At first
glance, the Itami Works complex of Sumitomo Electric
Industries Ltd. seems like any other generic Japanese
manufacturing plant in this tidy little industrial
suburb of Osaka. A cement wall, disguised by a row of
shrubbery, encloses a sprawling complex of gray or tan
buildings, some squat, some several stories tall. But
take a closer look, and you might notice that the guards
out front seem awfully vigilant, keeping close tabs on
the comings and goings.
And for good reason. In this factory, hidden among the
extruding machines, presses, and ovens churning out
wires, brakes, and synthetic diamonds, Sumitomo has just
quietly launched what will turn out to be one of the
great semiconductor advances of the 21st century: the
mass production of thin, crystal-clear disks of pure
gallium nitride.
These disks, more properly known as substrates or
wafers, are the foundation on which technicians
fabricate chips or devices. And ones made of gallium
nitride are key to long-lived and powerful laser diodes
that emit blue or ultraviolet light. The lasers, in
turn, will be the cornerstone of major new industrial
and consumer electronics goods, notably next-generation
DVD player-recorders and optical data-storage systems
for computers. The reason: thanks to its short
wavelength, blue light can write huge amounts of data on
a DVD—up to 27 GB on a standard-sized disk, almost six
times the storage capacity possible with ordinary red
laser diodes. It's enough to store more than two hours
of high-definition video or 13 hours of
standard-definition video.
Blue semiconductor lasers have been available for
several years, but until Sumitomo's breakthrough, they
had to be built on substrates of sapphire or silicon
carbide. Gallium nitride lasers deposited on those
substrates are plagued by poor reliability, low
production yield, and low output power. Semiconductor
specialists have long known that the devices would work
much better on gallium nitride substrates, but until
now, no one could figure out how to make them. Kensaku
Motoki, manager of the Advanced Material Group for
Sumitomo Electric Industries, a diverse,
multibillion-dollar company involved in everything from
high-power electrical cables to a host of exotic
semiconductors, has pulled it off. Here, during an
interview at the Itami Works, he peers through the
evidence: a transparent, colorless disk 50 mm in
diameter [see photo, "Wafer
Scale"]. To a semiconductor specialist, it's
a little miracle, and with manufacturing just starting
and R and D still ongoing, it has a price to match: US
$10 000. For comparison, a silicon wafer with a diameter
six times as large costs just $200. Roughly 1000 diodes
can be produced on one 50-mm gallium nitride wafer,
Motoki notes, but those devices are still so costly that
you won't be seeing blue-laser DVD systems in your local
Wal-Mart any time soon.
Nevertheless, the high prices aren't deterring
consumer electronics companies from offering the first
DVD recorders, with the blue laser diodes, albeit with
price tags high enough to limit sales mainly to the
well-to-do. Last spring, Tokyo-based Sony Corp. was the
first consumer electronics company to begin offering
next-generation DVD recorders, for roughly $3800. Sony
leads a consortium called Blu-ray Disc, which is pushing
one of two competing standards for the design of the
discs, players, and recorders that use blue lasers. The
group includes 10 major consumer electronics companies,
among them Hitachi, Matsushita, Royal Philips
Electronics, and Samsung. The other standard, Advanced
Optical Disc (AOD), has been proposed by Toshiba and
NEC, but at press time no AOD-based products were on the
market.
Though the blue laser systems are pricey now, their
costs will come down as their manufacturers gain
experience, and it's expected that the market for blue
laser diodes will climb, as will sales of blue
light-emitting diodes (LEDs) used for solid-state
lighting. Sales of the two are expected to reach more
than $4.7 billion by 2007, according to Strategies
Unlimited, in Mountain View, Calif.
Such projected growth is driving a whirlwind of
research, much of it in Japan, into the development of
blue laser diodes and gallium nitride substrates. And a
hint of the fierceness of the competition surfaces
during an interview at Sumitomo, when Motoki, pressed by
this reporter to be allowed to tour the secret gallium
nitride laboratory, offers a compromise. She can peer in
a window, but must promise not to write about what she
sees in there.
Infra-red and red laser diodes, such as those in
today's CD and DVD systems, have been around for
decades; blue ones have been around for less than 10
years and in commercial quantities for only about five
years. Shuji Nakamura (M), now a professor of materials
at the University of California, Santa Barbara,
developed a blue gallium nitride LED in 1993 at Nichia
Chemical Industries Ltd. (now Nichia Corp.) in
Tokushima, Japan, and, two years later, the first
gallium nitride laser diode.
In an LED's semiconductor layer, electrons recombine
with holes—places in a semiconductor's valence band
that are missing an electron—and give up energy as a
photon. The color of the light is characteristic of the
semiconductor material, and it is determined by the
difference in energy between the material's valence and
conduction bands, two bands that can be occupied by
electrons in the substance. Gallium nitride is called a
"wide bandgap" material because the difference between
the valence and conduction bands is great—so great, in
fact, that photons of visible light just slip right
through the material without being absorbed. That's why
substrates of gallium nitride are transparent.
A laser diode also works by recombining electrons and
holes. But one difference between a laser diode and an
LED is that in the laser, electrons and holes need a
nudge from a passing photon to recombine. As the photons
bounce back and forth between mirrored surfaces at each
end of the laser, they nudge more and more electrons and
holes to recombine, creating more and more photons, all
with the same phase, direction, and polarity—the
characteristic of a laser. One end of the laser is
designed to let out a narrow beam of the photons, while
keeping enough of them inside to sustain the lasing
action.
With no substrates of pure gallium nitride available,
Nakamura built his devices on a thin layer of gallium
nitride deposited on a sapphire substrate. The thin
layer was a single-crystal, meaning that the atoms
occupy positions that form a regular pattern. Today,
almost all gallium nitride LEDs and lasers are still
made in much the same way, at places like Cree
Semiconductor and Nichia.
Winner: Gallium Nitride
Goal: Build
high quality gallium nitride wafers as substrates for
blue and ultraviolet laser diodes
Why It's a
Winner: The wafers will be the foundation for
the next generation of DVD recorders
Organization:
Sumitomo Electric Industries
Center of
Activity: Itami Works, Itami, Japan
Number of People on the
Project: 50
Budget: US
$40 000 000
But devices built with sapphire substrates are plagued
with a type of defect called a dislocation. Gallium
nitride and sapphire have different crystal structures:
the distance between the atoms in the sapphire crystal
is 16 percent greater than that in gallium nitride. So
when you form one crystal on top of the other, you get a
mismatch where the two meet, a boundary area where the
regular pattern of atoms suddenly shifts. It creates
stress in the gallium nitride crystal that causes the
atoms in the gallium nitride to misalign, producing the
dislocations.
Like geological fault lines, these dislocations reach
up into the gallium nitride, producing flaws that rob
any devices built in the gallium nitride of performance
and lifetime, according to Masami Tatsumi, Sumitomo's
general manager of advanced materials R and D
laboratories. Laser diodes built on a layer of gallium
nitride that has been grown directly on a sapphire
substrate can have dislocation densities of
108/cm2
to
109/cm2
and lifetimes of less than 100 hours. "That's not good
enough for DVD players," he notes.
Dislocations are a grave concern for laser diodes
because electrons collide with them, causing the
electrons to recombine with holes without creating
photons, thus destroying the lasing action.
Sapphire substrates have other problems as well. For
one thing, they're difficult to split into pieces—a
process called cleaving—having atomically smooth
surfaces. That makes it hard to produce those mirrorlike
surfaces on each end of the gallium nitride that reflect
(or transmit) the photons. Lack of smooth surfaces
reduces the amount of light coming out of the laser.
Gallium nitride crystals, on the other hand, cleave
smoothly, making it much easier to create smooth surfaces.
Another difficulty is that sapphire is an insulator.
That's a problem because, after all, the laser devices
made on it are diodes. They must have electrical
connections on each side of the active region where
photons are produced. But the fact that the substrate
side of the device is an insulator forces device
designers into some fairly unattractive configurations.
To begin with, the designers have no choice but to put
both electrical contacts next to each other on the side
opposite the substrate. And with both of the laser's
electrical contacts on the top of the device, the
electrons are constricted to flow across a thin layer on
the top surface, which has a high resistance, Tatsumi
says [see illustration, "Making Light"].
The higher resistance means that more input power is
needed to pump light out of the device, and higher power
reduces its lifetime. Also, since both electrodes are
side by side, the device is twice as large as it would
be if one electrode could be placed on the back side of
the substrate. Gallium nitride, in contrast, is a
semiconductor, so one electrode can be placed on the
bottom of the substrate below the laser, eliminating all
those power problems.
With all the advantages of gallium nitride substrates
over sapphire, why aren't they everywhere already? The
reason is that the standard technique used to make
single-crystal substrates of gallium arsenide or silicon
simply doesn't work for gallium nitride.
For example, Motoki explains, single crystals of
gallium arsenide are made by putting ordinary,
polycrystalline pieces of the material in a glass
vessel, called a boat, and melting a circular zone of
the material by heating it in a resistance furnace.
Moving the heater from one end of the boat to the other
also moves the circular melt zone. As the material is
left to cool, it forms into a single crystal. The
cylinder that results, called a boule, is then cut into
wafers, salami style, and polished. The technique can't
be used for gallium nitride, Motoki explains, because
the nitrogen evaporates out of the crystal as it grows,
so the gallium and nitrogen atoms don't bond. To keep
the nitrogen in, you'd need pressures of tens of
thousands of atmospheres, which are difficult to realize
in a commercial process.
In 1995, when Motoki first began to look into
producing substrates for blue light-emitting devices, he
realized that so many patents had been issued for
manufacturing gallium nitride on sapphire that he had
better look for a different angle. "I wondered what
approach would be completely original and what market
would be possible without encroaching on the patents of
other companies," he told IEEE Spectrum. He decided to
try to produce stand-alone gallium nitride substrates,
an area where there were few, if any, patents, and where
Sumitomo could be "on top of the world."
Basically, he puts gallium nitride on substrates of
gallium arsenide, and then gets rid of the gallium
arsenide to leave stand-alone wafers of gallium nitride.
The trick, as always, is minimizing the dislocations
between the two materials so that the final gallium
nitride substrates are as defect-free as possible.
Among gallium arsenide's advantages is the fact that
substrates of the material are readily available because
they're used to fabricate high-speed circuits for
cellphones. Sumitomo itself manufactures and sells them.
Drawbacks include the fact that it melts at 1238 ºC;
growing gallium nitride on top of gallium arsenide
requires a temperature of more than 1000 ºC. At that
temperature, so close to gallium arsenide's melting
point, the material is very soft and reacts with the
ammonia gas that supplies the nitrogen needed to form
gallium nitride. "We had to prevent the reaction of
ammonia and gallium arsenide," says Motoki. "I can't
tell you how we did it, but we put in a lot of effort to
establish the process."
To put the thick layer of gallium nitride on the
gallium arsenide substrate, he uses a standard
chip-making technique called hydride vapor-phase
epitaxy. Then he dissolves and grinds away the gallium
arsenide, and finally polishes both sides of the
remaining gallium nitride layer to a clear shine. It's
the same basic process he used in 2000 to produce the
first sizable stand-alone single-crystal gallium nitride substrate.
But Motoki's work was far from over, because, just as
with gallium nitride and sapphire, the atomic spacings
in gallium arsenide and gallium nitride differ, and
that, again, leads to dislocations. So Motoki developed
a technique for producing regions with very low
dislocation density by forcing the dislocations into a
small area, leaving regions of low dislocation density elsewhere.
Here's how it works. Gallium nitride crystals grow in
the shape of hexagons [see photo "Saying No to
Disclocations"]. At first, each hexagon is
separate. But as growth continues, the hexagons begin to
merge, creating pits in the regions where the bases of
the hexagons come together. The dislocations formed on
the side surface of the pit propagate toward the center
of the pit as the material grows. The upshot is that in
the part of the crystal near the pits, the dislocation
density is very high, while in the rest of the crystal,
it's very low.
Using this technique, Sumitomo researchers reduced the
number of dislocations in the low-density regions to
fewer than
106/cm2.
But the areas of high dislocation density were
positioned randomly and it was difficult to make
low-defect gallium nitride lasers, which are several
hundred micrometers long. So over the next two years,
they developed a method for positioning the location of
the pits to leave larger areas relatively
dislocation-free. By 2002, they were able to produce
areas over 100 µm wide and far more than 500 µm long
with dislocation densities of less than 2 x
105/cm2—an
area big enough for a laser diode. Defect densities of
gallium nitride on sapphire substrates have come down to
about 5 x 106/cm2.
At the 2002 International Conference on Solid State
Devices and Materials, held in September in Nagoya,
Japan, Sony researchers were able to report that, using
one of Sumitomo's low-dislocation-density substrates,
they had built and tested a gallium nitride blue-violet
laser diode with an expected lifetime of over 100 000
hours. In the conference's extended abstracts, the
researchers reported that the area of low dislocation
density extended for more than 150 µm and the minimum
density was 2.8 x
105/cm2.
"This number," the Sony team wrote, "implies the
presence of only 3 to 9 dislocations for a laser...with
an area of 10-5
cm2....Therefore, it is
possible that a number of laser[s]...will contain no
dislocations at all considering the 1.5 µm width of
these [laser diodes]."
It's good, but not yet good enough. The researchers
tested the laser at 30 mW in an ambient temperature of
60° C. That output power is required for recording on
laser discs. But at that power level, it will take more
than an hour and a half to fill up a laser disc with
data. Increasing the recording speed requires higher
output power levels, again, shortening the laser diode's
lifetime. Therefore, to maintain acceptable lifetimes at
faster writing speeds, the number of dislocations must
come down still further.
Motoki and his team are confident that by improving
the control of the manufacturing process, they will be
able to reduce dislocations even more. Meanwhile,
Sumitomo is shipping substrates to many customers
developing blue-violet lasers. The company is now
ramping up production with a goal of 500 substrates per month.
Masamichi Yokogawa, Sumitomo's general manager of the
Epi-Solution Division, anticipates that demand for
blue-violet lasers for next-generation DVDs will begin
to take off as early as 2005. Eventually, demand will
reach levels comparable to those for the red and
infrared gallium arsenide laser diodes used in today's
DVD and CD systems—that's about 30 million laser diodes
per month for red and 100 million for infrared, and a
combined market, in 2002, of $1.4 billion, according to
Strategies Unlimited.
He expects that the market for industrial applications
will begin to grow even sooner—as early as this year.
Such applications could include medical instruments,
printers, and maybe even light sources for semiconductor
lithography tools that now use mercury lamps.
His company has taken a two-pronged approach to
furthering the technology, building the manufacturing
infrastructure at the same time as it pushes ahead with
research. As a result, there's a good deal of mixing of
research and development and manufacturing.
On the R and D side, engineers are developing the
techniques for growing the crystals and then polishing
the wafers. "This is a very special material, unlike
gallium arsenide or indium phosphide. It requires a
special polishing method," Yokogawa says.
On the manufacturing side, developing the special
techniques and machines is difficult, because no company
has ever done what Sumitomo is now doing. In
manufacturing, the most important goals are to improve
the reproducibility and the production yield of the
substrates and to reduce the manufacturing cost.
Yokogawa hopes engineers can cut the price of the
substrates by a factor of 5 to 10 within two years.
That would bring them more or less in line with the
price of gallium nitride-coated sapphire wafers, which
are sold by Cree, Nichia, Toyoda-Gosei, and others,
according to Deepa Doraiswamy, research analyst for
Frost and Sullivan. At press time, prices for the wafers
were not available.
With such a potentially lucrative market, it's certain
that other companies are not standing still, either.
Fumio Orito, deputy general manager of the Science and
Technology Office of Mitsubishi Chemical Corp., in
Tokyo, told Spectrum that Mitsubishi is working with
universities and other companies to develop alternatives
to sapphire as a substrate material for gallium nitride.
It also wants to develop bulk growth techniques, which
could be cheaper than the Sumitomo technique and result
in fewer dislocations because there is no sapphire or
gallium arsenide substrate.
Specialists knew that blue laser diodes work
better on gallium nitride substrates but nobody could
figure out how to make them
Mitsubishi's approach to making single-crystal gallium
nitride is a modification of the method used to make
zinc oxide substrates. To make the gallium nitride
crystals, gallium metal and gallium nitride powder are
combined with ammonia and ammonium chloride at
moderately high temperatures of from 300 to 500 ºC and
pressures of 200 to 500 megaPascals (about 20005000
atmospheres). The work is still preliminary. But so far,
the researchers have succeeded in producing only small
shards of gallium nitride a couple of millimeters across
and a centimeter or so long.
At the GE Global Research Center in Niskayuna, N.Y.,
researchers are pursuing a technique similar to
Mitsubishi's, but with even higher temperatures and
pressures: 600 to 1000 ºC and 500 to 2000 megaPascals
(500020 000 atmospheres). They have been able to
produce single-crystal gallium nitride substrates 12 mm
thick with an area of 15 by 18
mm2. Researchers have made
considerable progress, says Mark P. D'Evelyn, manager of
GE Global's Ceramic Processing Laboratory, and have
measured defect densities less than
200/cm2. But much more work
remains before the product is ready to be
commercialized.
Meanwhile, ATMI Inc., in Danbury, Conn., is using an
approach similar to Sumitomo's, but with a starting
substrate of sapphire instead of gallium arsenide. ATMI
scientists grow the desired thickness of gallium
nitride, then remove the sapphire to leave a
free-standing layer of single-crystal gallium nitride.
The company has begun to sell engineering quantities of
50-mm wafers with uniform dislocation densities of
106/cm2.
An advantage of the uniformity, says Allan Salant, the
company's manager of development engineering, is that
laser diodes built on its wafers are not restricted in
device size or location.
In total, the number of companies and research
institutions developing gallium nitride substrates has
climbed to more than 20. And the rate at which the
technology is advancing is testimony to the importance
of this material. At this time, there is little doubt
that we will have commercial quantities of
low-dislocation-density gallium nitride substrates in
the near future. The questions are only by what methods
and from whom.