Self-Assembled Nanostructures for High-Performance Sensor Applications

1. INTRODUCTION

A variety of advanced devices, including monitoring systems, medical diagnostic equipment, wearable electronics, and the Internet of Things (IoT), operate in environments where physical, chemical, and biological properties are constantly changing, and sensors can be used to detect and quantify these changes in real time [1-3].

As devices become increasingly personalized and miniaturized, sensors face the critical challenge of delivering exceptional performance with ultraminiaturized form factors. To meet these demands, the nanostructuring of sensor materials has emerged as a key strategy for maximizing the surface area in confined spaces, thereby transcending mere size reduction to significantly enhance sensor sensitivity and selectivity [4-6]. Consequently, the development of large-area-compatible, cost-effective, and readily integrable nanoscale fabrication processes for sensor materials is vital for advancing sensor applications.

Various nanopatterning techniques have been explored to obtain precise nanoscale architectures. Although conventional top-down lithography represents a proven, highly precise nanopatterning strategy for designing materials at the nanoscale, its deployment in the nanostructuring of sensor materials encounters several challenges such as high equipment costs, low throughput over large areas, and limited versatility in generating complex architectures that are vital for optimal sensor performance. Therefore, nanopatterning exploiting self-assembly behavior is a novel strategy for the scalable and cost-effective nanopatterning of sensor materials [7-9].

Self-assembly provides a powerful bottom-up approach that enables the spontaneous formation of ordered nanostructures from basic building blocks through intrinsic material properties and intermolecular forces. Moreover, by precisely controlling the arrangement of atoms and molecules at the nanoscale, self-assembly yields highly uniform structures [10,11]. Based on this uniformity, self-assembled nanostructures can form hierarchical architectures with tunable feature sizes and large active surface areas. These attributes translate directly into enhanced sensitivity, faster response times, and improved selectivity [12]. Furthermore, such nanostructures can be processed under mild conditions and integrated into diverse substrates, making them ideally suited for the large-scale manufacturing of next-generation sensor platforms.

In this review, we focus on recent advances in self-assembled nanostructures for high-performance sensor applications, highlighting the design principles, fabrication strategies, and case studies that illustrate how bottom-up nanoscale architectures can overcome current limitations and pave the way toward next-generation sensing platforms. In particular, by presenting the key research achievements in gas, optical, biological, and strain sensors, this review provides a comprehensive understanding of the advantages afforded by self-assembled nanostructures in each field.

2. GAS SENSOR

Self-assembled structures obtained from molecular building blocks such as block copolymers (BCPs) enable the design of material surfaces with controlled geometries and porosities at the nanoscale. In chemiresistive gas sensing, these structural features enhance the molecular adsorption and transport efficiency by increasing the surface area of the material, exposing active sites, and forming interconnected diffusion networks.

As a representative example, Yun et al. fabricated two-dimensional (2D) molybdenum disulfide (MoS₂) nanomesh–based sensors by exploiting a BCP self-assembly nanolithography strategy and demonstrated their flexible application by transferring them onto a polymer substrate (Fig. 1 (a)) [13]. As shown in Fig. 1 (b), the resulting nanomesh structure provides a highly porous network with abundant exposed edge sites, which facilitates gas adsorption and diffusion, thereby enhancing NO₂ sensing sensitivity and selectivity. Furthermore, the MoS₂ nanomesh exhibited superior sensitivity under humid conditions (80% relative humidity, RH), which was attributed to synergistic charge transfer between NO₂ and pre-adsorbed water molecules, leading to amplified resistance changes in p-type MoS₂ channels (Fig. 1 (c)).

Fig. 1.

Gas-sensor devices based on materials structurally engineered via self-assembled nanopatterns. (a) Schematic of dry etching for MoS2 nanomesh. (b) MoS2 nanomesh transferred onto flexible shrinkage film. (c) NO₂ sensing response of MoS₂ nanomesh and film (1–5 ppm, 80% RH) and selective property of nanomesh toward 1 ppm of various gas molecules. Adapted from Ref. [13]. (d) Schematic overview of the synthesis of Pt-functionalized BCP microparticles and their application in formaldehyde sensing using Pt/SnO₂ hollow frameworks. (e) Selectivity of Pt (0.10)/SnO2 HFs for the detection of HCHO against various analytes and scanning electron microscopy (SEM) image of Pt/SnO₂. (f) Dynamic resistance traces of SnO2 HFs (bottom) and Pt (0.10)/SnO2 HFs (top) in response to HCHO concentrations from 1 to 5 ppm. Adapted from Ref. [14]. (g) Schematic of hierarchical Pd-nanomesh fabrication via multilevel self-assembly, cross-sectional SEM image of PS colloid monolayer on cylindrical BCP, and SEM image of the resulting Pd-mesh structure. (h) Schematic of the integration of a hierarchical mesh for an electrical and optical dual-sensing device. (i) Photographic images of the color change of an integrated sensing device before and after exposure to H2 and absolute change in resistance upon H2 exposure. Adapted from Ref. [15].

Koo et al. developed a formaldehyde sensor based on Pt-decorated SnO₂ hollow frameworks (Pt/SnO₂ HFs) by using self-assembled poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) porous microparticles as templates [14]. As shown in Fig. 1 (d), solvent evaporation induced BCP self-assembly within the emulsion droplets, forming a bicontinuous microporous structure. Platinum precursors were selectively adsorbed onto the P4VP domains via electrostatic interactions, followed by SnO₂ sputter deposition and calcination to yield hollow honeycomb-like structures with uniformly embedded Pt nanoparticles. This hierarchical framework allowed efficient gas transport and catalytic activation at the Pt sites. The resulting sensor exhibited outstanding selectivity toward formaldehyde, with a response of 31.4 (R_air/R_gas at 5 ppm), far exceeding its responses to other interfering gases (Fig. 1 (e)). The dynamic sensing profile exhibited fast response/recovery cycles and a low detection limit of 10 ppb, confirming linear and reproducible responses across a range of concentrations and demonstrating the effectiveness of Pt decoration compared to pure SnO₂ (Fig. 1 (f)).

Yang et al. introduced a hydrogen sensor with a hierarchical mesh structure fabricated via multiscale self-assembly using poly(styrene-block-methyl methacrylate) (PS-b-PMMA) and PS colloidal particles [15]. A hierarchical template—nanoscale cylinders formed by BCP microphase separation overlain by hexagonally arranged microspheres from colloidal self-assembly—produced a multiscale porous mesh (Fig. 1 (g)). A transparent and conductive Pd nanomesh obtained by sequential etching and Pd deposition, was integrated with a tungsten trioxide (WO₃) layer, whose hydrogen-induced optical changes enabled combined chemiresistive and gasochromic sensing mechanisms (Fig. 1 (h)). The resulting sensor demonstrated high transparency (>90%) and mechanical flexibility, with consistent resistance changes across varying H₂ concentrations (Fig. 1 (i)). The expanded porous network promoted fast hydrogen diffusion and accelerated Pd-hydride formation, yielding rapid and reversible sensing responses.

Recent advances in gas-sensing technology using materials morphologically engineered via self-assembled nanopatterns have demonstrated that increased porosity and surface area directly support efficient gas diffusion and adsorption. Moreover, their compatibility with low-modulus, high-transparency substrates enables their integration into wearable and distributed sensor systems, thereby meeting the growing demand for real-time environmental monitoring.

3. OPTICAL SENSOR

Photonic architectures precisely engineered at the nanoscale using molecular self-assembly form the basis of high-performance optical sensors by providing customized geometries, optically modified surfaces, and spatial regularity. Nano-optical scaffolds modulate electromagnetic interactions at interfaces, offering improved sensitivity and adaptability to multidimensional devices. Moreover, functionalized surfaces enhance molecular specificity, thereby improving the selectivity in optical-sensing environments.

Scherrer et al. [16] introduced self-assembled monolayers (SAMs) of alkyne-terminated thiols onto lithographically patterned gold nanohole arrays to fabricate responsive optical-sensing layers (Fig. 2 (a)). The SAM localized the click reaction within plasmonically active regions, enabling surface-enhanced Raman spectroscopy (SERS) to capture bond-specific spectral shifts in real time (Fig. 2 (b)). This setup enabled the selective, label-free monitoring of interfacial reactions through the synergistic effects of chemical confinement and optical-field enhancement.

Fig. 2.

Optical-sensor devices made with self-assembled nanostructures. (a) Schematic of a monocrystalline Si chip with Au nanohole arrays and SEM image of an Au nanohole array. (b) Time-resolved SERS monitoring of surface click reaction. Adapted from Ref. [16]. (c) SEM image of the nanoporous MoS2 thin film transistor. (d) Dependence of ΔVTH on the incident photon energy (Pinc) and corresponding sensitivity of nanoporous and pristine MoS₂ phototransistors. Adapted from Ref. [17]. (e) Process steps for the fabrication of an ultra-thin Au gap plasmon-absorber system, top-view SEM image and scanning transmission electron microscopy image of the Au bilayer metasurface. (f) Maximum absorption as a function of spacer thickness (HAu), obtained by experiments (continuous lines) and compared to simulations (dashed lines). Adapted from Ref. [18]. (g) Schematic of interfacial self-assembly and transfer of AuNP@PNIPAM monolayers onto optical-fiber end face and SEM images of varied surface topography. (h) Sensing studies performed by cover-index variation for the SLR mode at P = 600 nm. Adapted from Ref. [19].

Moreover, Park et al. developed a nanoporous oS₂ photodetector by employing a lithography strategy based on block copolymer self-assembly to fabricate a nanopatterned template [17]. This bottom-up patterning approach enabled the fabrication of highly ordered porous architectures, significantly increasing the surface-to-volume ratio and introducing edge-rich domains (Fig. 2 (c)). Nanoscale features contributed to enhanced light–matter interactions and facilitated the efficient separation and transport of photogenerated charge carriers. Compared to pristine MoS₂ films, the nanostructured counterparts exhibited markedly improved optical sensitivity. Moreover, their photoresponses varied systematically with both the wavelength and intensity of the incident light, indicating that the band structure was modulated by nanoscale confinement (Fig. 2 (d)). These findings highlight the strategic engineering of self-assembled nanostructures to enhance the optoelectronic performance of 2D semiconductor-based photodetectors.

Cummins et al. [18] introduced a scalable strategy for the fabrication of tunable optical absorbers using self-assembled PS-b-PMMA templates. The optical-absorber fabrication process involves the directing of BCP self-assembly to form vertically aligned nanodomains for a nanoporous mask, followed by the sequential deposition of Cr and Au and growth of an Al₂O₃ spacer layer (Fig. 2 (e)). The resulting metasurface exhibited highly ordered Au nanodots on top of the dielectric layers, and the systematic modulation of the nanodot height and spacer thickness enabled precise control over the plasmonic resonance characteristics (Fig. 2 (f)). Among the various structural configurations, the 68 nm-diameter Au nanodots on top of 15 nm Al₂O₃ spacers exhibited absorption exceeding 95% at λ ≈650 nm. This strong resonance was attributed to the vertical-gap plasmon coupling between the patterned nanostructures and underlying metallic layer. This study demonstrates how self-assembly can replace top-down lithography by engineering large-area metasurfaces with tunable optical properties, making them suitable for transparent or flexible optoelectronic platforms.

Kularia et al. [19] used poly(styrene-b-ethylene oxide) (PS-b-PEO) self-assembled templates to guide the formation of periodic gold nanoparticle (AuNP)-based plasmonic arrays on optical-fiber end-faces (Fig. 2 (g)). Gold-poly(N-isopropylacrylamide) core–shell nanoparticles (Au@PNIPAM) were drop-cast and assembled at the air–water interface, followed by transfer via dip coating. This process yielded a monolayer hexagonal lattice with nanoscale uniformity across the curved fiber surface, as confirmed by SEM imaging. Optical characterization revealed sharp extinction peaks originating from surface lattice resonance (SLR) in addition to the typical localized surface plasmon resonance (LSPR) (Fig. 2 (h)). These SLR features showed high refractive-index sensitivity and narrow linewidths, especially when the refractive index of the surrounding medium was close to that of the array environment, achieving a figure of merit as high as ~138 RIU⁻¹. The integration of self-assembled arrays into nonplanar substrates demonstrates the expansion of BCP-driven patterning into fiber-integrated sensing, offering scalable fabrication, high sensitivity, and spectral tunability.

These examples collectively highlight the broad utility of self-assembled nanostructures in advanced optical-sensor technologies. By tailoring precise geometric configurations and material interfaces at the nanoscale, self-assembly enables enhanced control over light–matter interactions, facilitating sensitive and selective optical readouts. Through plasmonic-field enhancement, bandgap modulation, and resonance tuning, these bottom-up approaches provide versatile and scalable routes for functional device architectures. As the demand for compact, high-resolution, and integration-ready optical sensors increases, self-assembly has become a powerful strategy for realizing next-generation platforms with minimal reliance on complex lithography or bulk processing.

4. BIO SENSOR

Biosensors play an essential role in real-time health monitoring and early disease detection for individuals. With the rapid advancement of healthcare technologies, the demand for highly sensitive, responsive, and cost-effective biosensors has increased. One of the most promising strategies for achieving these requirements is the incorporation of nanostructures formed via self-assembly [20]. Compared with traditional top-down approaches, bottom-up self-assembly techniques offer advantages for creating precise and functional nanostructures, such as nanopores, nanorings, and nanodot arrays. These self-assembled nanostructures increase the specific surface area, thereby enhancing the likelihood of interaction with target biomolecules, and enable the desired size control, offering high sensitivity for the target. Self-assembly is inherently compatible with flexible substrates and large-area processing, making it ideal for scalable and wearable biosensor applications.

Chang et al. introduced a self-assembled AuNP ring structure formed through an interfacial self-assembly process between hydrophilic and hydrophobic regions and developed it as a label-free biosensor [21]. Biotin molecules were anchored to the PNIPAM-functionalized AuNP rings, enabling the detection of the target biomolecule streptavidin (Fig. 3 (a)) [22]. The biotin-anchored structures, treated with streptavidin at concentrations of 0, 10, 20, 40, 60, 80, and 100 nM, exhibited a blue shift in the LSPR spectra, corresponding to a structural transition from ring to disk (Fig. 3 (b)). An analysis of LSPR wavelength shifts for different protein streptavidin, whereas non-specific proteins such as bovine serum albumin (BSA) and AffiniPure Goat Anti-Rabbit IgG (AGRI) produced no significant shift, demonstrating high selectivity. (Fig. 3 (c)). This nanoring-based structural platform offers both high selectivity and high sensitivity, making it ideally suited for label-free biosensing applications.

Fig. 3.

Bio Sensors engineered with self-assembled nanopattern for high sensitivity. (a) 2D AFM image of the biotin-modified APCR. (b) LSPR spectra of the APCR. (c) High sensitivity of the streptavidin concentration. Adapted from Ref. [21]. (d) Nanoporous structure of the BCP self-assembly. (e, f) High sensitivity of the complementary DNA. Adapted from Ref. [23]. (g) Au dot array via BCP self-assembly. (h) Highly selective anchoring of DNA origami, followed by hybridization. Adapted from Ref. [26].

Fornerod et al. presented a nanoporous-based electrochemical biosensing platform using BCP self-assembly, enabling large-area and cost-effective fabrication [23]. The hexagonally packed nanoporous structure formed through BCP self-assembly features pores approximately 50 nm in diameter with necks around 20 nm (Fig. 3 (d)).

This self-assembled scaffold operates via the nanopore blockage (NB) mechanism, in which nanopores functionalized with single-stranded DNA (ssDNA) capture probes selectively hybridized with complementary target DNA, resulting in an increase in charge transfer resistance upon hybridization [24,25]. The use of BCP self-assembly enables precise tuning of nanopore dimensions to match the size of the target analyte, providing a key advantage (Fig. 3 (e)). As shown in Fig. 3 (f), the hybridization process reaches near-equilibrium within 20 minutes, enabling rapid and efficient analysis of complementary DNA strands. This work demonstrates significant advancement toward a portable, rapid, and cost-effective nucleic acid detection platform that overcomes the limitations of conventional detection methods.

Ranasinghe et al. developed a precise alignment strategy for DNA origami through BCP self-assembly [26]. To overcome the limited selectivity of conventional electrostatic attachment methods, hexagonally arranged Au nanodot arrays were fabricated via self-assembled PS-b-PMMA thin films (Fig. 3 (g)). DNA-coated Au nanorods aligned along the DNA origami templates, confirming the precise surface localization. (Fig. 3 (h)) showed DNA origami selectively anchored onto self-assembled Au nanodot array via BCP, electrostatic binding of DNA origami and hybridization with Au nanorods coated with complementary DNA strands. [27,28]

This directed placement of DNA origami offers cost-effective and scalable alternative to traditional top-down lithography. It enables large-area, parallel nanopatterning with strong potential for future applications in plasmonic, nanoelectronics, and bottom-up device integration [29,30].

5. STRAIN SENSOR

Strain sensors are key components in wearable and biomedical applications, where real-time detection of body motion and physiological changes is critical for health monitoring, early diagnosis, and injury prevention [31].

Recent advancements have shifted focus towards flexible, stretchable, and conformal sensors that can operate reliably under dynamic deformation. Various building blocks—including block copolymers, nanocrystals, and colloidal particles—inherently form highly ordered, periodic architectures, an attribute that benefits strain sensors by enabling tunable mechanical responses, consistent structural deformation, and precise nanoscale control of sensing domains. These self-assembly systems facilitate the fabrication of strain sensors with multifunctionality, such as simultaneous electrical and optical response, and enable low-cost, large-area, and scalable manufacturing without the need for complex lithography or patterning.

Park et al. reported a strain sensor based on self-assembled BCP Photonic Crystal (PC) film with periodic in-plane lamellae structure aligned parallel to the film surface [32,33]. The sensor consists of a three-layer structure, incorporating a lamellar film formed by self-assembled PS-b-P2VP, embedded within an elastomeric Polydimethylsiloxane (PDMS) matrix and sandwiched between ion-conductive hydrogel electrodes (Fig. 4 (a)). It presented a highly stretchable capacitive sensor capable of visualizing strain, making it highly suitable for applications such as skin-mounted wearable motion detection. Excellent response time stability was also demonstrated, with the switching time remaining constant at approximately 80 ms even under varying strain conditions (Fig. 4 (b)). Furthermore, it exhibited high repeatability, showing no significant change in capacitance after 5000 stretch/release cycles at 50% strain (Fig. 4 (c)). Under applied strain, a reduction in film thickness resulted in a blue shift in the reflected structural color, due to the decreased periodicity of the BCP lamellae [34]. This structural change enabled simultaneous visual and electrical detection of strain via both color modulation and capacitance variation. This study highlights the potential of BCP-based structural color sensors to integrate visual and electrical strain sensing within a single film, made possible by the unique self-assembly behavior of BCPs and the integration of PDMS and ion-conductive hydrogels.

Fig. 4.

Strain sensor engineered with self-assembled nanopattern for high stability and repeatability. (a) SEM image of cross-sectioned BCP SC: IG in PDMS layer. (b-c) response time stability and high repeatability for BCP SC sensor. Adapted from Ref. [32]. (d) TEM image of BaTiO3 nano-cubes self-assembled onto glass fiber fabric. (e) The output current of FPS under 0-50 N linear forces. (f)The evaluated response time of FPS (19 ms). (g) dynamic pushing test for 3000 cycles under 50 N and 1 Hz. Adapted from Ref. [35]. (h) Colloidal crystal monolayer self-assembled via surface tension gradient. (i) repeatability and flexibility of conductive nanoparticle self-assembly and transfer printing strategy. (j) Schematic of the self-powered finger motion sensor. (IHN-BCP/Ionic gel) Adapted from Ref. [37]. (k) The stability of IHN-BCP under 30% RH over 10,000 cycles. Adapted from Ref. [38].

Zhou et al. developed a flexible piezoelectric sensor (FPS) based on 10 nm BaTiO₃ nano cubes self-assembled onto glass fiber fabric (GFF) [35]. During solvent evaporation, strong interactions between the oleic acid ligands on the nanotube surface and hydroxyl groups on the GFF surface facilitated face-to-face alignment, leading to a uniformly ordered nano cube array (Fig. 4 (d)) [36]. Under periodic 0~50 N linear forces, the FPS exhibited a high sensitivity of 101.09 nA/kPa in the low force range (0~10 N) (Fig. 4 (e)) and a short response time of 1 ms (Fig. 4 (f)). Additionally, a dynamic push test over 3,000 cycles under a 50 N load demonstrated the high repeatability of the sensor (Fig. 4 (g)). Owing to its excellent mechanical stability and intrinsic flexibility that enables conformal integration with curved surfaces, the FPS demonstrates strong potential for a wide range of wearable sensing platforms, including biosensing, handwriting recognition, and broader applications in IoT and human–machine interfaces.

Xuan et al. proposed a novel surface tension gradient-driven self-assembly for ultrafast fabrication of colloidal crystals [37]. This approach utilizes the surface tension gradient at the liquid–air interface to induce a Marangoni effect, enabling the formation of highly ordered colloidal crystal monolayers over large areas within seconds (Fig. 4 (h)). Highly ordered micropatterns printed onto low modulus substrates such as PDMS and polyurethane exhibited high mechanical durability and stable performance under bending and stretching conditions, demonstrating excellent repeatability and flexibility (Fig. 4 (i)). The surface-tension-gradient-based self-assembly method presented in this study offers a next-generation, low-cost, high-resolution, and large-area nano structuring strategy, holding great potential for strain sensor applications.

Kim et al. developed a hybrid sensor platform integrating a triboelectric nanogenerator (TENG) with a humidity-responsive SC material, enabling a self-powered motion-sensing display that allows for simultaneous detection and visualization of human motion [38]. The hybrid sensing component is composed of a self-assembled PS-b-P2VP BCP with an interpenetrated hydrogel network (IHN) (Fig. 4 (j)). This BCP–IHN film can respond to both vertical and lateral finger-sliding motions via contact-mode triboelectrification, concurrently inducing SC variations.

The device demonstrated high stability and durability, maintaining its open-circuit voltage with no observable degradation of over 10,000 cycles under 30% relative humidity (RH) (Fig. 4 (k)). The BCP–IHN–based hybrid sensor device demonstrates its potential as an extended strain-sensing technology by leveraging humidity-coupled mechanical deformation and optical modulation.

4. CONCLUSIONS

This review highlights the critical role of self-assembled nanostructures in advancing next-generation sensor technologies, with particular emphasis on gas, biological, optical, and strain sensors. These nanostructures exhibit outstanding sensitivity, selectivity, and stability and are realised without the need for complex lithographic methods. As a bottom-up fabrication approach, self-assembly enables cost-effective and scalable production over large areas, making it highly compatible with emerging sensor applications. Moreover, the ability to engineer hierarchical and porous architectures improves the sensor switching speed and analyte-detection accuracy, making these sensors attractive for flexible and wearable bio-integrated applications. These advances underscore the innovative potential of self-assembled nanostructures in sensor engineering and are expected to drive the development of practical, scalable, and next-generation sensing solutions across diverse applications.

However, realizing the next generation of sensing solutions requires further research. Future efforts should focus on the development of multicomponent or stimuli-responsive materials capable of forming complex, biomimetic, and even dynamically reconfigurable structures. Furthermore, integrating these nanostructures into multimodal systems for simultaneous detection or with self-powered technologies, such as TENGs, is crucial for creating truly autonomous devices. The synergy with artificial intelligence and computational science also presents a transformative opportunity, enabling the optimized inverse design of nanostructures and sophisticated analysis of sensor data. Finally, bridging the gap between laboratory success and industrial applications, establishing robust and standardized manufacturing processes to ensure reproducibility and reliability over large areas remains a challenge. Addressing these prospects will accelerate the development of practical, scalable, and ubiquitous sensing solutions across diverse fields, from personalized healthcare to environmental monitoring.

Acknowledgments

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (Grant No. RS-2025-00513522).

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