With a simple coating, nanowires show a dramatic increase in efficiency and sensitivity

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This is a close-up view of a coated nanowire. Credit: Courtesy of Ken Crozier, Harvard School of Engineering and Applied Sciences.

By applying a coating to individual silicon nanowires, researchers at Harvard and Berkeley have significantly improved the materials' efficiency and sensitivity.

The findings, published in the May 20, 2011, issue of Nano Letters, suggest that the coated wires hold promise for photodetectors and energy harvesting technologies like solar cells.

Due to a large surface-to-volume ratio, nanowires typically suffer from a high surface recombination rate, meaning that photogenerated charges recombine rather than being collected at the terminals. The carrier lifetime of a basic nanowire is shortened by four to five orders of magnitude, reducing the material's efficiency in applications like solar cells to a few percent.

"Nanowires have the potential to offer high energy conversion at low cost, yet their limited efficiency has held them back," says Kenneth Crozier, Associate Professor of Electrical Engineering at the Harvard School of Engineering and Applied Sciences (SEAS).

With their latest work, Crozier and his colleagues demonstrated what could be promising solution. Making fine-precision measurements on single nanowires coated with an amorphous silicon layer, the team showed a dramatic reduction in the surface recombination.

Surface passivation has long been used to promote efficiency in silicon chips. Until now, surface passivation of nanowires has been explored far less.

The creation of the coating that passivated the surfaces of the nanowires was a happy accident. During preparation of a batch of single-crystal silicon nanowires, the scientists conjecture, the small gold particles used to grow the nanowires became depleted. As a result, they think, the amorphous silicon coating was simply deposited onto the individual wires.

Instead of abandoning the batch, Crozier and his team decided to test it. Scanning photocurrent studies indicated, astoundingly, almost a hundred-fold reduction in surface recombination. Overall, the coated wires boasted a 90-fold increase in photosensitivity compared to uncoated ones.

Co-author Yaping Dan, a postdoctoral fellow in Crozier's lab who spearheaded the experiments, suggests that the reason for the increased efficiency is that the coating physically extends the broken atom bonds at the single-crystalline silicon surface. At the same time, the coating also may form a high?electric potential barrier at the interface, which confines the photogenerated charge carriers inside the single-crystalline silicon.

"As far as we know, scientists have not done these types of precision measurements of surface passivation at the level of single nanowires," says Crozier. "Simply by putting a thin layer of amorphous silicon onto a crystalline silicon nanowire reduces the surface recombination nearly two orders of magnitude. We think the work will address some of the disadvantages of nanowires but keep their advantages."

Due to their increased carrier lifetime, the researchers expect that their wires will offer higher energy conversion efficiency when used in solar cell devices.

Provided by Harvard University (news : web)

Nanowires exhibit giant piezoelectricity

Nanowires exhibit giant piezoelectricity

Gallium nitride (GaN) and zinc oxide (ZnO) are among the most technologically relevant semiconducting materials. Gallium nitride is ubiquitous today in optoelectronic elements such as blue lasers (hence the blue-ray disc) and light-emitting-diodes (LEDs); zinc oxide also finds many uses in optoelectronics and sensors.

In the past few years, though, nanostructures made of these materials have shown a plethora of potential functionalities, ranging from single-nanowire lasers and LEDs to more complex devices such as resonators and, more recently, nanogenerators that convert mechanical energy from the environment (body movements, for example) to power electronic devices. The latter application relies on the fact that GaN and ZnO are also piezoelectric materials, meaning that they produce electric charges as they are deformed.

In a paper published online in the journal Nano Letters, Horacio Espinosa, the James N. and Nancy J. Farley Professor in Manufacturing and Entrepreneurship at the McCormick School of Engineering and Applied Science at Northwestern University, and Ravi Agrawal, a graduate student in Espinosa's lab, reported that piezoelectricity in GaN and ZnO nanowires is in fact enhanced by as much as two orders of magnitude as the diameter of the nanowires decrease.

"This finding is very exciting because it suggests that constructing nanogenerators, sensors and other devices from smaller nanowires will greatly improve their output and sensitivity," Espinosa said.

"We used a computational method called Density Functional Theory (DFT) to model GaN and ZnO nanowires of diameters ranging from 0.6 nanometers to 2.4 nanometers," Agrawal said. The computational method is able to predict the electronic distribution of the nanowires as they are deformed and, therefore, allows calculating their piezoelectric coefficients.

The researchers' results show that the piezoelectric coefficient in 2.4 nanometer-diameter nanowires is about 20 times larger and about 100 times larger for ZnO and GaN nanowires, respectively, when compared to the coefficient of the materials at the macroscale. This confirms previous computational findings on ZnO nanostructures that showed a similar increase in piezoelectric properties. However, calculations for piezoelectricity of GaN nanowires as a function of size were carried out in this work for the first time, and the results are clearly more promising as GaN shows a more prominent increase.

"Our calculations reveal that the increase in piezoelectric coefficient is a result of the redistribution of electrons in the nanowire surface, which leads to an increase in the strain-dependent polarization with respect to the bulk materials," Espinosa said.

The findings by Espinosa and Agrawal may have important implications for the field of energy harvesting as well as for fundamental science. For energy harvesting, where piezoelectric elements are used to convert mechanical to electrical energy in order to power electronic devices, these results point to an advantage in reducing the size of the piezoelectric elements down to the nanometer scale. Energy harvesting devices built from small-diameter nanowires should in principle be able to produce more electrical energy from the same amount of mechanical energy than their bulk counterparts.

In terms of fundamental science, these results further previous conclusions that matter at the nanoscale has different properties. It is clear now that by tailoring the size of nanostructures, their mechanical, electrical and thermal properties can be tuned as well.

"Our focus remains on understanding the fundamental principles governing the behavior of nanostructures as a function of their size," Espinosa and Agrawal say. "One of the most important issues that needs to be addressed is to obtain experimental confirmation of these results, and establish up to what size the giant piezoelectric effects remain significant."

Espinosa and Agrawal hope their work will spur new interest in the electromechanical properties of nanostructures, both from theoretical and experimental standpoints, in order to clear the path for the design and optimization of future nanoscale devices.

Coiled nanowires may hold key to stretchable electronics

Coiled nanowires may hold key to stretchable electronics

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Zhu's research team has created the first coils of silicon nanowire on a substrate that can be stretched to more than double their original length, moving us closer to developing stretchable electronic devices. Credit: Yong Zhu, North Carolina State University

Researchers at North Carolina State University have created the first coils of silicon nanowire on a substrate that can be stretched to more than double their original length, moving us closer to incorporating stretchable electronic devices into clothing, implantable health-monitoring devices, and a host of other applications.

"In order to create stretchable electronics, you need to put electronics on a stretchable substrate, but electronic materials themselves tend to be rigid and fragile," says Dr. Yong Zhu, one of the researchers who created the new nanowire coils and an assistant professor of mechanical and aerospace engineering at NC State. "Our idea was to create electronic materials that can be tailored into coils to improve their stretchability without harming the electric functionality of the materials."

Other researchers have experimented with "buckling" electronic materials into wavy shapes, which can stretch much like the bellows of an accordion. However, Zhu says, the maximum strains for wavy structures occur at localized positions – the peaks and valleys – on the waves. As soon as the failure strain is reached at one of the localized positions, the entire structure fails.

"An ideal shape to accommodate large deformation would lead to a uniform strain distribution along the entire length of the structure – a coil spring is one such ideal shape," Zhu says. "As a result, the wavy materials cannot come close to the coils' degree of stretchability." Zhu notes that the coil shape is energetically favorable only for one-dimensional structures, such as wires.

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Here you can see multiple images of the silicon nanocoil as it is being stretched. Credit: Yong Zhu, North Carolina State University

Zhu's team put a rubber substrate under strain and used very specific levels of ultraviolet radiation and ozone to change its mechanical properties, and then placed silicon nanowires on top of the substrate. The nanowires formed coils upon release of the strain. Other researchers have been able to create coils using freestanding nanowires, but have so far been unable to directly integrate those coils on a stretchable substrate.

While the new coils' mechanical properties allow them to be stretched an additional 104 percent beyond their original length, their electric performance cannot hold reliably to such a large range, possibly due to factors like contact resistance change or electrode failure, Zhu says. "We are working to improve the reliability of the electrical performance when the coils are stretched to the limit of their mechanical stretchability, which is likely well beyond 100 percent, according to our analysis."

Coiled nanowires may hold key to stretchable electronics

Coiled nanowires may hold key to stretchable electronics

Enlarge

Zhu's research team has created the first coils of silicon nanowire on a substrate that can be stretched to more than double their original length, moving us closer to developing stretchable electronic devices. Credit: Yong Zhu, North Carolina State University

Researchers at North Carolina State University have created the first coils of silicon nanowire on a substrate that can be stretched to more than double their original length, moving us closer to incorporating stretchable electronic devices into clothing, implantable health-monitoring devices, and a host of other applications.

"In order to create stretchable electronics, you need to put electronics on a stretchable substrate, but electronic materials themselves tend to be rigid and fragile," says Dr. Yong Zhu, one of the researchers who created the new nanowire coils and an assistant professor of mechanical and aerospace engineering at NC State. "Our idea was to create electronic materials that can be tailored into coils to improve their stretchability without harming the electric functionality of the materials."

Other researchers have experimented with "buckling" electronic materials into wavy shapes, which can stretch much like the bellows of an accordion. However, Zhu says, the maximum strains for wavy structures occur at localized positions – the peaks and valleys – on the waves. As soon as the failure strain is reached at one of the localized positions, the entire structure fails.

"An ideal shape to accommodate large deformation would lead to a uniform strain distribution along the entire length of the structure – a coil spring is one such ideal shape," Zhu says. "As a result, the wavy materials cannot come close to the coils' degree of stretchability." Zhu notes that the coil shape is energetically favorable only for one-dimensional structures, such as wires.

Enlarge

Here you can see multiple images of the silicon nanocoil as it is being stretched. Credit: Yong Zhu, North Carolina State University

Zhu's team put a rubber substrate under strain and used very specific levels of ultraviolet radiation and ozone to change its mechanical properties, and then placed silicon nanowires on top of the substrate. The nanowires formed coils upon release of the strain. Other researchers have been able to create coils using freestanding nanowires, but have so far been unable to directly integrate those coils on a stretchable substrate.

While the new coils' mechanical properties allow them to be stretched an additional 104 percent beyond their original length, their electric performance cannot hold reliably to such a large range, possibly due to factors like contact resistance change or electrode failure, Zhu says. "We are working to improve the reliability of the electrical performance when the coils are stretched to the limit of their mechanical stretchability, which is likely well beyond 100 percent, according to our analysis."