Hyeong Min Jin

Flexible and transferrable self-assembled nanopatterning on chemically modified graphene.

Figure 1 . (a) Transferrable self-assembled nanopatterning procedure. See text for details. SEM images of lamellar BCP nanotemplates transferred onto (b) right angled fracture edge of silicon wafer and (c) microscale ZnO hillock. (d) Photograph and (e) SEM image of cylindrical BCP nanotemplates transferred onto syringe needle surface. Block copolymer (BCP) self-assembly generates dense and periodic nanodomains, whose characteristic dimensions can be as small as 3 nm. [ 1–3 ] Such self-assembly in thin fi lms can create two-dimensional lithographic nanotemplates with pattern precision barely attainable by other methods. [ 4–9 ] Substantial progress in the synergistic integration of BCP selfassembly with e-beam lithography and ArF or other photolithography, demonstrates that this self-assembly based nanopatterning is a promising technology to complement the resolution limit of a conventional lithography. [ 10–20 ] Meanwhile, BCP self-assembled nanopatterning has been regarded as an intrinsic two-dimensional patterning method specifi cally useful for hard and fl at inorganic substrates. [ 4 , 21 ] The wellestablished processing steps involved with the formation of uniform thickness, ultrathin (typically less than 100 nm) BCP fi lm via spin casting and subsequent thermal/solvent annealing are generally considered incompatible to three-dimensional geometries or conventional fl exible polymer substrates with low chemical/thermal stability and surface roughness typically larger than nanoscale. In this work, mechanically robust but compliant chemically modifi ed graphene (CMG) fi lm [ 22 , 23 ] is introduced as a transferrable and disposable substrate for the self-assembled nanopatterning of nonplanar, fl exible, and even multistack device oriented structures. Taking advantage of the high chemical/ thermal stability, genuine atomic scale fl atness, and mechanical robustness with compliance, graphene based materials can be excellent substrates for nanopatterning (Supporting Information, Table S1). [ 24 , 25 ] While pristine graphene has a low surface energy, CMG prepared via

Au–Ag Core–Shell Nanoparticle Array by Block Copolymer Lithography for Synergistic Broadband Plasmonic Properties

Localized surface plasmon resonance of metallic nanostructures receives noticeable attention in photonics, electronics, catalysis, and so on. Core-shell nanostructures are particularly attractive due to the versatile tunability of plasmonic properties along with the independent control of core size, shell thickness, and corresponding chemical composition, but they commonly suffer from difficult synthetic procedures. We present a reliable and controllable route to a highly ordered uniform Au@Ag core-shell nanoparticle array via block copolymer lithography and subsequent seeded-shell growth. Size-tunable monodisperse Au nanodot arrays are generated by block copolymer self-assembly and are used as seed layers to grow Ag shells with variable thickness. The resultant Au@Ag core-shell nanoparticle arrays exhibit widely tunable broadband enhancement of plasmonic resonance, greatly surpassing single-element nanoparticle or homogeneous alloy nanoparticle arrays. Surface-enhanced Raman scattering of the core-shell nanoparticle arrays showed an enhancement factor greater than 270 from Au nanoparticle arrays.

Laser Writing Block Copolymer Self-Assembly on Graphene Light-Absorbing Layer

Recent advance of high-power laser processing allows for rapid, continuous, area-selective material fabrication, typically represented by laser crystallization of silicon or oxides for display applications. Two-dimensional materials such as graphene exhibit remarkable physical properties and are under intensive development for the manufacture of flexible devices. Here we demonstrate an area-selective ultrafast nanofabrication method using low intensity infrared or visible laser irradiation to direct the self-assembly of block copolymer films into highly ordered manufacturing-relevant architectures at the scale below 12 nm. The fundamental principles underlying this light-induced nanofabrication mechanism include the self-assembly of block copolymers to proceed across the disorder-order transition under large thermal gradients, and the use of chemically modified graphene films as a flexible and conformal light-absorbing layers for transparent, nonplanar, and mechanically flexible surfaces.

Laser Crystallization of Organic–Inorganic Hybrid Perovskite Solar Cells

Organic-inorganic hybrid perovskites attract enormous research interest for next generation solar energy harvest. Synergistic crystalline structures comprising organic and inorganic components enable solution processing of perovskite films. A reliable crystallization method for perovskites, compatible with fast continuous process over large-area flexible substrates, is crucial for high performance solar cell production. Here, we present laser crystallization of hybrid perovskite solar cells using near-infrared (NIR) laser (λ = 1064 nm). Crystalline morphology of CH3NH3PbI3 (MAPbI3) perovskite films are widely controllable with laser irradiation condition while maintaining film uniformity. Photothermal heating effectively assisted by interfacial photoconversion layers is critical for phase transformation without beam damage of multilayered device structures. Notably, laser crystallization attains higher device performances than conventional thermal annealing. Fast laser crystallization with manufacture level scan rate (1 m min(-1)) demonstrates inverted-type perovskite solar cells with 11.3 and 8.0% efficiencies on typical glass and flexible polymer substrates, respectively, without rigorous device optimization.

Highly tunable refractive index visible-light metasurface from block copolymer self-assembly

The refractive index of natural transparent materials is limited to 2–3 throughout the visible wavelength range. Wider controllability of the refractive index is desired for novel optical applications such as nanoimaging and integrated photonics. We report that metamaterials consisting of period and symmetry-tunable self-assembled nanopatterns can provide a controllable refractive index medium for a broad wavelength range, including the visible region. Our approach exploits the independent control of permeability and permittivity with nanoscale objects smaller than the skin depth. The precise manipulation of the interobject distance in block copolymer nanopatterns via pattern shrinkage increased the effective refractive index up to 5.10. The effective refractive index remains above 3.0 over more than 1,000 nm wavelength bandwidth. Spatially graded and anisotropic refractive indices are also obtained with the design of transitional and rotational symmetry modification.

Electrical Biomolecule Detection Using Nanopatterned Silicon via Block Copolymer Lithography

An electrical biosensor exploiting a nanostructured semiconductor is a promising technology for the highly sensitive, label-free detection of biomolecules via a straightforward electronic signal. The facile and scalable production of a nanopatterned electrical silicon biosensor by block copolymer (BCP) nano-lithography is reported. A cost-effective and large-area nanofabrication, based on BCP self-assembly and single-step dry etching, is developed for the hexagonal nanohole patterning of thin silicon films. The resultant nanopatterned electrical channel modified with biotin molecules successfully detects the two proteins, streptavidin and avidin, down to nanoscale molarities (≈1 nm). The nanoscale pattern comparable to the Debye screening length and the large surface area of the three-dimensional silicon nanochannel enable excellent sensitivity and stability. A device simulation confirms that the nanopatterned structure used in this work is effective for biomolecule detection. This approach relying on the scalable self-assembly principle offers a high-throughput manufacturing process for clinical lab-on-a-chip diagnoses and relevant biomolecular studies.

3D Tailored Crumpling of Block-Copolymer Lithography on Chemically Modified Graphene

Novel 3D self-assembled nanopatterning is presented via tailored crumpling of chemically modified graphene. Block-copolymer self-assembly formed on a layer of chemically modified graphene provides highly dense and uniform 2D nanopatterns, and the controlled crumpling of the chemically modified graphene by mechanical instabilities realizes the controlled 3D transformation of the self-assembled nanopatterns.

Device-oriented graphene nanopatterning by mussel-inspired directed block copolymer self-assembly

Directed self-assembly of a block copolymer is successfully employed to fabricate device-oriented graphene nanostructures from CVD grown graphene. We implemented mussel-inspired polydopamine adhesive in conjunction with the graphoepitaxy principle to tailor graphene nanoribbon arrays and a graphene nanomesh located between metal electrodes. Polydopamine adhesive was utilized for facile and damage-free surface treatment to complement the low surface energy of pristine graphene. Our process minimizes the damage to the ideal graphitic structures and electrical properties of graphene during the nanopatterning process. Multi-channel graphene nanoribbon arrays and a graphene nanomesh were successfully fabricated between metal electrodes.

Flash Light Millisecond Self-Assembly of High χ Block Copolymers for Wafer-Scale Sub-10 nm Nanopatterning

One of the fundamental challenges encountered in successful incorporation of directed self-assembly in sub-10 nm scale practical nanolithography is the process compatibility of block copolymers with a high Flory-Huggins interaction parameter (χ). Herein, reliable, fab-compatible, and ultrafast directed self-assembly of high-χ block copolymers is achieved with intense flash light. The instantaneous heating/quenching process over an extremely high temperature (over 600 °C) by flash light irradiation enables large grain growth of sub-10 nm scale self-assembled nanopatterns without thermal degradation or dewetting in a millisecond time scale. A rapid self-assembly mechanism for a highly ordered morphology is identified based on the kinetics and thermodynamics of the block copolymers with strong segregation. Furthermore, this novel self-assembly mechanism is combined with graphoepitaxy to demonstrate the feasibility of ultrafast directed self-assembly of sub-10 nm nanopatterns over a large area. A chemically modified graphene film is used as a flexible and conformal light-absorbing layer. Subsequently, transparent and mechanically flexible nanolithography with a millisecond photothermal process is achieved leading the way for roll-to-roll processability.

Nanodomain swelling block copolymer lithography for morphology tunable metal nanopatterning.

Ordered metal nanopatterns are crucial requirements for electronics, magnetics, catalysts, photonics, and so on. Despite considerable progress in the synthetic route to metal nanostructures, highly ordered metal nanopatterning over a large-area is still challenging. Nanodomain swelling block copolymer lithography is presented as a general route to the systematic morphology tuning of metal nanopatterns from amphiphilic diblock copolymer self-assembly. Selective swelling of hydrophilic nanocylinder domains in amphiphilic block copolymer films during metal precursor loading and subsequent oxygen based etching generates diverse shapes of metal nanopatterns, including hexagonal nanoring array and hexagonal nanomesh and double line array in addition to common nanodot and nanowire arrays. Solvent annealing condition of block copolymer templates, selective swelling of hydrophilic cylinder nanodomains, block copolymer template thickness, and oxygen based etching methods are the decisive parameters for systematic morphology evolution. The plasmonic properties of ordered Au nanopatterns are characterized and analyzed with finite differential time domain calculation. This approach offers unprecedented opportunity for diverse metal nanopatterns from commonly used diblock copolymer self-assembly.