History of Nanotechnology

History of Nanomaterials: From Prehistory to the Modern Age

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Although we may think of nanotechnology as a contemporary subject, the use of nanomaterials in human objects and paraphernalia can be traced back to ancient times.

Prehistoric use of nanomaterials can be traced back to Egypt, Indonesia and China. In ancient Egypt, the soot of oil lamps was used to make black pigments for writing on papyrus. Around the time of 2575 BC, the Egyptians were already producing the synthetic pigment Egyptian blue.

As a scientific subject ‘nanoscience’ began with the ancient Greeks. Indeed, the word nano is Greek for “dwarf.” In the fifth century BC, the philosopher Democritus, nowadays best known for the atomic theory of the universe, questioned whether matter was continuous and could be infinitely divided into smaller and smaller pieces, or alternatively made up of tiny, indivisible particles.

Roman artifacts from the fourth century BC containing nanoparticles can nowadays be observed in the British Museum. In the Americans, nanomaterials were used by advanced Mayan civilisations. Maya Blue was fabricated in the city of Chichen Itza in 800 AD. It is a brightly coloured azure pigment and a composite of nanomaterials comprising indigo dye combined (chemically) with clay nanopores. This combination renders the dye resistant to corrosion.

Between the 9^th and 17^th centuries AD, glimmering ceramic glazes were used in Islamic countries. During the 10^th century cementite nanowires and carbon nanotubes were used to give strength to wootz steel produced in India. In medieval Europe, nanoparticles were widely used to make stained-glass windows and in 16^th century Italy they were used in Renaissance pottery. Meanwhile, between the 13^th and 18^th centuries Ottoman techniques were used to produce “Damascus” steel blades containing carbon nanotubes.

Faraday Experiments with Nanoparticles

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In 1857 in a basement laboratory at the Royal Institution, London, physicist Michael Faraday mounted gold leaves onto microscope slides and, in what was an accidental discovery, he noticed a ruby coloured liquid upon washing them. The change in expected colour was due to the small size of the particles in solution. The finding led him to experiment further with the dispersion of gold nanoparticles suspended in liquid, subsequently producing different-coloured solutions under certain lighting conditions. Gold nanoparticles are an area of great interest in many areas of research, such as in cancer treatment. Gold nanoparticle size can be easily characterized by their absorbance profile, which can be measured using simple UV-Vis spectroscopy.

Tools of Nanotechnology in the Twentieth Century

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To visualise nanoparticles and better manipulate their characteristics, modern microscopy has proven crucial to the progress of nanotechnology. The twentieth century witnessed monumental developments in microscopical technology.

The traditional light microscope has been around since the 17^th century. By the early 20^th century, it had reached the theoretical limit of resolution ––around the width of a human hair strand. To surmount the limitations, a new kind of microscope was invented; one that used electrons instead of light.

Transmission Electron Microscope (TEM)

In 1931 Ernst Ruska and Max Knoll invented the Transmission Electron Microscope (and later won the Nobel Prize). This microscope promised to resolve matter to the atomic level of detail. At least in theory. But in practice, the TEM was constrained by the tools and techniques associated with its use, as well as by its own design. The microscope has since evolved. In 1991, Sumio Iijima and colleagues were able to visualise graphitic tubes or carbon nanotubes using TEM.

Scanning Tunnel Microscope (STM)

In 1981 two scientists, Gerd Binnig and Heinrich Rohrer, working at the IBM Zurich Research Laboratory, invented the Scanning Tunnel Microscope. The advent of STM enabled scientists and engineers to visualise and manipulate atoms. In 1986 Binnig and Rohrer won the Nobel Prize in physics. Later on, in 1990 Don Eigler and Erhad Schweizer, also both working at IBM, used STM to manipulate individual xenon atoms on a single-crystal nickel surface to create the “IBM” logo.

Atomic Force Microscope (AFM)

The advent of the STM in turn led to another new kind of instrument, the Atomic Force Microscope. AFM is used to scan nanostructures with a probe equipped with nanometre- wide tip. Movement is directed by atomic forces between the surface of the tip and the sample.

As demonstrated by Faraday, the properties of nanoparticles can differ from those at larger scales. There are two underlying reasons why this occurs:

1. Nanomaterials have a larger surface area comparative to the same mass of materials produced in a larger form. Materials are more chemically reactive at the nanoscale, which effects their strength and electrical properties. This applies even to materials that are inert in larger forms.
2. Quantum effects come into play at the nanoscale affecting the optical, electrical, and magnetic behaviour of materials.

The Age of Nanotechnology from Feynman to Nano-fabrication

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Feynman the Father of Nanotechnology

Richard Feynman is considered the father of modern nanotechnology. The American physicist and Nobel Prize laureate first introduced the idea of nanotechnology in 1959. At the annual meeting of the American Physical Society held at the California Institute of Technology (Caltech), Feynman presented the lecture “There’s Plenty of Room at the Bottom.” Here he conjectured on the notion of using machines to make smaller machines all down to the molecular level. Although seemingly fantastical at the time, Feynman asked: “why can’t we write the entire 24 volumes of the Encyclopaedia Britannica on the head of a pin?” The speech coincided with the advent of the integrated circuit spurring progress in computing.

Taniguchi Coins Term Nanotechnology

In 1974, Norio Taniguchi, a Japanese scientist based at the Tokyo Science University, Japan, presented a paper to the Society of Precision Engineering titled “On the Basic Concept of Nanotechnology.” Here he talked about the ability to engineer materials at nanometer levels. In the 1970s, electron beam lithography was in use at IBM, creating nanostructures and devices in the 40-70 nm range. The discovery of silicon microchips was the major driving force toward miniaturisation came from the electronics industry and a push for smaller, faster and more complex electronic devices.

Drexler and the Coming Era of Nanotechnology

With the advent of STM, the modern era of nanotechnology was truly underway. In 1986, MIT trained engineer K. Eric Drexler published the first book on nanotechnology “Engines of Creation: The Coming Era of Nanotechnology.” It led to the theory of “molecular engineering” becoming more widely known. Drexler also warned of the negatives of nanotechnology by discussing concepts like autonomous self-replication, which he called “grey-goo.” Later books on nanotechnology have continued to explore similar such ideas like that of the technological singularity, first conceived of by John von Neumann.

Building on biological principles

Much progress in nanotechnology has been inspired by the science of molecular biology. The natural processes involved in building and assembling biological structures involve a so-called ‘bottom-up’ approach. Biological materials like proteins, which made up of find individual monomeric particles called amino acids, are synthesised in a process involving the ‘molecular machines’ of the cell.

The development of nanotechnology has adopted this bottom-up approach, inspired by biological processes, in addition to an oppositely oriented ‘top-down’ approach, in which larger materials are broken down into smaller nanoparticles. The mini table given below gives examples of how material technological objects and functions have been founded on the biological principles of cellular life (table 1).

Table 1: Comparison between macroscopic and microscopic components.

Technology	Function	Molecular example
Struts, beams, casings	Transmit force, hold position	Microtubules, cellulose
Pumps	Move, fluids	Flagella, membrane proteins
Production lines	Construct devices	Enzyme systems, ribosomes

Source: Drexler, 1981, p. 5276.

In 1991, Drexler, Peterson and Pergamit published “Unbounding the Future: the Nanotechnology Revolution” in which they used the terms “nanobots” or “assemblers” for nano-processes in medical applications. This helped spur the rise of nanomedicine. Meanwhile nanoscience, in general, recieved generous investment in the 1990s. This buoyancy led to revolutionary new discoveries such as the existence of carbon nanotubes, for example. The ability to construct products with molecular precision revolutionised manufacturing. By the 2000s, nanomaterials were being used in consumer products such as wearable devices and clothing materials.

Modern fabrication techniques used in both nanoscience and technology involve:

• Thin film fabrication
• Lithography
• Engraving

The term encompassing the use of techniques at nanoscale depths is nanofabrication. Alternately, the term “supertechnology” is used and sometimes “extreme technology.” Manipulating materials at the nanoscale level has led to advances in efficiency and durability not realisable with traditional techniques. Devices and products can now be made much smaller, more lightweight and more flexible and this progress touches upon a range of industries from nanomedicine to microelectronics.

In the 21^st century, nanotechnology is a truly interdisciplinary pursuit touching nearly every field of science, including, but not limited to, physics, materials science, chemistry, biology, computer science and engineering. The above given definitions of nanoscience and nanotechnology were thus devised to reflect the interdisciplinary nature of these still emerging fields.

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References

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1. Ahire, S. A., et al. (2022) The Augmentation of nanotechnology era: A concise review on fundamental concepts of nanotechnology and applications in material science and technology. Results in Chemistry, 4, 100633. Doi: 10.1016/j.rechem.2022.100633.
2. Barhoum A, et al. (2022). Review on Natural, Incidental, Bioinspired, and Engineered Nanomaterials: History, Definitions, Classifications, Synthesis, Properties, Market, Toxicities, Risks, and Regulations. Nanomaterials, 12, (2): 177. Doi: 10.3390/nano12020177.
3. Bayda S. et al. (2019) The History of Nanoscience and Nanotechnology: From Chemical-Physical Applications to Nanomedicine. Molecules. 25 (1):112. Doi: 10.3390/molecules25010112.

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