New inexpensive way to grow silicon microwires for sensors, batteries and solar cells

New inexpensive way to grow silicon microwires for sensors, batteries and solar cells

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Molten droplets of copper, at top, dissolve silicon out of a surrounding silicon-rich gas, and then the silicon precipitates out at the bottom of the drop to gradually build up a silicon microwire. This microscope image has had color added for clarity. Image courtesy of Tonio Buonassisi

Microwires made of silicon -- tiny wires with a thickness comparable to a human hair — have a wide range of possible uses, including the production of solar cells that can harvest much more sunlight for a given amount of material than a conventional solar cell made from a thin wafer of silicon crystal. Now researchers from MIT and Penn State have found a way of producing such wires in quantity in a highly controlled way that could be scaled up to an industrial-scale process, potentially leading to practical commercial applications.

Other ways of making such wires are already known, and prototypes of solar cells made from them have been produced by several researchers. But these methods have serious limitations, says Tonio Buonassisi, MIT professor of mechanical engineering and a co-author of a paper on the new work that was recently published online in the journal Small, and will soon appear in the print edition. Most require several extra manufacturing steps, provide little control over the exact sizes and spacing of the wires, and only work on flat surfaces. By contrast, the new process is simple yet allows precise control over the wire dimensions and spacing, and could theoretically be done on any kind of curved, 3-D surface.

Microwires are thought to be capable of reaching efficiencies close to those of conventional solar cells in converting sunlight to electricity, but because the wires are so tiny they would do so using only a small fraction of the amount of expensive silicon needed for the conventional cells, thus potentially achieving major reductions in cost.

In addition to microwires’ potential use in solar cells, other researchers have proposed ways such microscopic wires could be used to build new kinds of transistors and integrated circuits, as well as electrodes for advanced batteries and certain kinds of environmental monitoring devices. For any of these ideas to be practical, however, there must be an efficient, scalable manufacturing method.

The new method involves heating and intentionally contaminating the surface of a silicon wafer with copper, which diffuses into the silicon. Then, when the silicon slowly cools, the copper diffuses out to form droplets on the surface. Then, when it is placed in an atmosphere of silicon tetrachloride gas, silicon microwires begin to grow outward wherever there is a copper droplet on the surface. Silicon in the gas dissolves into these copper droplets, and then after reaching a sufficient concentration begins to precipitate out at the bottom of the droplet, onto the silicon surface below. This buildup of silicon gradually elongates to form microwires each only about 10 to 20 micrometers (millionths of a meter) across, growing up from the surface. The whole process can be carried out repeatedly on an industrial manufacturing scale, Buonassisi says, or even could potentially be adapted to a continuous process.

The spacing of the wires is controlled by textures created on the surface — tiny dimples can form centers for the copper droplets — but the size of the wires is controlled by the temperatures used for the diffusion stage of the process. Thus, unlike in other production methods, the size and spacing of the wires can be controlled independently of each other, Buonassisi says.

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This new technique for growing microwires can produce strands that are very long in relation to their diameter. The rounded ?cap? at the wire?s top is a droplet of molten copper, while the wire itself is pure silicon. Image courtesy of Tonio Buonassisi

The work done so far is just a proof of principle, he says, and more work remains to be done to find the best combinations of temperature profiles, copper concentrations and surface patterning for various applications, since the process allows for orders-of-magnitude differences in the size of the wires. For example, it remains to be determined what thickness and spacing of wires produces the most efficient solar cells. But this work demonstrates a potential for a kind of solar cell based on such wires that could significantly lower costs, both by allowing the use of lower grades of silicon (that is, less-highly refined), since the process of wire growth helps to purify the material, and by using much smaller amounts of it, since the tiny wires are made up of just a tiny fraction of the amount needed for conventional silicon crystal wafers. “This is still in a very early stage,” Buonassisi says, because in deciding on a configuration for such a solar cell “there are so many things to optimize.”

Michael Kelzenberg, a postdoctoral scholar at the California Institute of Technology who has spent the last five years doing research on silicon microwires, says that while others have used the copper-droplet technique for growing microwires, “What's really new here is the method of producing those liquid metal droplets.” While others have had to place the droplets of molten copper on the silicon plate, requiring extra processing steps, “Buonassisi and his colleagues have shown that metal can be diffused into the growth substrate beforehand, and through careful heating and cooling, the metal droplets will actually form on their own — with the correct position and size.”

Kelzenberg adds that his research group has recently demonstrated that silicon microwire solar cells can equal the efficiency of today’s typical commercial solar cells. “I think the greatest challenge remaining is to show that this technique is more cost-effective or otherwise beneficial than other catalyst metal production methods,” he says. But overall, he says, some version of silicon microwire technology “has the potential to enable dramatic cost reductions” of solar panels.

The paper was co-authored by Vidya Ganapati ’10, doctoral student David Fenning, postdoctoral fellow Mariana Bertoni, and research specialist Alexandria Fecych, all in MIT’s Department of Mechanical Engineering, and postdoctoral researcher Chito Kendrick and Professor Joan Redwing of Pennsylvania State University. The work was supported by the U.S. Department of Energy, the Chesonis Family Foundation and the National Science Foundation.

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This story is republished courtesy of MIT News (http://web.mit.edu/newsoffice/), a popular site that covers news about MIT research, innovation and teaching.

Better batteries from the bottom up

Better batteries from the bottom up

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A nanostructured lithium ion battery developed at Rice University may charge faster and last longer than Li ion batteries in current use. Nanowires with a PMMA polymer coating, seen in a transmission electron microscope image at right, solve a long-standing problem of forming ultrathin electrolyte layers around nanostructured electrode materials. (Credit: Ajayan Lab/Rice University)

(PhysOrg.com) -- Rice University researchers have moved a step closer to creating robust, three-dimensional microbatteries that would charge faster and hold other advantages over conventional lithium-ion batteries. They could power new generations of remote sensors, display screens, smart cards, flexible electronics and biomedical devices.

The batteries employ vertical arrays of nickel-tin nanowires perfectly encased in PMMA, a widely used polymer best known as Plexiglas. The Rice laboratory of Pulickel Ajayan found a way to reliably coat single nanowires with a smooth layer of a PMMA-based gel electrolyte that insulates the wires from the counter electrode while allowing ions to pass through.

The work was reported this week in the online edition of the journal Nano Letters.

"In a battery, you have two electrodes separated by a thick barrier," said Ajayan, professor in mechanical engineering and materials science and of chemistry. "The challenge is to bring everything into close proximity so this electrochemistry becomes much more efficient."

Ajayan and his team feel they've done that by growing forests of coated nanowires -- millions of them on a fingernail-sized chip -- for scalable microdevices with greater surface area than conventional thin-film batteries. "You can't simply scale the thickness of a thin-film battery, because the lithium ion kinetics would become sluggish," Ajayan said.

"We wanted to figure out how the proposed 3-D designs of batteries can be built from the nanoscale up," said Sanketh Gowda, a graduate student in Ajayan's lab. "By increasing the height of the nanowires, we can increase the amount of energy stored while keeping the lithium ion diffusion distance constant."

The researchers, led by Gowda and postdoctoral researcher Arava Leela Mohana Reddy, worked for more than a year to refine the process.

"To be fair, the 3-D concept has been around for a while," Reddy said. "The breakthrough here is the ability to put a conformal coat of PMMA on a nanowire over long distances. Even a small break in the coating would destroy it." He said the same approach is being tested on nanowire systems with higher capacities.

The process builds upon the lab's previous research to build coaxial nanowire cables that was reported in Nano Letters last year. In the new work, the researchers grew 10-micron-long nanowires via electrodeposition in the pores of an anodized alumina template. They then widened the pores with a simple chemical etching technique and drop-coated PMMA onto the array to give the nanowires an even casing from top to bottom. A chemical wash removed the template.

They have built one-centimeter square microbatteries that hold more energy and that charge faster than planar batteries of the same electrode length. "By going to 3-D, we're able to deliver more energy in the same footprint," Gowda said.

They feel the PMMA coating will increase the number of times a battery can be charged by stabilizing conditions between the nanowires and liquid electrolyte, which tend to break down over time.

The team is also studying how cycling affects nanowires that, like silicon electrodes, expand and contract as lithium ions come and go. Electron microscope images of nanowires taken after many charge/discharge cycles showed no breaks in the PMMA casing -- not even pinholes. This led the researchers to believe the coating withstands the volume expansion in the electrode, which could increase the batteries' lifespans.

Bad virus put to good use: Breakthrough batteries

Bad virus put to good use: Breakthrough batteries

December 7, 2010 By Melissa Corley

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SEM images of nickel-coated TMV arrays patterned using photolithography onto a silicon wafer Credit: University of Maryland, College Park

(PhysOrg.com) -- Viruses have a bad rep--and rightly so. The ability of a virus to quickly and precisely replicate itself makes it a destructive scourge to animals and plants alike. Now an interdisciplinary team of researchers at the University of Maryland's A. James Clark School of Engineering and College of Agriculture and Natural Resources, brought together by Professor Reza Ghodssi, is turning the tables, harnessing and exploiting the "self-renewing" and "self-assembling" properties of viruses for a higher purpose: to build a new generation of small, powerful and highly efficient batteries and fuel cells.

The rigid, rod-shaped Tobacco mosaic virus (TMV), which under an electron microscope looks like uncooked spaghetti, is a well-known and widespread plant virus that devastates tobacco, tomatoes, peppers, and other vegetation. But in the lab, engineers have discovered that they can harness the characteristics of TMV to build tiny components for the lithium ion batteries of the future. They can modify the TMV rods to bind perpendicularly to the metallic surface of a battery electrode and arrange the rods in intricate and orderly patterns on the electrode. Then, they coat the rods with a conductive thin film that acts as a current collector and finally the battery's active material that participates in the electrochemical reactions.

As a result, the researchers can greatly increase the electrode surface area and its capacity to store energy and enable fast charge/discharge times. TMV becomes inert during the manufacturing process; the resulting batteries do not transmit the virus. The new batteries, however, have up to a 10-fold increase in energy capacity over a standard lithium ion battery.

"The resulting batteries are a leap forward in many ways and will be ideal for use not only in small electronic devices but in novel applications that have been limited so far by the size of the required battery," said Ghodssi, director of the Institute for Systems Research and Herbert Rabin Professor of Electrical and Computer Engineering at the Clark School. "The technology that we have developed can be used to produce energy storage devices for integrated microsystems such as wireless sensors networks. These systems have to be really small in size--millimeter or sub-millimeter--so that they can be deployed in large numbers in remote environments for applications like homeland security, agriculture, environmental monitoring and more; to power these devices, equally small batteries are required, without compromising in performance."

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TMV's nanostructure is the ideal size and shape to use as a template for building battery electrodes. Its self-replicating and self-assembling biological properties produce structures that are both intricate and orderly, which increases the power and storage capacity of the batteries that incorporate them. Because TMV can be programmed to bind directly to metal, the resulting components are lighter, stronger and less expensive than conventional parts.

Three distinct steps are involved in producing a TMV-based battery: modifying, propagating and preparing the TMV; processing the TMV to grow nanorods on a metal plate; and incorporating the nanorod-coated plates into finished batteries. It takes an interdisciplinary team of UM scientists and their students to make each step possible.

James Culver, a member of the Institute for Bioscience and Biotechnology and a professor in the Department of Plant Science and Landscape Architecture, and researcher Adam Brown had already developed genetic modifications to the TMV that enable it to be chemically coated with conductive metals. For this project they extract enough of the customized virus from just a few tobacco plants grown in the lab to synthesize hundreds of battery electrodes. The extracted TMV is then ready for the next step.

Scientists produce a forest of vertically aligned virus rods using a process developed by Culver's former Ph.D. student, Elizabeth Royston. A solution of TMV is applied to a metal electrode plate. The genetic modifications program one end of the rod shaped virus to attach to the plate. Next these viral forests are chemically coated with a conductive metal, mainly nickel. Other than its structure, no trace of the virus is present in the finished product, which cannot transmit a virus to either plants or animals. This process is patent-pending.

Ghodssi, materials science Ph.D. student Konstantinos Gerasopoulos, and former postdoctoral associate Matthew McCarthy (now a faculty member at Drexel University) have used this metal-coating technique to fabricate alkaline batteries with common techniques from the semiconductor industry such as photolithography and thin film deposition.

While the first generation of their devices used the nickel-coated viruses for the electrodes, work published earlier this year investigated the feasibility of structuring electrodes with the active material deposited on top of each nickel-coated nanorod, forming a core/shell nanocomposite where every TMV particle contains a conductive metal core and an active material shell. In collaboration with Chunsheng Wang, a professor in the Department of Chemical and Biomolecular Engineering, and his Ph.D. student Xilin Chen, the researchers have developed several techniques to form nanocomposites of silicon and titanium dioxide on the metalized TMV template. This architecture both stabilizes the fragile, active material coating and provides it with a direct connection to the battery electrode.

In the third and final step, Chen and Gerasopoulos assemble these electrodes into the experimental high-capacity lithium-ion batteries. Their capacity can be several times higher than that of bulk materials and in the case of silicon, higher than that of current commercial batteries.

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SEM image of Ni/TiO2 nanocomposite electrode (top), cross-section TEM image of an individual nanorod showing the core/shell nanostructure Credit: University of Maryland, College Park

"Virus-enabled nanorod structures are tailor-made for increasing the amount of energy batteries can store. They confer an order of magnitude increase in surface area, stabilize the assembled materials and increase conductivity, resulting in up to a10-fold increase in the energy capacity over a standard lithium ion battery," Wang said.

A bonus: since the TMV binds metal directly onto the conductive surface as the structures are formed, no other binding or conducting agents are needed as in the traditional ink-casting technologies that are used for electrode fabrication.

"Our method is unique in that it involves direct fabrication of the electrode onto the current collector; this makes the battery's power higher, and its cycle life longer," said Wang.

The use of the TMV virus in fabricating batteries can be scaled up to meet industrial production needs. "The process is simple, inexpensive, and renewable," Culver adds. "On average, one acre of tobacco can produce approximately 2,100 pounds of leaf tissue, yielding approximately one pound of TMV per pound of infected leaves," he explains.

At the same time, very tiny microbatteries can be produced using this technology. "Our electrode synthesis technique, the high surface area of the TMV and the capability to pattern these materials using processes compatible with microfabrication enable the development of such miniaturized batteries," Gerasopoulos adds.

While the focus of this research team has long been on energy storage, the structural versatility of the TMV template allows its use in a variety of exciting applications. "This combination of bottom-up biological self-assembly and top-down manufacturing is not limited to battery development only," Ghodssi said. "One of our lab's ongoing projects is aiming at the development of explosive detection sensors using versions of the TMV that bind TNT selectively, increasing the sensitivity of the sensor. In parallel, we are collaborating with our colleagues at Drexel and MIT to construct surfaces that resemble the structure of plant leaves. These biomimetic structures can be used for basic scientific studies as well as the development of novel water-repellent surfaces and micro/nano scale heat pipes."