PHOTO: John Dominis/Time & Life
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ZnO TO THE RESCUE: Zinc oxide absorbs and can emit ultraviolet light.
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High-definition DVD movies and players based on blue
lasers have only just arrived on the market, but already
a new generation is in sight, promising another fivefold
increase in storage density. First-generation discs
relying on red lasers could store about 5 gigabytes of
data, and blue lasers have taken that to 50 GB. But if
disc-player laser wavelengths could be pushed down into
the ultraviolet part of the spectrum, disc densities
could be hiked up to as much as 250 GB.
Brilliantly white light-emitting diodes also could be
made from UV devices, accelerating replacement of
inefficient incandescent lightbulbs and dull compact
fluorescents by LEDs. A practical deep-ultraviolet LED
would be especially valuable because “if you have UV,
you can excite anything in the visible,” says David
Look, director of the semiconductor research center at
Wright State University, in Dayton, Ohio. “You could
have pure red, blue, and green phosphors. Then you
excite them in any proportion to get any color.”
The key to making UV-emitting devices is likely to be
zinc oxide: it’s a better material than gallium nitride
for making these devices, because it naturally emits
(and absorbs) at those wavelengths more efficiently [see
photo, “ZnO to the Rescue”]. Plus it is cheap and
abundant—zinc is used in drugs and sunscreens—and is
easy to grow into wafers that are virtually defect-free.
Gallium nitride, apart from being expensive and harder
to grow, emits closer to blue in practice; many of the
LEDs made from gallium nitride that are on the market
today and claim to be UV really are operating more in
the deep violet region of 350 to 370 nanometers.
The main hurdle to making zinc oxide devices has been
getting stable, reliable p-type material—material with
an excess of holes, or electron deficiencies. Making an
LED or laser diode requires a junction between p-type
and n-type material. But when some of the zinc oxide is
engineered to act as p-type material, it tends to revert
to its natural n-type state after a few months, which
would cause a device to fail. In contrast, blue LEDs
made from gallium nitride have expected lifetimes of
100 000 hours, or over 10 years.
A small Columbia, Mo.–based start‑up called
MOXtronics, a spin-off from the University of Missouri,
has made a big advance in solving stability and
manufacturing problems. By using an alloy of beryllium
with zinc oxide, the company has made prototype
ultraviolet LEDs. When coated with phosphors, the LEDs
can generate white, blue, green, and red light.
Henry White, a professor of physics at the University
of Missouri and a cofounder of MOXtronics, says that the
new LEDs have the potential to reach wavelengths as low
as 200 nm, which is deep in the UV region. He expects
the devices’ efficiencies and output power to compete
with those of today’s white LEDs, made of gallium
nitride, in two to three years. The company is also in
the process of making UV laser diodes, he says.
The white produced by such LEDs is soft and bright,
unlike that emitted by the sort‑of‑white LEDs made right
now by coating blue LEDs with a yellow phosphor,
observes Wright State’s Look. He believes that zinc
oxide has a very good shot at meeting the difficult
demands of the solid-state white light market, which
analysts predict will dominate over incandescent and
fluorescent bulbs by 2025, saving US $150 billion a year
in power in the United States alone.
White says MOXtronics’s devices are stable—though he
does not specify just how long they last—because they
use arsenic to dope the zinc oxide in order to make
their p-type material. Most research efforts heretofore
have focused on doping zinc oxide with nitrogen or
phosphorus. White and his colleague Yungryel Ryu have
developed a technique called hybrid beam deposition,
which uses a zinc oxide plasma and an oxygen plasma to
deposit thin zinc oxide films. Beryllium, arsenic, and
other dopants can be added during the process to grow p-
and n-type beryllium–zinc oxide alloys. Beryllium is
added to widen the bandgap—the energy difference between
the valence and the conduction bands—in order to get UV emissions.
Reliance on beryllium could be a problem. Shengbai
Zhang, a senior scientist at the National Renewable
Energy Laboratory, in Golden, Colo., points out that
beryllium could be toxic to workers during fabrication
and that people might therefore be reluctant to use it.
But the gaseous arsine used in gallium arsenide red LEDs
raises the same safety concerns, Zhang says. “If you can
avoid [beryllium], that’s easiest, but if you use it,
then…you need careful control,” he says.
There are other issues that will have to be addressed.
Both Zhang and Look single out the imperative need for a
convenient way of making p-type material that lasts for
more than two years. White says that MOXtronics’s hybrid
beam deposition should be relatively easy to scale and
use with commercially available wafer growth machines,
but the company has not shown this yet.
Meanwhile, a crucial advance in making p-type material
came last year from China, which, along with Japan and
Korea, leads the United States in zinc oxide research,
Look says. Researchers at Zhejiang University, in
Hangzhou, doped zinc oxide with lithium and nitrogen
using a standard pulsed laser deposition method to get
high-quality p‑type material that has lasted for more
than 16 months.
If these methods prove easy to use for mass-producing
zinc oxide LEDs and laser diodes, it could be the kind
of breakthrough that launched gallium nitride technology
in 1993. “Somebody needs to come up with a very cheap
manufacturing technique that’s reliable,” Look says, “a
recipe to make good, solid p-type material that anybody
can reproduce.”