion stability over extended periods. Even with a relatively low molecular weight for PF (weight-average molecular weight\u0026thinsp;~\u0026thinsp;12 kDa), this BCP significantly enhances sorting efficiency and maintains high dispersion stability with excellent stability for one year in current polymer sorting studies.\u003csup\u003e\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e Furthermore, coil-conjugated-coil triblock copolymers comprising oligomeric PF (\u003cem\u003eM\u003c/em\u003e\u003csub\u003en\u003c/sub\u003e ~ 6 kDa) and polystyrene coils exhibited even higher selectivity than conventional homopolymers.\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e From the above reports, introducing non-polar segments significantly bolsters sorting capabilities and long-term stability. Hence, systematic investigation into interactions contributed by non-polar segments remains necessary to clarify their influence on both stability and sorting efficiency throughout the entire sorting process.\u003c/p\u003e \u003cp\u003eIn this work, block copolymers (BCPs) based on polyfluorene (PF) with varied soft segment architectures, including linear diblock and miktoarm configurations, were investigated and illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. Specifically, the miktoarm configuration is thought to incorporate steric hindrance elements that modify nanotube-nanotube interactions, thereby reducing reaggregation tendencies. In contrast to previous studies that relied on step-growth polycondensation for PF-based polymer synthesis aimed at SWCNT sorting,\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e,\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e this study employed the Suzuki-Miyaura catalyst transfer polycondensation (SCTP) method using a triolborate-type fluorene monomer.\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e This approach carries out the precise synthesis of end-functionalized PF-based BCPs with narrow dispersity to effectively control the SWCNT sorting results.\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e Poly(\u003cem\u003eε\u003c/em\u003e-caprolactone) (PCL) is selected as a promising soft segment candidate for studying the SWCNTs sorting due to van der Waals interactions among polymer chains,\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e which supports the PF wrapping process on SWCNTs during sorting, resulting in stable dispersion and enhanced sorting performance.\u003c/p\u003e \u003cp\u003eFurthermore, PCL of linear diblock copolymers and miktoarm star polymers can be precisely synthesized via living ring-opening polymerization.\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e Hence, the influence of PCL-based BCPs on SWCNT sorting was thoroughly investigated by evaluating the sorting efficacy of various molecular weights and architectures of PCL-\u003cem\u003eb\u003c/em\u003e-PF and PCL\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF. Among these polymers, PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e (linear BCPs) and (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e (branched BCPs) demonstrated optimal dispersion yield and selectivity, with (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e exhibiting exceptional stability over 1 year which is the longest duration observed without aggregate formation. These polymers effectively disperse s-SWCNTs, primarily around 1.145 nm in diameter, resulting in high performance in thin-film transistor devices based on sorted s-SWCNT random networks. Atomic force microscopy-based infrared spectroscopy (AFM-IR) cPRICE\u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003e \u003cb\u003eSynthesis of PF-based block copolymer.\u003c/b\u003e Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea presents a synthetic schematic for the PF-containing block copolymers (BCPs) with poly(\u003cem\u003eε\u003c/em\u003e-caprolactone) (PCL) as the soft segment. The BCP synthesis involves the preparation of hydroxy-terminated PF via Suzuki-Miyaura catalyst transfer polycondensation (SCTP) of a triolborate-type fluorene monomer (M3) followed by ring-opening polymerization (ROP) of ε-caprolactone. Here, the SCTP of M3 monomer, as previously reported by the group, offers an efficient and versatile strategy for synthesizing end-functionalized PFs with relatively narrow dispersity.\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e \u003cb\u003eSupplementary Scheme 1\u003c/b\u003e outlines the detailed synthetic route for M3. To investigate the influence of BCP molecular parameters on the sorting ability of SWCNT, both the linear AB diblock copolymer with different PF and PCL length (PF-\u003cem\u003eb\u003c/em\u003e-PCL) and the A\u003csub\u003e3\u003c/sub\u003eB-type miktoarm star polymers ((PCL)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF) were synthesized.\u003c/p\u003e \u003cp\u003eFor synthesizing the PF-\u003cem\u003eb\u003c/em\u003e-PCL and (PCL)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF, the PFs with one and three hydroxyl groups at the terminal (HO-PF and (HO)\u003csub\u003e3\u003c/sub\u003e-PF, respectively) were first prepared via the SCTP using different initiators (\u003cb\u003eSupplementary Schemes 2 and 5\u003c/b\u003e). To identify the end-group structure of the obtained HO-PF and (HO)\u003csub\u003e3\u003c/sub\u003e-PF, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) measurements were conducted, revealing periodic molecular ion peaks ranging from approximately 1,000 to 5,000 Da (\u003cb\u003eSupplementary Fig.\u0026nbsp;1a\u003c/b\u003e). The peak spacing of 332 Da for both products matched well with the theoretical molecular weight of a PF monomer unit (332.25 Da), indicating that the product consisted of repeating units of dihexyl fluorene. The peaks at \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e of 1770.95 and 1849.91, are assignable to the desired HO-PF with the \u003cem\u003eω\u003c/em\u003e-chain end structures of H or Br, respectively. Similarly, the peaks at \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e of 1889.13 and 1929.21 observed in the MALDI-TOF MS of (HO)\u003csub\u003e3\u003c/sub\u003e-PF are assignable to the desired (HO)\u003csub\u003e3\u003c/sub\u003e-PF with the ω-chain end structures of H or Br, respectively (\u003cb\u003eSupplementary Fig.\u0026nbsp;1b\u003c/b\u003e). The number-averaged molecular weight calculated from the \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR spectrums (\u003cem\u003eM\u003c/em\u003e\u003csub\u003en,NMR\u003c/sub\u003e) of HO-PFs is 9100 Da and 5800 Da; (HO)\u003csub\u003e3\u003c/sub\u003e-PF is 6200 Da, which exhibited relatively narrower dispersity (\u003cem\u003e\u0026ETH;\u003c/em\u003e) values (\u003cb\u003eSupplementary Table\u0026nbsp;1\u003c/b\u003e) of 1.74, 1.59, and 1.64, respectively.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eSince the terminal hydroxyl group serves as the initiating point for ROP, the subsequent ROP of \u003cem\u003eε\u003c/em\u003e-caprolactone from HO-PF and (HO)\u003csub\u003e3\u003c/sub\u003e-PF give rise PF-\u003cem\u003eb\u003c/em\u003e-PCL and (PCL)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF, respectively (\u003cb\u003eSupplementary Schemes 3 and 6\u003c/b\u003e). Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed displays the size-exclusion chromatography (SEC) traces of the obtained PF-\u003cem\u003eb\u003c/em\u003e-PCL and (PCL)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF from HO-PF and (HO)\u003csub\u003e3\u003c/sub\u003e-PF after the ROP steps. Shifting towards the higher molecular weight region compared to the elution peak of the PF macroiniaitors confirmed the successful chain extension of PCL segment from the terminal hydroxyl groups. The \u003cem\u003e\u0026ETH;\u003c/em\u003e\u003csub\u003e\u003cem\u003eM\u003c/em\u003e\u003c/sub\u003e values estimated from the SEC measurement (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) indicate relatively narrow (1.36\u0026ndash;1.48) for the BCPs. The \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR signals from the benzyl group (Aromatic, 7.68\u0026ndash;7.86 ppm; 5.19 ppm), PF backbone (Aromatic, 7.68\u0026ndash;7.86 ppm; a, 0.76\u0026ndash;1.26 ppm; b, 2.13 ppm), and PCL backbone (d, 2.31 ppm; e, 1.26\u0026ndash;1.68 ppm; f, 4.06 ppm; g, 3.65 ppm) were observed in the \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea), with each signal appropriately attributed to the structure of the target PF-\u003cem\u003eb\u003c/em\u003e-PCL and (PCL)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF. Molecular weight and \u003cem\u003e\u0026ETH;\u003c/em\u003e of the PF and PF-containing BCPs used in this study are summarized in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and \u003cb\u003eSupplementary Table\u0026nbsp;1\u003c/b\u003e.\u003c/p\u003e \u003cp\u003eIn addition to the BCP comprising PF and PCL, a series of BCP with different soft segments were also synthesized. To investigate the influence of soft segment structure, three monomers with six-membered cyclic structures, poly(\u003cem\u003eδ\u003c/em\u003e-valerolactone) (PVL), polylactide (PLA), and poly(trimethylene carbonate) (PTMC), were utilized for the ROP using HO-PF\u003csub\u003e6k\u003c/sub\u003e macroinitiator.\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e Thease monomers vary in their in-ring functionalities: ester for \u003cem\u003eδ\u003c/em\u003e-valerolactone (\u003cem\u003eδ\u003c/em\u003eVL), diester for lactide (LA), and carbonate for trimethylene carbonate (TMC), as illustrated in \u003cb\u003eSupplementary Schemes 7, 8, and 9\u003c/b\u003e, respectively, giving the soft segments with varied chemical characteristics.\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e The NMR spectra and SEC traces of BCPs are shown in \u003cb\u003eSupplementary Fig.\u0026nbsp;2.\u003c/b\u003e\u003c/p\u003e \u003cp\u003e \u003cb\u003ePolymer Characterization.\u003c/b\u003e First, to elucidate how the BCP molecular weight and architecture affect the fundamental polymer characteristics, PF, PCL-\u003cem\u003eb\u003c/em\u003e-PF, and (PCL)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF polymers were subjected to the UV-visible absorption and photoluminescence (PL) spectral measurements, as well as thermogravimetric and differential scanning calorimetry (DSC) analyses (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec and S3). As the molecular weight of PF increases, a red-shifted absorption peak occurs, shifting from 381 nm for PF\u003csub\u003e6k\u003c/sub\u003e to 382 nm for PF\u003csub\u003e9k\u003c/sub\u003e, attributed to the increased backbone length.\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e Similarly, higher molecular weight results in red-shifted PL peaks, transitioning from 418 to 421 nm due to increased aggregation of PF. Moreover, the absorption and emission results of the PF-\u003cem\u003eb\u003c/em\u003e-PCL copolymer show negligible differences compared to those of the PF homopolymer, suggesting that the incorporation of the PCL block has a negligible effect on the optical properties and formation of the PF.\u003c/p\u003e \u003cp\u003eThe thermal behavior of the BCPs was examined through TGA traces recorded from 20 to 550\u0026deg;C under a nitrogen atmosphere (\u003cb\u003eSupplementary Fig.\u0026nbsp;3b\u003c/b\u003e). The HO-PF\u003csub\u003e6k\u003c/sub\u003e and HO-PF\u003csub\u003e9k\u003c/sub\u003e polymers demonstrate the 5% weight loss temperature (\u003cem\u003eT\u003c/em\u003e\u003csub\u003ed, 5%\u003c/sub\u003e) at approximately 377\u0026deg;C and 411\u0026deg;C, respectively. The BCPs display \u003cem\u003eT\u003c/em\u003e\u003csub\u003ed, 5%\u003c/sub\u003e ranging from 363 to 378\u0026deg;C, indicating their overall high thermal stability. The thermal properties of films comprising PCL-blocked BCPs were assessed using DSC, as depicted in \u003cb\u003eSupplementary Fig.\u0026nbsp;3c\u003c/b\u003e. A summary of all thermal transitions and the corresponding PCL crystallinity (\u003cem\u003eX\u003c/em\u003e\u003csub\u003ePCL\u003c/sub\u003e) values is provided in \u003cb\u003eSupplementary Table\u0026nbsp;2\u003c/b\u003e. It was observed that as the molecular weight of the PCL increased, the corresponding increase in the melting temperature and \u003cem\u003eX\u003c/em\u003e\u003csub\u003ePCL\u003c/sub\u003e was evident in the PCL segment. The melting enthalpies and crystallization of branched architectures are lower than linear ones, attributed to the constrained mobility of densely packed monomers near the branch points.\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e In addition, wide-angle X-ray scattering (WAXS) analysis (\u003cb\u003eSupplementary Fig.\u0026nbsp;3d\u003c/b\u003e) also exhibits a slight enhancement in the crystallinity of PCL, particularly evident in the (110), (111), and (200) planes, with increasing molecular weight of the PCL block.\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003e\u003cb\u003eSynthesis of PF-based BCP\u003c/b\u003e \u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"8\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMacroinitiator\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003e[monomer]\u003csub\u003e0\u003c/sub\u003e\u003c/p\u003e \u003cp\u003e/[initiator]\u003csub\u003e0\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003econv. (%)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003cem\u003eM\u003c/em\u003e\u003csub\u003en,NMR\u003c/sub\u003e\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e(g mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u003cem\u003eM\u003c/em\u003e\u003csub\u003en,SEC\u003c/sub\u003e \u003csup\u003e\u003cem\u003ec\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e(g mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003cem\u003e\u0026ETH;\u003c/em\u003e \u003csup\u003e\u003cem\u003ec\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eYield (%)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePCL\u003csub\u003e6k\u003c/sub\u003e\u003cem\u003e-b\u003c/em\u003e-PF\u003csub\u003e9k\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eHO-PF\u003csub\u003e9k\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e60/1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e88.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e15,000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e25,500\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e83.2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePCL\u003csub\u003e12k\u003c/sub\u003e\u003cem\u003e-b\u003c/em\u003e-PF\u003csub\u003e9k\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e120/1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e95.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e21,600\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e33,600\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e88.2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePCL\u003csub\u003e6k\u003c/sub\u003e\u003cem\u003e-b\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\" morerows=\"2\" rowspan=\"3\"\u003e \u003cp\u003eHO-PF\u003csub\u003e6k\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e60/1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e93.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e11,400\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e21,500\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.36\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e65.1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePCL\u003csub\u003e12k\u003c/sub\u003e\u003cem\u003e-b\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e120/1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e87.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e17,600\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e26,800\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.36\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e74.8\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePCL\u003csub\u003e17k\u003c/sub\u003e\u003cem\u003e-b\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e180/1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e84.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e22,800\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e32,900\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.48\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e88.4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e(PCL\u003csub\u003e4k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u003cem\u003e-b\u003c/em\u003e- PF\u003csub\u003e6k\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003e(HO)\u003csub\u003e3\u003c/sub\u003e-PF\u003csub\u003e6k\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e120/1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e78.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e17,300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e31,300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.48\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e63.3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e(PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u003cem\u003e-b\u003c/em\u003e- PF\u003csub\u003e6k\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e180/1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e94.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e22,300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e43,800\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.43\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e72.3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003csup\u003e \u003cem\u003ea\u003c/em\u003e \u003c/sup\u003ePolymerization conditions: temperature, r.t.-90\u0026deg;C; atmosphere, Ar; [Macroinitiator]\u003csub\u003e0\u003c/sub\u003e/[TBD]\u0026thinsp;=\u0026thinsp;1/1. \u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003eDetermined by \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR spectrum in CDCl\u003csub\u003e3\u003c/sub\u003e. \u003csup\u003e\u003cem\u003ec\u003c/em\u003e\u003c/sup\u003eDetermined by SEC in THF using PSt standards.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSorting of SWCNTs by conjugated polymers.\u003c/b\u003e \u003c/p\u003e \u003cp\u003eIn our previous studies, we demonstrated the successful sorting of SWCNTs using polyfluorene (PF) copolymers with low weight-average molecular weight (\u003cem\u003eM\u003c/em\u003e\u003csub\u003ew\u003c/sub\u003e \u0026le; 12 kDa).\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e,\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e Low molecular weight conjugated polymers offer several advantages during synthesis, including easier control of polymerization, reduced synthesis time and cost, and enhanced purity of polymer. However, excessively short polymers fail to provide sufficient interaction with SWCNTs, leading to low dispersion and reaggregate during centrifugation. Despite these challenges, our previous work showed that PF copolymers with low \u003cem\u003eM\u003c/em\u003e\u003csub\u003ew\u003c/sub\u003e could still successfully sort SWCNTs, attributed to the ability of longer PI segments to create non-polar van der Waals interactions between the nanotubes. Therefore, the interaction contributed from the soft segment is crucial to study the sorting ability of polymers with different weight-average molecular weights. In this investigation, we intentionally designed PF BCPs with different soft segment structures to explore their sorting capabilities and the interaction between the hybrids. SWCNTs of diameter ranging from 0.89 to 2.04 nm, synthesized via the chemical vapor deposition (CVD) method as previously reported,\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e were dispersed in toluene using the PF-based BCPs. The sorting steps followed a similar procedure for PF-based polymer dispersions in previous work.\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e After sonication and ultracentrifugation, the supernatant portion was extracted for optical investigations.\u003c/p\u003e \u003cp\u003ePhotoluminescence excitation (PLE) measurements provide evidence regarding the chirality and diameters of individual s-SWCNTs among the sorted nanotubes. This method excludes metal SWCNTs due to their lack of fluorescence and eliminates the bundles of aggregation since they quench luminescence and broaden optical transitions.\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e,\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e The positions of SWCNT resonances were plotted using the scheme proposed by Weisman and Bachilo.\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e As Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea illustrates, PLE measurements indicate minimal sorting by HO-PF\u003csub\u003e9k\u003c/sub\u003e, a relatively short homopolymer, as its π-π interactions with SWCNTs remain insufficient to counteract competing interactions between polymer-wrapped SWCNTs or between polymers.\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e In sharp contrast, incorporating PCL\u003csub\u003e6k\u003c/sub\u003e or PCL\u003csub\u003e12k\u003c/sub\u003e segments into the short PF polymers significantly enhances the signal intensity, particularly for species (10,9) and (15,1) (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb and \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec), suggesting that PCL strongly augments favorable polymer-SWCNT interactions. To further substantiate that the polymer-SWCNT interaction serves as a key factor by PCL segment, PF\u003csub\u003e6k\u003c/sub\u003e diblock copolymers with shorter PF segments were designed. The HO-PF\u003csub\u003e6k\u003c/sub\u003e homopolymer also lacks effective sorting as illustrated in \u003cb\u003eSupplementary Fig.\u0026nbsp;4\u003c/b\u003e. The synthesis of PCL\u003csub\u003e6k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e and PCL\u003csub\u003e12k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e exhibit significant emission peaks from s-SWCNTs (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed and \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ee), with selectivity for major semiconducting species (15,1) and (12,4), indicating a marked enhancement in sorting efficiency through PCL segment. Hence, to achieve effective sorting, the role of non-conjugated coil interactions introduced by the PCL segments predominantly governs the interactions between the BCP and SWCNT, while the π-π interactions from the polymer backbone remain limited. \u003cb\u003eSupplementary Fig.\u0026nbsp;5a\u003c/b\u003e shows that the hydrodynamic radius (\u003cem\u003eR\u003c/em\u003e\u003csub\u003eh\u003c/sub\u003e) of PCL\u003csub\u003e6k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e9k\u003c/sub\u003e is larger than that of PCL\u003csub\u003e6k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e in solutions assessed by dynamic light scattering (DLS), indicating that longer conjugated-segment in BCPs may facilitate aggregation.\u003csup\u003e\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e According to the above sorting performance, the two types of copolymers with PF\u003csub\u003e9k\u003c/sub\u003e and PF\u003csub\u003e6k\u003c/sub\u003e exhibit minor differences. Therefore, PF\u003csub\u003e6k\u003c/sub\u003e is selected as the conjugated segment to further investigate the effect of the soft segment.\u003c/p\u003e \u003cp\u003eThe extended coil segment length of PCL\u003csub\u003e17k\u003c/sub\u003e in PF\u003csub\u003e6k\u003c/sub\u003e was specifically designed to strengthen interactions with the nanotube surface, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ef. This configuration results in a remarkably concentrated sorting with a narrower chirality distribution, prominently for (12,4) SWCNTs with a diameter of 1.145 nm. To our knowledge, this represents the shortest PF segment demonstrating high sorting efficiency, attributed to the enhanced polymer-SWCNT interaction through non-covalent interactions. Increasing coil segment length in short PF-based BCPs reduces the attractive forces between conjugated polymer-wrapped SWCNTs, mitigating reaggregation and thereby enhancing sorting efficiency. Further exploration of interaction effects between polymer-wrapped SWCNTs by the introduction of branched PCL in BCPs creates steric hindrance to reduce π-π interactions and stabilize polymer-wrapped SWCNTs. Results confirm that branched PCL chains improve selective interactions with specific nanotube chiralities, even where π-π stacking provides weak contributions, as seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eg and \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eh. Compared to linear PCL\u003csub\u003e6k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e and PCL\u003csub\u003e12k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e, the branched (PCL\u003csub\u003e4k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e with shorter PCL segments per branch shows more selective PLE spectrum demonstrates the enrichment of the major semiconducting species (12,4) SWCNTs sorted by the branched BCPs. Additionally, (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e also achieves significant enrichment of SWCNTs with (12,4) chirality, further validating the effectiveness of the branched PCL approach.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ei displays the names of the seven polymers employed and a chirality map of the SWCNTs, covering a diameter range of approximately 0.9\u0026ndash;1.2 nm, as determined from optical measurements. In this map, pale-yellow hexagons represent successfully selected SWCNT species, with the colors of the rhombuses inside indicating which BCPs can selectively sort the specific tubes. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ej depicts a schematic illustration of the sorting process mechanism using the designed BCPs in toluene. Toluene enhances the selective dispersal of individual SWCNTs and promotes the propensity of PF to adopt a helical structure in this solvent.\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e,\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e Within the suspension, π-π stacking interaction between the PF backbone and the SWCNT surface dominates the binding energy between the PF and nanotubes, facilitating the adsorption of polymers onto the SWCNTs.\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e The PCL segment provides abundant physical interactions, primarily van der Waals forces,\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e to enhance sorting results and acts as a barrier among nanotubes to prevent the reaggregation of sorted SWCNTs.\u003c/p\u003e \u003cp\u003eThe absorption ratios between the first (M\u003csub\u003e11\u003c/sub\u003e) interband transition of metallic tubes, and the second (S\u003csub\u003e22\u003c/sub\u003e) and third (S\u003csub\u003e33\u003c/sub\u003e) interband transitions of semiconducting tubes provide a qualitative measure of the proportion of metallic SWCNTs remaining in the sorted tubes.\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e,\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ek illustrates the absorption spectrum of sorted SWCNTs exhibiting these three bands. Both PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e and (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e-wrapped SWCNTs exhibit the absence of the metallic absorption band, while the intensity of the semiconducting absorption bands is notably pronounced. Furthermore, the separated semiconducting SWCNTs, enriched to approximately 90% purity as assessed using \u003cb\u003eSupplementary Eq.\u0026nbsp;1\u003c/b\u003e (refer to \u003cb\u003eSupplementary Table\u0026nbsp;3\u003c/b\u003e),\u003csup\u003e\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e,\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e,\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e were sorted by these two BCPs. This indicates their potential as candidates for achieving higher yields and purer s-SWCNTs and paves the way for subsequent investigation into the stability and application of SWCNTs wrapped with different BCP architectures.\u003c/p\u003e \u003cp\u003eLong-term stability of dispersion is crucial for maintaining consistent s-SWCNT performance in electronic applications. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003el and \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003em illustrate the impact of BCP architecture on dispersion stability, evaluated through UV-Vis absorption spectroscopy. Over one year, the linear BCP, PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e, maintained 76% of its initial S\u003csub\u003e22\u003c/sub\u003e peak intensity (as calculated by \u003cb\u003eSupplementary Eq.\u0026nbsp;2\u003c/b\u003e), with the decrease attributed to gradual reaggregation and sedimentation.\u003csup\u003e\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e Furthermore, it is particularly noteworthy that the absorption intensity of the branched BCP-wrapped tubes, (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e, remained consistent with the initial profile after one year (stability ratio\u0026thinsp;~\u0026thinsp;95%) at room temperature, exhibiting the ultrahigh stability of branched BCP-wrapped SWCNT hybrids in solution within current polymer sorting studies. The improvement in long-term stability achieved by (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e is attributed to the inherent steric hindrance provided by the branched PCL segments, which act as barriers between conjugated block-wrapped SWCNTs. This strategy increases free volume and van der Waals interactions, creating additional unoccupied space that reduces reaggregation tendencies.\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e,\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e,\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e DLS data (\u003cb\u003eSupplementary Fig.\u0026nbsp;5b\u003c/b\u003e) indicates that BCPs with a branched PCL moiety exhibit a smaller radius compared to a linear PCL block, providing advantages in maintaining polymer-SWCNT hybrid stability without significant impact from the polymer in suspension. The stability of both linear and branched polymer-wrapped SWCNT solutions is further supported by PLE mapping (\u003cb\u003eSupplementary Fig.\u0026nbsp;6\u003c/b\u003e), where a narrow chirality distribution persists even after one year. Demonstration of the molecular weight and architecture of the model coil segments, PCL, do significantly influence the properties and stability of the sorted SWCNTs, emphasizing the importance of designing the soft segment interactions within the sorting system.\u003c/p\u003e \u003cp\u003eTo extend the concept of soft segments playing a critical role in SWCNT sorting to various chemical structures, PVL, PLA, and PTMC with varying degrees of polarity were introduced into PF-based BCPs and assessed through optical absorption spectra, as shown in \u003cb\u003eSupplementary Fig.\u0026nbsp;7a and 7b\u003c/b\u003e. Dispersions of metallic and semiconducting SWCNTs were quantified by calculating the area under the absorption spectra (\u003cb\u003eSupplementary Table\u0026nbsp;4\u003c/b\u003e). Among these studied BCPs, PCL\u003csub\u003e6k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e reveals the highest purity of semiconducting SWCNTs, while PTMC\u003csub\u003e6k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e results in almost absent in absorption intensity. This trend correlates with the polarity order of the soft segments (CL\u0026thinsp;\u0026lt;\u0026thinsp;VL\u0026thinsp;\u0026lt;\u0026thinsp;LA\u0026thinsp;\u0026lt;\u0026thinsp;TMC),\u003csup\u003e21,40,41\u003c/sup\u003e suggesting that lower polarity enhances efficiency and selectivity in the toluene solution system. The stronger affinity between more polar segments and metallic SWCNTs reduces the purity of SWCNTs.\u003csup\u003e\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e Moreover, the PCL with better solubility in toluene improves the dispersion of nanotubes within the polymer matrix, which is crucial for achieving a uniform distribution of SWCNTs. These effects lead to a higher sorting yield and improved purity in PCL-based systems, highlighting the potential of the PCL segment for efficient SWCNT separation. The PLE results also unveiled the selective ability of different soft segment polymers, even when transitioning to the polar LA units, which retained their selectivity despite having a shorter molecular weight. The PLE maps (\u003cb\u003eSupplementary Fig.\u0026nbsp;7c-f\u003c/b\u003e) also illustrate the increasing broad emission and decreasing selectivity of SWCNTs solutions sorted by relative polar BCPs, highlighting the potential effectiveness of PCL in sorting SWCNTs.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eApplication in Transistors using Sorted SWCNTs.\u003c/b\u003e To further confirm the enrichment of s-SWCNT through the BCPs sorting method, Raman spectra were measured under various excitation wavelengths. Under 532 nm excitation (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea), the metallic radial breathing mode (RBM) peaks disappeared post-sorting, while the broad semiconducting RBM peaks persisted, indicating the removal of most metallic species.\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e,\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e Upon 633 nm laser excitation (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb), a stronger RBM peak at 200 cm⁻\u0026sup1;, characteristic of metallic tubes, was observed in pristine SWCNTs but significantly reduced in sorted SWCNTs.\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e Additionally, the G band Raman spectra of metallic and semiconducting nanotubes show differences under 633 nm excitation (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec).\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e The broad G⁻ peak, which indicates metallic nanotubes, was significantly decreased in the sorted SWCNTs compared to the pristine SWCNTs. These results demonstrate that metallic tubes were effectively removed after sorting with PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e and (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e. This sorting method offers a pathway to produce enriched s-SWCNT materials, which have promising potential for testing in semiconductor-based electronics.\u003c/p\u003e \u003cp\u003eTherefore, the bottom-gate top-contact device configuration was employed to construct random SWCNT networks on SiO\u003csub\u003e2\u003c/sub\u003e (300 nm)/Si wafers using a simple solution coating method, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed. The transfer curve and atomic force microscopy (AFM) height image of a typical TFT device are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ee. The hole charge carrier mobility was observed across 10 fabricated devices ranging from 3.29 to 4.84 cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e V\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (average: 4.02 cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e V\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e and from 9.26 to 13.00 cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e V\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (average: 11.47 cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e V\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e. Detailed electrical characteristics, including hysteresis sweeps and the square root of the source-drain current, are presented in \u003cb\u003eSupplementary Fig.\u0026nbsp;8\u003c/b\u003e and \u003cb\u003eSupplementary Table\u0026nbsp;5\u003c/b\u003e. As shown in \u003cb\u003eSupplementary Fig.\u0026nbsp;8a and 8b\u003c/b\u003e, the dual sweeps of the sorted SWCNT devices exhibit a noticeable hysteresis loop, attributed to the PF with excellent hole-trapping ability.\u003csup\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e,\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e The square root of the source-drain current and the output curve of transistors fabricated with sorted SWCNTs are presented in \u003cb\u003eSupplementary Fig.\u0026nbsp;8e and 8f\u003c/b\u003e. The most promising transistor achieved a high mobility of 19.68 cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e V\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and an on/off ratio of 2.6\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\times\\:\\)\u003c/span\u003e\u003c/span\u003e10\u003csup\u003e3\u003c/sup\u003e (\u003cb\u003eSupplementary Fig.\u0026nbsp;9\u003c/b\u003e). In addition, SWCNTs sorted with PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e and (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e solutions, stored for one year, were fabricated devices to evaluate performance (\u003cb\u003eSupplementary Fig.\u0026nbsp;10\u003c/b\u003e). The average hole charge carrier mobilities reached 3.71 and 9.42 cm\u003csup\u003e2\u003c/sup\u003e V\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively, both exhibiting excellent electrical properties. These results demonstrate that even after one year in solution, the polymer-SWCNT hybrids maintained uniform dispersion and retained electrical characteristics. The strong interaction between polymers and SWCNTs complicates the removal of polymer wrapping, which may reduce charge transport between s-SWCNTs due to potential charge-trapping effects. Nevertheless, electrical performance remains exceptional, revealing the viability of s-SWCNTs sorted by PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e and (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e for semiconductor applications requiring long-term stability.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eTopology and Mechanical Properties of Sorted SWCNTs.\u003c/b\u003e To verify the presence of BCPs wrapped around the surface of SWCNTs, AFM-based infrared spectroscopy (AFM-IR) was employed to gain critical insights into the distribution of polymer components within thin films on the SiO\u003csub\u003e2\u003c/sub\u003e/Si substrate, as depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea-d.\u003csup\u003e\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e The FTIR spectra (\u003cb\u003eSupplementary Fig.\u0026nbsp;11\u003c/b\u003e) reveal a significantly stronger absorbance signal at 1726 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e in the BCPs compared to SWCNTs. This peak corresponds to the C\u0026thinsp;=\u0026thinsp;O stretching vibration, indicating the presence of the PCL molecule within the BCPs.\u003csup\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e Hence, the IR laser was tuned to 1726 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to excite the PCL phase for AFM-IR map measurement. The height image obtained from AFM (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed) provides insight into the morphology of the tubes, while the corresponding AFM-IR absorption map (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee) highlights regions of higher amplitude (depicted in red) where the tubes are situated. These red regions signify areas of higher polymer concentration, suggesting effective wrapping of the CNT tube surfaces by the polymer. The intensity of amplitude at points 1 and 2 for SWCNTs sorted by PCL\u003csub\u003e17k\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e, and at points 3 and 4 for SWCNTs sorted by (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e, is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ef, which evidences that the intensity of points 1 and 3 (tubes) is stronger than that of points 2 and 4 (wafer), confirming the successful wrapping of the SWCNTs surfaces by the BCPs.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe discrepancy in surface mechanical properties, including Derjaguin-Muller-Toporov (DMT) modulus, dissipation, and adhesion, between thin films of (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e, SWCNTs, and their hybrid materials was investigated using PeakForce Quantitative Nanomechanical Mapping (QNM) AFM, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e. The pure BCP sample (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea) exhibits evident phase separation, the characteristic also observed in PF-\u003cem\u003eblock\u003c/em\u003e-poly(\u003cem\u003eδ\u003c/em\u003e-decanolactone) (PF-\u003cem\u003eb\u003c/em\u003e-PDL) films, which contributes to the tight packing of PF blocks promoted by intermolecular π-π interactions, while the softer PCL blocks with lower modulus form an amorphous matrix around the PF fibers.\u003csup\u003e\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e, \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e, \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/sup\u003e This phase separation is further elucidated by the mechanical properties analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003em) exhibited through line profiles obtained at specific locations (indicated by arrows) in the AFM images in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb-d, which reveal higher modulus, and lower dissipation and adhesion in the PF domain region than PCL domain region. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ee depicts the morphology of pure SWCNTs fabricated without polymer sorting, exhibiting significant aggregation for larger tube sizes (\u0026gt;\u0026thinsp;40 nm height) compared to sorted SWCNTs (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ei). The surface mechanical properties of pure SWCNTs are exhibited in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ef-h \u003cb\u003eand\u003c/b\u003e Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003en. AFM-IR verification confirms polymer coating on the surfaces of sorted SWCNT, leading to lower modulus but higher dissipation and adhesion compared to pure SWCNTs, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ej-l and Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eo. Notably, the adhesion image and adhesion line profile of SWCNTs sorted by the BCPs were significantly observed in the increased adhesion force at the tube edges, indicating the presence of polymer on the exterior of the tubes.\u003c/p\u003e \u003cp\u003eForce-displacement (F-δ) curves (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ep) obtained at specific locations (indicated by arrows) over particles in the AFM images also provide mechanical properties of different materials. The energy dissipation (ED) is measured from the area hysteresis between the approach and withdrawal curves.\u003csup\u003e\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e The larger area between the curves for BCPs compared to tubes indicates lower stiffness and higher viscosity. Moreover, the slope of the F-δ curve in the repulsive force (RF) region directly reflects polymer stiffness, which is softer compared to pure nanotubes.\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e This observation is consistent with the smaller slope of repulsive forces observed in sorted SWCNTs compared to pure tubes, indicating the softer and less viscous behavior of the sorted SWCNTs. Despite the soft polymer wrapping the SWCNT surface, the conductivity of the SWCNTs within the polymer matrix is evident through current measurements using tunneling AFM (TUNA) mode, as depicted in \u003cb\u003eSupplementary Fig.\u0026nbsp;12\u003c/b\u003e. The brighter areas in \u003cb\u003eSupplementary Fig.\u0026nbsp;12b\u003c/b\u003e correspond to the nanotube material, demonstrating a noticeable current flow, which confirms the efficient charge transport ability of SWCNTs within the BCPs matrix.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eIn summary, the critical role of block copolymer architecture is in achieving both high selectivity and long-term stability in semiconducting single-walled carbon nanotube (s-SWCNT) dispersions. The introduction of a PCL segment into PF-based BCPs not only modulates SWCNT sorting but also enhances dispersion stability by providing steric hindrance and additional van der Waals interactions. The linear PF-\u003cem\u003eb\u003c/em\u003e-PCL copolymers with longer PCL segments demonstrated increased selectivity of sorted nanotubes demonstrated. Moreover, the branched (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e architecture exhibited superior performance, maintaining exceptional dispersion stability for over one year, attributed to the enhanced steric hindrance introduced by the branched structure, which prevents reaggregation and stabilizes polymer-wrapped SWCNT hybrids in solution. Both linear and branched block copolymers achieved narrow distributions of SWCNT chirality around 1.145 nm in diameter and purity of approximately 90% semiconducting nanotubes. Investigation with alternative soft segments of varying polarity further demonstrated that lower polarity enhances sorting selectivity in the toluene system, suggesting the dominant influence of van der Waals interactions between the nanotubes. The AFM-based analyses, including Nano-IR and QNM measurements, provided direct evidence of polymer wrapping and the mechanical influence on SWCNT hybrids in the thin film state. Thin-film transistors fabricated from branched BCP-wrapped nanotubes exhibited high performance with hole mobilities reaching 11.47 cm\u0026sup2; V⁻\u0026sup1; s⁻\u0026sup1;. Therefore, this study provides a valuable strategy for adjusting both polymer-nanotube and nanotube-nanotube interactions by designing block copolymer architectures to improve SWCNT sorting efficiency and dispersion stability.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e \u003cb\u003eSynthesis of PF-\u003c/b\u003e \u003cb\u003eb\u003c/b\u003e \u003cb\u003e-PCL.\u003c/b\u003e Tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct Pd\u003csub\u003e2\u003c/sub\u003e(dba)\u003csub\u003e3\u003c/sub\u003e\u0026bull;CHCl\u003csub\u003e3\u003c/sub\u003e.\u003csup\u003e\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e 1,8-Diazabicyclo[5.4.0]-undec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 4-iodobenzyl alcohol, 4-iodobenzyl bromide, \u003cem\u003eε\u003c/em\u003e-caprolactone (\u003cem\u003eε\u003c/em\u003e-CL), \u003cem\u003erac\u003c/em\u003e-lactide (\u003cem\u003erac\u003c/em\u003e-LA), sodium hydride (NaH; 60% dispersion in paraffin liquid), tetrabutylammonium iodide (TBAI), \u003cem\u003etrans\u003c/em\u003e-2-[3-(4-\u003cem\u003etert-\u003c/em\u003ebutylphenyl)-2-methyl-2-propylidene]malononitrile, and 2,2-bis(hydroxymethyl)-1,3-propanediol were purchased from Tokyo Chemical Industry Co., Ltd. (TCI) and used as received. Dry-dichloromethane (CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e), dry-dimethylformamide (DMF), dry-tetrahydrofuran (THF), and dry-toluene were purchased from Kanto Chemical Co., Inc. and used as received. 1,1,1-Tris(hydroxymethyl)ethane, tri(\u003cem\u003etert\u003c/em\u003e-butyl)phosphine (\u003cem\u003et\u003c/em\u003e-Bu\u003csub\u003e3\u003c/sub\u003eP), and tripotassium phosphate (K\u003csub\u003e3\u003c/sub\u003ePO\u003csub\u003e4\u003c/sub\u003e) were purchased from Fujifilm Wako Pure Chemical Co. and used as received. \u003cem\u003erac\u003c/em\u003e-Lactide (\u0026gt;\u0026thinsp;98.0%) was purified by recrystallization (twice) from dry toluene and stored in a glovebox. DBU (\u0026gt;\u0026thinsp;98.0%) and \u003cem\u003eε\u003c/em\u003e-CL (\u0026gt;\u0026thinsp;99.0%) were purified by distillation over CaH\u003csub\u003e2\u003c/sub\u003e under reduced pressure and stored in a glovebox. Dry-CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e (\u0026gt;\u0026thinsp;99.5%; water content, \u0026lt;\u0026thinsp;0.001%), dry-THF (\u0026gt;\u0026thinsp;99.5%; water content, \u0026lt;\u0026thinsp;0.001%), and dry-toluene (\u0026gt;\u0026thinsp;99.5%; water content, \u0026lt;\u0026thinsp;0.001%) were further purified using an MBRAUN MB-SPS Compact solvent purification system equipped with a MB-KOL-C column and MB-KOL-A column (for dry-toluene), a MB-KOL-A column and a MB-KOL-A column (for dry-CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e), or a MB-KOL-A column and a MB-KOL-M Type 1 column (for dry-THF), which were then directly used for the polymerizations.\u003c/p\u003e \u003cp\u003e \u003cb\u003ePreparation of SWCNT/PF-\u003c/b\u003e \u003cb\u003eb\u003c/b\u003e \u003cb\u003e-PCL dispersions.\u003c/b\u003e Single-walled carbon nanotubes (SWCNTs; d\u0026thinsp;\u0026le;\u0026thinsp;2.0 nm) were prepared according to the reported methods.\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e For all SWCNT dispersions, a mixture consisting of 0.15 mg mL\u003csup\u003e-\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e of SWCNTs and 0.00009 mmol mL\u003csup\u003e-\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e of polymer was added to 10 mL of toluene. The mixture was sonicated for 1.5 h in the cup horn of a high-power sonicator (Qsonica) used at 490 W. The temperature of the sample was kept constant at 4\u0026deg;C in the cooling bath during sonication. Immediately after sonication, the dispersion was centrifuged at 48000 g for 3 h (Beckman Avanti J-26 Hitachi) for samples used to fabricate field effect transistors. The upper supernatant was taken and used for further measurements. The pure SWCNTs (1.7mg) were dispersed in 10 mL of n-methyl pyrrolidinone (NMP). This solution was sonicated at an amplitude level of 490 W for 30 min in the cooling bath. Then, the centrifuge at 6,000 rpm for 30 min to dissociate the undispersed CNT. The upper supernatant was taken and used for further measurements.\u003c/p\u003e \u003cp\u003e \u003cb\u003eThin film and device fabrication.\u003c/b\u003e Thin films of pure polymer dissolved in toluene (5 mg mL\u003csup\u003e-\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) were spin-cast on SiO\u003csub\u003e2\u003c/sub\u003e/Si substrates at a spinning rate of 1000 rpm for 60 s. Subsequently, the films underwent thermal annealing at 170 ℃ for 20 min. The supernatant solution of pure CNT was slowly spray-coated on a Si wafer at 200 ℃ to form a thin film. Field-effect transistor (FET) devices were fabricated on highly doped n-type Si (100) wafers with a 300 nm SiO\u003csub\u003e2\u003c/sub\u003e layer. The semiconducting layer was spin-coated onto SiO\u003csub\u003e2\u003c/sub\u003e/Si substrates at 1000 rpm for 60 s from a prepared polymer-SWCNT suspension at room temperature and in ambient conditions. Devices were thermally annealed at 120\u0026deg;C for 1 h to remove residual solvent. Top-contact gold electrodes (50 nm) were deposited by evaporation through a shadow mask, defining the channel length (L) and width (W) as 50 \u0026micro;m and 1000 \u0026micro;m, respectively. Transistor measurements were carried out using a Keithley 4200 semiconductor parameter analyzer (Keithley Instruments Inc., Cleveland, OH, USA).\u003c/p\u003e \u003cp\u003e \u003cb\u003eAnalytical measurements.\u003c/b\u003e \u003cem\u003eGlovebox.\u003c/em\u003e The polymerization was carried out in an MBRAUN stainless steel glovebox equipped with a gas purification system (molecular sieves and copper catalyst) and a dry Ar atmosphere (H\u003csub\u003e2\u003c/sub\u003eO, O\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;1 ppm). The moisture and oxygen contents in the glovebox were monitored by an MB-MO-SE 1 moisture sensor and an MB-OX-SE 1 oxygen sensor, respectively.\u003c/p\u003e \u003cp\u003e \u003cem\u003eNuclear magnetic resonance (NMR).\u003c/em\u003e The \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR (400 MHz) and \u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003eC NMR (100 MHz) spectra were obtained by a JEOL JNM-ECS400 instrument or a JEOL JNM-ECX400P instrument at 25 \u0026ordm;C.\u003c/p\u003e \u003cp\u003e \u003cem\u003eSize exclusion chromatography (SEC).\u003c/em\u003e The size exclusion chromatography (SEC) was performed at 40\u0026deg;C in THF (flow rate, 1.0 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) using a Shodex GPC-101 gel permeation chromatography system (Shodex DU-2130 dual pump, Shodex RI-71-S reflective index detector, and Shodex ERC-3125SN degasser) equipped with a Shodex KF-G guard column (4.6 mm \u0026times; 10 mm; particle size, 8 \u0026micro;m) and two Shodex KF-804L columns (linear, 8 mm \u0026times; 300 mm). The number-average molecular weight (\u003cem\u003eM\u003c/em\u003e\u003csub\u003en,SEC\u003c/sub\u003e) and the dispersity (\u003cem\u003e\u0026ETH;\u003c/em\u003e) of the polymers were calculated based on polystyrene calibrations.\u003c/p\u003e \u003cp\u003e \u003cem\u003eMatrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS).\u003c/em\u003e MALDI-TOF MS measurement of the polymer was carried out in the reflector mode using an ABSCIEX TOF/TOF/5800 equipped with a 337 nm nitrogen laser (3 ns pulse width). The MALDI-TOF MS samples were prepared by depositing a mixture of the polymer and matrix in THF onto a sample plate. A 1:80 (v/v) ratio of [PF (1.0 g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e in THF)]/[\u003cem\u003etrans\u003c/em\u003e-2-[3-(4-\u003cem\u003etert\u003c/em\u003e-butylphenyl)-2-methyl-2-propylidene]malononitrile (10 g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e in THF)] was used.\u003c/p\u003e \u003cp\u003e \u003cem\u003eThermogravimetric analysis (TGA).\u003c/em\u003e The TGA experiments were performed using a Hitachi High-Tech Science STA200RV under nitrogen atmosphere. The obtained block copolymers were heated from 30 \u0026ordm;C to 550 \u0026ordm;C at the heating rate of 10 \u0026ordm;C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003cem\u003eDifferential scanning calorimetry (DSC).\u003c/em\u003e The thermal properties of the samples were measured by a Hitachi High-Tech Science DSC7000X differential scanning calorimeter (DSC) under a nitrogen atmosphere. The obtained block copolymers were heated from 30\u0026deg;C to 270 \u0026ordm;C at a rate of 30 \u0026ordm;C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, staying at 270 \u0026ordm;C for 5 min to erase thermal history. Then the sample was cooled to -70 \u0026ordm;C at a rate of 20 \u0026ordm;C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, keeping at -70 \u0026ordm;C for 5 min. Finally, the sample was heated to 270 \u0026ordm;C at a rate of 10 \u0026ordm;C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003cem\u003eWide-angle X-ray scattering (WAXS).\u003c/em\u003e The WAXS measurements of the obtained polymers were performed at the BL-6A beamline of the Photon Factory in the High Energy Accelerator Research Organization (KEK, Tsukuba, Japan) using X-ray beams with λ\u0026thinsp;=\u0026thinsp;0.150 nm at room temperature. The scattering data were collected by a 2D detector (PILATUS3 100K (Dectris Ltd.)), where the samples-to-detector distance was set to be around 25 cm for WAXS measurement. The scattering angle (\u003cem\u003eθ\u003c/em\u003e) was calibrated using silver behenate (Nagara Science Co., Ltd) as the standard and derived the scattering vector (\u003cem\u003eq\u003c/em\u003e) from Bragg\u0026rsquo;s equation (|\u003cem\u003eq\u003c/em\u003e| =(4\u003cem\u003eπ\u003c/em\u003e/\u003cem\u003eλ\u003c/em\u003e)sin(\u003cem\u003eθ\u003c/em\u003e/2)). The polymer solids or powders were sandwiched by two pieces of Kapton tapes with a spacer of a stainless washer, which were applied for the measurement.\u003c/p\u003e \u003cp\u003e \u003cem\u003eUltraviolet-visible-near infrared (UV-Vis-NIR) absorption spectroscopy.\u003c/em\u003e The absorption spectra measurements were performed using a UV-Vis/NIR spectrophotometer (model V-676 JASCO) at a wavelength range of 500\u0026ndash;1500 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003cem\u003ePhotoluminescence excitation (PLE) measurement.\u003c/em\u003e The measurements of photoluminescence excitation (PLE) spectra were performed using a fluorescence spectrophotometer (model Fluorolog 3, HORIBA Scientific Japan) at an excitation wavelength range of 400\u0026ndash;1000 nm and an emission wavelength range of 1000\u0026ndash;1600 nm.\u003c/p\u003e \u003cp\u003e \u003cem\u003eDynamic Light Scattering (DLS).\u003c/em\u003e DLS measurements were carried out using a Zetasizer Nano ZS instrument (He-Ne laser, 633 nm, max 4 mW, Malvern Panalytical Ltd). A micro quartz cuvette (ZEN2112, Hellma Analytics) was used. Measurements were carried out at 25\u0026deg;C with a 60 s equilibration time. A cumulant analysis performed using the inbuilt software of the instrument was used to determine the z-average radius.\u003c/p\u003e \u003cp\u003e \u003cem\u003eRaman spectroscopy.\u003c/em\u003e Raman spectral measurements were conducted by using a JASCO 5100 spectrometer (JASCO, Japan) under green laser excitation (λ\u0026thinsp;=\u0026thinsp;532 nm) and red laser excitation (λ\u0026thinsp;=\u0026thinsp;633 nm).\u003c/p\u003e \u003cp\u003e \u003cem\u003eElectrical parameter analyzer.\u003c/em\u003e The electrical properties of OFET were measured by Keithley 4200-SCS semiconductor parameter analyzer at room temperature in a completely dark and inert N\u003csub\u003e2\u003c/sub\u003e-filled glove box.\u003c/p\u003e \u003cp\u003e \u003cem\u003eAttenuated Total Reflectance-Fourier transform infrared spectroscopic (ATR-FTIR).\u003c/em\u003e IR spectra were tested using ATR-FTIR (PerkinElmer, USA).\u003c/p\u003e \u003cp\u003e \u003cem\u003eAtomic force microscope (AFM).\u003c/em\u003e The morphology of thin films was measured by tapping mode AFM from Bruker Dimension ICON. The mechanical properties were measured by quantitative nanomechanical mapping (QNM) from Bruker Dimension Icon. The probe used a model of RTESPA-150 with a nominal spring constant (k) 6.0 N/m and a resonant frequency (f\u003csub\u003e0\u003c/sub\u003e) of 150 Hz. Tunneling-AFM (TUNA) is a method for measuring ultra-low currents on low-conductive samples. A DC bias is applied between the sample and the conductive tip as the tip scans the sample in contact mode. A PtIr-coated tip with 0.01\u0026ndash;0.025 Ωcm Antimony (n) doped Si was used.\u003c/p\u003e \u003cp\u003e \u003cem\u003eAtomic force microscopy with nanoscale infrared spectroscopy (Nano-IR AFM).\u003c/em\u003e The device surface morphology was measured using a nanoIR3 AFM-IR from Anasys Instruments (Santa Barbara, CA) coupled to a MIRcat-QT quantum cascade mid-infrared laser operating at 1470 kHz in ranges 917\u0026ndash;1700 and 1900\u0026ndash;2230 cm\u003csup\u003e-\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e. AFM-IR data were collected in tapping mode using a gold-coated AFM probe [spring constant (\u003cem\u003ek\u003c/em\u003e)\u0026thinsp;=\u0026thinsp;40 N m\u003csup\u003e-\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e and resonant frequency (f\u003csub\u003eo\u003c/sub\u003e)\u0026thinsp;=\u0026thinsp;300 kHz].\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors thankfully acknowledge the financial support from the National Science and Technology Council in Taiwan (NSTC 111-2628-E-011-008-MY3, 113-2811-E-011-008-MY2, and 113-2124-M-011-002) and JSPS Fund for the Promotion of Joint International Research (No. 21KK0096). The authors also appreciate the financial support provided by “the Sustainable Electrochemical Energy Development Center (SEED Center)” from The Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education of Taiwan. The WAXS study was approved by the Photon Factory Program Advisory Committee (Proposal No. 2023G574). T.S. thanks the funding support from the Frontier Chemistry Center\u0026nbsp;(Hokkaido University), the Photo-Excitonic Project (Hokkaido University),\u0026nbsp;the Creative Research Institution (CRIS, Hokkaido University), and the List\u0026nbsp;Sustainable Digital Transformation Catalyst Collaboration Research Platform (List-PF, Hokkaido University).\u0026nbsp;H.Z. amd X.G. thanks the funding support from Office of Naval Research (ONR) under the contract number N00014-23-1-2063 to enable the AFM-IR meausrments.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor\u003c/strong\u003e\u003cstrong\u003eContributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eM.-N.C. and Y.-C.C. conceived the idea and designed the experiments. I.T. and S.T. designed the studied conjugated block polymers. A.M. and I.R. synthesized the conjugated block polymers and characterized their properties using NMR, SEC, MALDI-TOF MS, TGA, DSC, and WAXS. M.-N.C. conducted the fabrication of SWCNT sorting and thin-film transistors and characterized them by UV-Vis-NIR, PLE, DLS, Raman, electrical measurements, ATR-FTIR, and AFM analyses. H.Z. performed the Nano-IR AFM experiments. H. Q.-A. and C. K.-L. carried out the AFM with QNM. L. Y.-T. contributed to the TUNA measurements. L. W.-T. and C. W.-H. synthesized the SWCNTs. X.G., I.T., and Y.-C.C. supervised the project and contributed to all aspects of the analysis. M.-N.C. organized the data, analyzed the results, and wrote the manuscript under the guidance of M. M. M., X.G., C. W.-H., I.T., S.T., and Y.-C.C.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics declarations\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eCompeting\u0026nbsp;interests\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eWang J, Lei T (2020) Separation of semiconducting carbon nanotubes using conjugated polymer wrapping. Polymers 12:1548\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSamanta SK, Fritsch M, Scherf U, Gomulya W, Bisri SZ, Loi MA (2014) Conjugated polymer-assisted dispersion of single-wall carbon nanotubes: the power of polymer wrapping. Acc Chem Res 47:2446\u0026ndash;2456\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFujigaya T, Nakashima N (2015) Non-covalent polymer wrapping of carbon nanotubes and the role of wrapped polymers as functional dispersants. 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Organometallics 31:2302\u0026ndash;2309\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-5631674/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5631674/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe challenge of maintaining long-term stability in dispersed nanotube solutions arises in the case of sorting semiconducting single-walled carbon nanotubes (s-SWCNTs) with conjugated homopolymers. A strategic approach that enhances steric hindrance between nanotubes is desirable to inhibit re-aggregation effectively. This study systematically investigates interactions between BCP-SWCNTs, assessing molecular weight and steric factors by introducing a nonpolar poly(\u003cem\u003eε\u003c/em\u003e-caprolactone) (PCL) segment into the lowest-molecular-weight polyfluorene (PF) as a demonstration. Employing a (PCL\u003csub\u003e6k\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PF\u003csub\u003e6k\u003c/sub\u003e miktoarm architecture achieves highly selective dispersions of s-SWCNTs with 1.145 nm diameters, attaining exceptional dispersion stability for over one year without re-aggregation. Thin-film transistors fabricated from these dispersions exhibit hole mobility up to 11.47 cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e V\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e without additional washing treatment. This structural design of the soft segment emerges as a powerful strategy to modulate SWCNT-SWCNT interactions, highlighting the significant role of branched, soft segment-based conjugated BCPs in enhancing both sorting selectivity and dispersion stability.\u003c/p\u003e","manuscriptTitle":"Block Copolymer Architectures for Modulating Interactions to Enhance Selectivity and Stability of s-SWCNT Dispersions","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-03-20 09:23:14","doi":"10.21203/rs.3.rs-5631674/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"718871e7-e84a-40cd-a1e1-809812145700","owner":[],"postedDate":"March 20th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":41978057,"name":"Physical sciences/Materials science/Materials for devices/Electronic devices"},{"id":41978058,"name":"Physical sciences/Nanoscience and technology/Nanoscale materials/Carbon nanotubes and fullerenes"}],"tags":[],"updatedAt":"2025-03-20T09:23:27+00:00","versionOfRecord":[],"versionCreatedAt":"2025-03-20 09:23:14","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5631674","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5631674","identity":"rs-5631674","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}