Blue light-emitting diode

Blue transitions motivate wide-bandgap semiconductors, but a large band gap alone cannot guarantee efficient emission. Gallium nitride has a direct band gap; indium gallium nitride composition tunes the transition energy.^[ref]

For an emitted photon, with frequency $\nu$ and vacuum wavelength $\lambda$,where $h$ is the Planck constant and $c$ the vacuum speed of light. Multiplying energy by wavelength gives $hc=1239.841984\mathrm{eV}\mathrm{nm}$. Thus chosen wavelengths $450\mathrm{nm}$ and $630\mathrm{nm}$ correspond to $2.75520\mathrm{eV}$ and $1.96800\mathrm{eV}$: blue requires more energy per photon than red. A stipulated transition energy $3.40\mathrm{eV}$ instead gives $364.659\mathrm{nm}$, in the ultraviolet. These are conversions, not measured emission lines.

For near-edge emission, $E_{\gamma }\approx E_g$ estimates the photon energy from the emitting material's band gap. Quantum well confinement or impurity transitions can change it. The 1994 blue light-emitting diode used zinc-doped indium gallium nitride, emitting below its near-edge transition.^[ref]

The measured forward terminal electric potential difference $V_f$ is also not fixed by $E_g/q$, where $q$ is the elementary charge. It depends on electric current, temperature, contacts and series electrical resistance. Even the simple Shockley diode equation with series electrical resistance has $V_f=V_j+I{R}_s$, whereas an optical transition does not acquire an extra energy $qI{R}_s$ merely because the contact drop increases. Consequently, extracting a band gap from one terminal-voltage reading is not justified.

Isamu Akasaki chose metalorganic vapour-phase epitaxy and sapphire, which tolerated hot ammonia. Large lattice mismatch hindered film growth. In 1985, Hiroshi Amano and Isamu Akasaki's group developed an aluminium nitride epitaxial buffer layer deposited before hotter gallium nitride growth. The buffer supplies initial growth sites; growing islands join into a continuous film. It improves growth without making the lattices identical. Isamu Akasaki separately credits Shuji Nakamura's 1991 gallium nitride buffer.^[ref]

The 1986 growth paper reports a vertical metalorganic vapour-phase epitaxy reactor, source gases mixed just before delivery to slanted sapphire, and subsequent gallium nitride growth over aluminium nitride. Surface microscopy, X-ray diffraction and photoluminescence tested different aspects of the result. Buffered and unbuffered growth supplied the comparison. Its reported preparation conditions should not be replaced by one universal buffer temperature: the later lecture's account of the first low-temperature trial and the paper's parameter study describe different stages of development.^[ref]

A magnesium acceptor impurity in gallium nitride accepts a valence band Electron, leaving a mobile electron hole. Hydrogen passivation of magnesium acceptors in gallium nitride suppresses this activity. Post-growth activation restores existing impurities' electrical activity; ionization of active acceptor impurities supplies mobile electron holes. Adding magnesium alone is insufficient.^[ref]

In 1989, Hiroshi Amano, Masahiro Kito, Kazumasa Hiramatsu and Isamu Akasaki obtained p-type semiconductor conduction in magnesium-doped gallium nitride using low-energy Electron beam irradiation. Hiroshi Amano recalls initially resistive samples, an unreliable hot-probe test, then Masahiro Kito's Hall effect confirmation. A junction irradiated in an M-shaped region emitted in that pattern. Treatment, carrier-sign measurement and spatial emission supplied different evidence. Earlier zinc-doped samples brightened under irradiation without becoming p-type semiconductors: brightness alone did not prove the carrier sign.^[ref]

Shuji Nakamura, Takashi Mukai, Masayuki Senoh and Naruhito Iwasa's 1992 thermal-activation paper established another route using annealing in nitrogen. Their companion study compared already conducting films heated in nitrogen with films heated in ammonia: the latter became highly resistive again. Its hydrogen-complex explanation connected this atmosphere dependence to acceptor impurity passivation. These are thermal treatment and atmosphere comparisons, distinct from the earlier Electron beam intervention; neither observation alone images an individual hydrogen complex.^[ref][ref]

Shuji Nakamura's two-flow metalorganic chemical vapor deposition reactor, gallium nitride buffer, thermal activation and improved indium gallium nitride growth enabled bright double heterostructure devices, followed by thinner quantum well devices.^[ref]

The original 1994 paper by Shuji Nakamura, Takashi Mukai and Masayuki Senoh describes a sapphire/gallium nitride-buffer device with zinc-doped indium gallium nitride emission and aluminium gallium nitride confinement. After nitrogen annealing, etching exposed the n-side for a separate contact. At room temperature, varied forward electric currents gave emission spectra and optical-output curves alongside a current-voltage characteristic. At $20\mathrm{mA}$: $1.5\mathrm{mW}$ output, $450\mathrm{nm}$ peak wavelength, $3.6\mathrm{V}$ terminal electric potential difference. The peak stayed nearly fixed across the current series. The paper omits a complete calibrated collection apparatus; comparisons with earlier devices change several preparation details.^[ref]