Bottom-Up Fabrication of DNA-Templated Electronic Nanomaterials and Their Characterization

Abstract

Bottom-up fabrication using DNA is a promising approach for the creation of nanoarchitectures. Accordingly, nanomaterials with specific electronic, photonic, or other functions are precisely and programmably positioned on DNA nanostructures from a disordered collection of smaller parts. These self-assembled structures offer significant potential in many domains such as sensing, drug delivery, and electronic device manufacturing. This review describes recent progress in organizing nanoscale morphologies of metals, semiconductors, and carbon nanotubes using DNA templates. We describe common substrates, DNA templates, seeding, plating, nanomaterial placement, and methods for structural and electrical characterization. Finally, our outlook for DNA-enabled bottom-up nanofabrication of materials is presented.

Keywords: DNA origami; DNA templates; electrical characterization; nanofabrication.

Figure 1

Schematic of DNA-templated material assembly. (a) DNA strands serve as a building material using (a₁) dsDNA or (a₂) ssDNA. (b) The DNA strands form templates: (b₁) a dsDNA or (b_2–5) DNA origami structures: triangle, rectangle, bar, or octahedron. (c) Types of seeds: (c₁,c₂) metal cations in solution, (c₃) inorganic nanoparticles, or (c₄) inorganic nanorods. (d) Seeding methods: (d₁) non-site-specific seeding on a dsDNA and (d_2–4) site-specific seeding on DNA origami: triangle, rectangle, or bar. (e) Plating techniques: (e₁) electroless/chemical reduction, (e₂) photochemical, and (e₃) electrochemical. (f) Metallized DNA templates: (f₁) dsDNA, (f_2–4) DNA origami structures: triangle, rectangle, or bar. (g) Characterization techniques: (g₁) AFM, SEM, or TEM, or (g₂) electron-beam formation of 2-terminal and 4-terminal probe connections.

Figure 2

DNA alignment techniques. (a) (i) AFM images of dsDNA/Au−Fe₃O₄ NP conjugates aligned on silicon substrates under magnetic fields in different directions. (ii) Immobilization procedure for dsDNA/Au−Fe₃O₄ NP conjugates on silicon substrates. Reprinted from Liu et al. [71] Copyright 2018 American Chemical Society. (b) Directed assembly of porphyrin-labeled DNA origami on a Teflon resist after e-beam exposure. Reprinted from Shaali et al. [72] Copyright 2017 Royal Society of Chemistry. (c) DNA origami with single-stranded linkers and attached Cy5 placement on binding sites created via e-beam patterning to make negatively charged carboxylate groups in a background of hydrophobic methyl groups. Reprinted from Gopinath et al. [32] Copyright 2016 Springer-Nature. (d) Experimental strategy for making a hexagonally ordered pattern of nanoholes in a thin Au film on a Si wafer, which is used to direct the adsorption of DNA origami nanostructures. Reprinted from Brassat et al. [69] Copyright 2018 American Chemical Society.

Figure 3

Site-specific seeding on DNA origami templates. (a) Schematic illustration of triangular DNA origami building block design and assembly. Reprinted from Zhang et al. [61] Copyright 2018 Wiley-VCH Verlag. (b) Mold-constraint growth procedure for gold nanostructures. Reprinted from Helmi et al. [92] Copyright 2014 American Chemical Society. (c) Gold bowtie nanostructures based on DNA origami: representation of the experiment. Reprinted from Zhan et al. [62] Copyright 2018 Wiley-VCH Verlag. (d) DNA origami designs and a step-by-step fabrication procedure for different nanostructures. Reprinted from Shen et al. [59] Copyright 2018; distributed under a Creative Commons Attribution License 4.0 (CC BY).

Figure 4

Plating technologies. (a) Schematic illustration of employing the assemble, grow, and lift-off strategy to construct a pre-designed gold nanostructure. Reprinted from Luo et al. [55] Copyright 2020 The Royal Society of Chemistry. (b) Formation of a continuous rectangular Au nanostructure by attaching Au NRs to DNA origami. Reprinted from Uprety et al. [91] Copyright 2017 American Chemical Society. (c) Process flow presenting electrode fabrication made by photoresist (1) and silicon dioxide (2), followed by suspending DNA between the electrodes, and metallization by vapor deposition. Reprinted from Brun et al. [35] Copyright 2017 Wiley-VCH Verlag.

Figure 5

Semiconductors in DNA-based nanofabrication. (a) CdS NRs. Reprinted from Weichelt et al. [67] Copyright 2019 Wiley-VCH Verlag. (b) Te NRs. Reprinted with permission from Aryal et al. [56] Copyright 2020 Springer. (c) Octaniline organic semiconductor assembly with DNA. Reprinted from Wang et al. [104] Copyright 2017 Wiley-VCH Verlag. (d) Fullerene clusters associated with DNA strands. Reprinted from Vittala et al. [102] Copyright 2017 Wiley-VCH Verlag.

Figure 6

DNA-related assembly of CNTs. Placement of DNA end-functionalized CNTs onto DNA origami templates with different angles. Reprinted from Pei et al. [109] Copyright 2019 American Chemical Society.

Figure 7

DNA-related assembly of CNTs. (a) DNA origami platforms for cutting CNTs with designated lengths. Reprinted from Atsumi et al. [111] Copyright 2018 American Chemical Society. (b) Assembling CNT arrays with controlled inter-CNT pitch. Reprinted from Sun et al. [70] Copyright 2020 American Association for the Advancement of Science.

Figure 8

Electrical characterization of DNA-templated nanomaterials. (a) Two-terminal connection with patterns made via photolithography. Reprinted from Brun et al. [35]. Copyright 2017 Wiley-VCH Verlag. (b) Two-terminal connection patterned via EBL. Reprinted from Zhan et al. [63]. Copyright 2017 American Chemical Society. (c) Four-terminal connections patterned via EBL. Reprinted from Bayrak et al. [68]. Copyright 2018 American Chemical Society. (d) Four-terminal connections patterned via EBID. Reprinted with permission from Aryal et al. [60]. Copyright 2018 American Chemical Society. (e) I–V curves (left) for two-terminal measurement and (right) based on the voltage drop determined in four-terminal measurements. Reprinted with permission from Aryal et al. [60]. Copyright 2018 American Chemical Society.