New Family of Tiny Crystals Glow Bright in LED Lights

JUNE 7, 2013

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Laue microdiffraction pattern acquired from a nanoribbon in experiments at the APS.

Minuscule crystals that glow different colors may be the missing ingredient for white light-emitting diode (LED) lighting that illuminates homes and offices as effectively as natural sunlight. So say researchers who studied europium aluminate nanocrystals using four x-ray beamlines at the U.S. Department of Energy Office of Science’s Advanced Photon Source (APS).

Light-emitting diodes offer substantial energy savings over incandescent and fluorescent lights and are easily produced in single colors such as red or green commonly used in traffic lights or children's toys.

Developing an LED that emits a broad spectrum of warm white light on par with sunlight has proven tricky, however. LEDs, which produce light by passing electrons through a semiconductor material, often are coupled with materials called phosphors that glow when excited by ultraviolet radiation from the LED.

"But it's hard to get one phosphor that makes the broad range of colors needed to replicate the sun," said John Budai, a scientist in Oak Ridge National Laboratory's (ORNL’s) Materials Science and Technology Division. "One approach to generating warm-white light is to hit a mixture of phosphors with ultraviolet radiation from an LED to stimulate many colors needed for white light."

Budai is working with a team of scientists from the University of Georgia (UGA), ORNL, and Argonne National Laboratory to understand a new group of crystals that might yield the right blend of colors for white LEDs as well as other uses. Zhengwei Pan's group at UGA grew the nanocrystals using europium oxide and aluminum oxide powders as the source materials because the rare-earth element europium is known to be a dopant, or additive, with good phosphorescent properties.

"What's amazing about these compounds is that they glow in lots of different colors—some are orange, purple, green or yellow," Budai said. "The next question became: Why are they different colors? It turns out that the atomic structures are very different."

The group has been studying the atomic structure of the materials using high-brightness x-rays from the Argonne APS in order to work out how the atoms are arranged in each of the different crystal types. The different-colored phosphors exhibit distinct diffraction patterns when they are hit with x-rays, enabling the researchers to analyze the crystal structure.

Argonne X-ray Science Division beamline 11-BM-B was utilized for x-ray powder diffraction experiments, 20-BM-B for x-ray absorption near edge structure spectroscopy measurements, and 34-ID-E for polychromatic Laue microdiffraction studies from individual nanocrystals. Most recently, the group has collected micro-crystallography data at ChemMatCARS beamline 15-ID-B, also at the APS, in order to refine the detailed atomic positions in the different phosphors.

Two of the three types of crystal structures in the group of phosphors had never been seen before, which can probably be attributed to the crystals' small size, Budai said.

"Only the green ones were a known crystal structure," Budai said. "The other two, the yellow and blue, don't grow in big crystals; they only grow with these atomic arrangements in these tiny nanocrystals. That's why they have different photoluminescent properties."

"What that means in terms of how the electrons around the atoms interact to make light is much harder," Budai said. "We haven't completely solved that yet. That's the continuing research. We have a lot of clues, but we don't know everything."

The knowledge gained through their atomic-scale analysis is helping the research team improve the phosphorescent crystals. Different factors in the growth process—temperature, powder composition, and types of gas used—can change the final product. A fundamental understanding of all the parameters could help the team to perfect the recipe and improve the crystals' ability to convert energy into light.

Advancing the material's luminescence efficiency is the key to making it useful for commercial LED products and other applications; the new nanocrystals may turn out to have other practical photonic uses beyond phosphors for LEDs. Their ability to act as miniature "light pipes" when the crystal quality is high enough could lend them to applications in fiber-optic technologies, Budai said.

"You can keep growing the crystals and measuring them, or you can understand why it's doing what it's doing, and figure out how to make it better. That's what we're doing—basic research. We have to figure out nature first."

See: Feng Liu1, John D. Budai2, Xufan Li1, Jonathan Z. Tischler2, Jane Y. Howe2, Chengjun Sun3, Richard S. Meltzer1, and Zhengwei Pan1*, "New Ternary Europium Aluminate Luminescent Nanoribbons for Advanced Photonics," Adv. Funct. Mater. 23 (16), 1998-2006 (2013). DOI:10.1002/adfm.201202539

Author affiliations: 1University of Georgia, 2Oak Ridge National Laboratory, 3Argonne National Laboratory

Correspondence: *panz@uga.edu

Z.W.P. acknowledges funding support from the National Science Foundation (CAREER DMR-0955908). J.D.B. and J.Z.T. were supported by the Materials Sciences and Engineering Division, Basic Energy Sciences Program, U.S. Department of Energy Office of Science. ChemMatCARS is mainly supported by the National Science Foundation/Department of Energy under grant number NSF/CHE-0822838. Sector 20 beamlines are supported by the U.S. Department of Energy (DOE) Basic Energy Sciences, a Major Resources Support grant from the Natural Sciences and Engineering Research Council of Canada, the University of Washington, the Canadian Light Source, and the Advanced Photon Source. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy Office of Science under Contract No. DE-AC02-06CH11357.

The original ORNL press release by Morgan McCorkle can be found here.

The Advanced Photon Source at Argonne National Laboratory is one of five national synchrotron radiation light sources supported by the U.S. Department of Energy’s Office of Science to carry out applied and basic research to understand, predict, and ultimately control matter and energy at the electronic, atomic, and molecular levels, provide the foundations for new energy technologies, and support DOE missions in energy, environment, and national security. To learn more about the Office of Science x-ray user facilities, visit http://science.energy.gov/user-facilities/basic-energy-sciences/.

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