Light-emitting diode
Blue LED

The first blue -violet LED using magnesium-doped gallium nitride was made at Stanford University in 1972 by Herb Maruska and Wally Rhines, doctoral students in materials science and engineering. At the time Maruska was on leave from RCA Laboratories, where he collaborated with Jacques Pankove on related work. In 1971, the year after Maruska left for Stanford, his RCA colleagues Pankove and Ed Miller demonstrated the first blue electroluminescence from zinc-doped gallium nitride, though the subsequent device Pankove and Miller built, the first actual gallium nitride light-emitting diode, emitted green light.

In 1974 the U.S. Patent Office awarded Maruska, Rhines, and Stanford professor David Stevenson a patent for their work in 1972 (U.S. Patent US3819974 A). Today, magnesium-doping of gallium nitride remains the basis for all commercial blue LEDs and laser diodes. In the early 1970s, these devices were too dim for practical use, and research into gallium nitride devices slowed.

In August 1989, Cree introduced the first commercially available blue LED based on the indirect bandgap semiconductor, silicon carbide (SiC). SiC LEDs had very low efficiency, no more than about 0.03%, but did emit in the blue portion of the visible light spectrum.

In the late 1980s, key breakthroughs in GaN epitaxial growth and p-type doping ushered in the modern era of GaN-based optoelectronic devices. Building upon this foundation, Theodore Moustakas at Boston University patented a method for producing high-brightness blue LEDs using a new two-step process in 1991. In 2015, a US court ruled that three Taiwanese companies had infringed Moustakas's prior patent, and ordered them to pay licensing fees of not less than US$13 million.

Two years later, in 1993, high-brightness blue LEDs were demonstrated by Shuji Nakamura of Nichia Corporation using a gallium nitride (GaN) growth process. These LEDs had efficiencies of 10%. In parallel, Isamu Akasaki and Hiroshi Amano of Nagoya University were working on developing the important GaN deposition on sapphire substrates and the demonstration of p-type doping of GaN. This new development revolutionized LED lighting, making high-power blue light sources practical, leading to the development of technologies like Blu-ray.

Nakamura was awarded the 2006 Millennium Technology Prize for his invention. Nakamura, Hiroshi Amano, and Isamu Akasaki were awarded the Nobel Prize in Physics in 2014 for "the invention of efficient blue light-emitting diodes, which has enabled bright and energy-saving white light sources."

In 1995, Alberto Barbieri at the Cardiff University Laboratory (GB) investigated the efficiency and reliability of high-brightness LEDs and demonstrated a "transparent contact" LED using indium tin oxide (ITO) on (AlGaInP/GaAs).

In 2001 and 2002, processes for growing gallium nitride (GaN) LEDs on silicon were successfully demonstrated. In January 2012, Osram demonstrated high-power InGaN LEDs grown on silicon substrates commercially, and GaN-on-silicon LEDs are in production at Plessey Semiconductors. As of 2017, some manufacturers are using SiC as the substrate for LED production, but sapphire is more common, as it has the most similar properties to that of gallium nitride, reducing the need for patterning the sapphire wafer (patterned wafers are known as epi wafers). Samsung, the University of Cambridge, and Toshiba are performing research into GaN on Si LEDs.

Toshiba has stopped research, possibly due to low yields. Some opt for epitaxy, which is difficult on silicon, while others, like the University of Cambridge, choose a multi-layer structure, in order to reduce (crystal) lattice mismatch and different thermal expansion ratios, to avoid cracking of the LED chip at high temperatures (e.g. during manufacturing), reduce heat generation and increase luminous efficiency. Sapphire substrate patterning can be carried out with nanoimprint lithography.

GaN-on-Si is difficult but desirable since it takes advantage of existing semiconductor manufacturing infrastructure. It allows for the wafer-level packaging of LED dies resulting in extremely small LED packages.

GaN is often deposited using metalorganic vapour-phase epitaxy (MOCVD), and it also uses lift-off.
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