Multiple Ink Nanolithography: Toward a Multiple-Pen Nano-Plotter

Hong, Seok Hoon; Zhu, Jin; Mirkin, Chad A.

doi:10.1126/science.286.5439.523

Cited by 551 publications

(383 citation statements)

References 30 publications

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“…One concern with scanning probe lithography is the serial nature of the process and low throughput. Two approaches are in progress to address these issues: automating the nanofabrication (66-70) and͞or using parallel probes (70)(71)(72)(73). Nanostructures of SAMs are sufficiently stable, at least 40 h without observable desorption in pure solvent and 8 h without observable exchange in thiol solutions (50).…”

Section: Precise Positioning Of Small Molecules and Proteins On Surfamentioning

confidence: 99%

Positioning protein molecules on surfaces: A nanoengineering approach to supramolecular chemistry

Liu

Amro

2002

Proc. Natl. Acad. Sci. U.S.A.

183

158

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We discuss a nanoengineering approach for supramolecular chemistry and self assembly. The collective properties and biofunctionalities of molecular ensembles depend not only on individual molecular building blocks but also on organization at the molecular or nanoscopic level. Complementary to ''bottom-up'' approaches, which construct supramolecular ensembles by the design and synthesis of functionalized small molecular units or large molecular motifs, nanofabrication explores whether individual units, such as small molecular ligands, or large molecules, such as proteins, can be positioned with nanometer precision. The separation and local environment can be engineered to control subsequent intermolecular interactions. Feature sizes as small as 2 ؋ 4 nm 2 (32 alkanethiol molecules) are produced. Proteins may be aligned along a 10-nm-wide line or within two-dimensional islands of desired geometry. These high-resolution engineering and imaging studies provide new and molecular-level insight into supramolecular chemistry and self-assembly processes in bioscience that are otherwise unobtainable, e.g., the influence of size, separation, orientation, and local environment of reaction sites. This nanofabrication methodology also offers a new strategy in construction of two-and three-dimensional supramolecular structures for cell, virus, and bacterial adhesion, as well as biomaterial and biodevice engineering. S upramolecular chemistry has become an area of intense research (1-4), partly inspired by biological ensembles in nature, such as collagen and enzymes or protein assemblies in general. In nature, the collective properties and biofunctionalities of these ensembles depend not only on the individual molecular units but also (perhaps even more importantly) on the organization at the molecular or nanoscopic level (1, 2, 4, 5). Such organization dependence can be attributed to polyvalent interactions in biological systems (6). ''Bottom-up'' approaches have been taken to mimic nature and have resulted in creative synthesis of small molecular units (7,8) and large molecular motifs (9). These molecular building blocks contain the desired charge, polarization, or chemical functionalities that will affect intermolecular interactions such as van der Waals forces, hydrogen bonding, polar attractions, and͞or hydrophobic interactions (7-9). These interactions dictate the subsequent assembly into supramolecular structures (4, 9-11). Complementary to these synthetic approaches, we explore whether individual units such as small molecular ligands or large molecules such as proteins can be positioned with nanometer precision by using nanoengineering methodologies. The separation and local environment can be engineered to influence subsequent intermolecular interactions.Micrometer-sized patterns of biomolecules can be produced by using relatively well known microfabrication technologies. Without using templates, DNA micropatterns may be directly produced by using photolithography (12)(13)(14). Micropatterns of proteins have also been ...

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Section: Precise Positioning Of Small Molecules and Proteins On Surfamentioning

confidence: 99%

Positioning protein molecules on surfaces: A nanoengineering approach to supramolecular chemistry

Liu

Amro

2002

Proc. Natl. Acad. Sci. U.S.A.

183

158

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“…[1][2][3][4][5][6] In particular, a great expectation was placed on the biological and biomedical applications of tubular nanomaterials. [7][8][9] As one of the most important materials of the carbon family, C 60 has many unique properties, such as, fluorescence and biological activities, [10][11][12] which makes it a potential functional material.…”

Section: Introductionmentioning

confidence: 99%

High pressure and high temperature induced polymerization of C60 nanotubes

Liu

Yao

et al. 2011

CrystEngComm

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. et al. (2011) High pressure and high temperature induced polymerization of C 60 nanotubes.CrysteEngComm, 13 (10) Abstract C 60 nanotubes with outer diameters ranging from 400 to 800nm were polymerized at 1.5 GPa, 573 K and 2.0 GPa, 700 K, respectively. Raman and photoluminescence (PL) spectroscopy were employed to characterize the polymeric phases of the treated samples. Both Raman and PL spectra showed that the C 60 nanotubes transformed into the dimer (D) and orthorhombic (O) phases under the two different conditions, respectively. The photoluminescence peaks were tuned from visible to near infrared range. Comparative studies indicated that C 60 nanotubes were more difficult to polymerize than bulk C 60 material under the same conditions due to the nanoscale size effect in the C 60 nanotubes.

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“…The rinsed tips were blown dry in filtered N 2 gas and cleaned with ozone for 5 min. AFM tips were coated with octadecanethiol (ODT) by vapor deposition [11] in a glass weighing bottle filled with 100 mg of ODT and heated to 60 ± C for 30 min. Fresh gold surfaces were prepared from mica-peeled gold [12], which provides reproducible polycrystalline surfaces with a roughness of ϳ0.2 nm rms.…”

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confidence: 99%

Thiol Diffusion and the Role of Humidity in “Dip Pen Nanolithography”

2002

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The radii of octadecanethiol spots deposited by an atomic force microscope tip onto a gold surface were studied as a function of contact time and humidity. The deposition is well described by twodimensional diffusion from an annular source of constant concentration, with a surface diffusion coefficient of 8400 nm 2 s 21 , independent of humidity. Facile transfer is observed even after near continuous deposition for more than 24 h in a dry N 2 environment, indicating that a water meniscus is not required. DOI: 10.1103/PhysRevLett.88.156104 PACS numbers: 68.37.Ps, 68.43.Jk, 81.16.Nd, 81.16.Rf Since the first use of alkanethiols by Nuzzo and Allara [1] to form a self-assembled monolayer (SAM) on a gold surface, the number of applications for thiolated hydrocarbons has increased rapidly [2], ranging from resists for electronics to biosensor substrates. The major advantages offered by thiol SAMs include long-term stability, versatility in terminal functionality, and ease of use. Perhaps the most attractive feature is their utility for forming small, reproducible surface features outside of a clean room. For example, facile creation of micron-scale patterns has been demonstrated by "stamping" thiols onto a surface using a flexible polymer master, a technique known as microcontact printing (mCP) [3]. Even smaller, nanometer-scale features can be patterned from thiols using the recently developed "Dip Pen Nanolithography" (DPN) [4], where alkanethiols are "written" via transfer from an atomic force microscope (AFM) tip to a surface. The prospect of nanometer-scale control over physical dimensions combined with the flexible terminal group chemistry makes thiol patterning a critical component of many proposed nanotechnologies.Because alkanethiol patterning is emerging as a key technique for nanofabrication, it is crucial that the mechanisms of deposition -and thereby the ultimate technological potential-be understood. The most important process of the deposition may be diffusion, which controls both the extent and the quality of an alkanethiol SAM. As previously noted in a study of mCP [5], the spatial resolution of a pattern is fundamentally limited by diffusion of the thiol "ink." First, diffusion of the thiol beyond the initial contact area causes the pattern to be wider than the stamp (for mCP) or the AFM tip terminus (for DPN). Although there have been a few attempts to measure the diffusion rate of thiols on gold [5][6][7][8], these measurements have been mostly phenomenological and thus have not reported diffusion coefficients. A second, more subtle, effect of diffusion is its role in the phase transition that occurs during SAM deposition: At a critical surface concentration, the adsorbed thiols reorient from a prone to a standing orientation. This change in orientation affects physical properties of the SAM, such as friction, as well as important chemical properties, such as its ability to mask the substrate from an etchant [9].Another important issue in determining the overall potential of DPN is the role of ...

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Multiple Ink Nanolithography: Toward a Multiple-Pen Nano-Plotter

Cited by 551 publications

References 30 publications

Positioning protein molecules on surfaces: A nanoengineering approach to supramolecular chemistry

Positioning protein molecules on surfaces: A nanoengineering approach to supramolecular chemistry

High pressure and high temperature induced polymerization of C60 nanotubes

Thiol Diffusion and the Role of Humidity in “Dip Pen Nanolithography”

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