Conventional LEDs are made from a variety of inorganic semiconductor materials. The following table shows the available colors with wavelength range, voltage drop, and material:

Color Wavelength [nm] Voltage drop [ΔV] Semiconductor material
Infrared λ > 760 ΔV < 1.63 Gallium arsenide (GaAs)
Aluminium gallium arsenide (AlGaAs)
Red 610 < λ < 760 1.63 < ΔV < 2.03 Aluminium gallium arsenide (AlGaAs)
Gallium arsenide phosphide (GaAsP)
Aluminium gallium indium phosphide (AlGaInP)
Gallium(III) phosphide (GaP)
Orange 590 < λ < 610 2.03 < ΔV < 2.10 Gallium arsenide phosphide (GaAsP)
Aluminium gallium indium phosphide (AlGaInP)
Gallium(III) phosphide (GaP)
Yellow 570 < λ < 590 2.10 < ΔV < 2.18 Gallium arsenide phosphide (GaAsP)
Aluminium gallium indium phosphide (AlGaInP)
Gallium(III) phosphide (GaP)
Green 500 < λ < 570 1.9 < ΔV < 4.0 Traditional green:
Gallium(III) phosphide (GaP)
Aluminium gallium indium phosphide (AlGaInP)
Aluminium gallium phosphide (AlGaP)
Pure green:
Indium gallium nitride (InGaN) / Gallium(III) nitride (GaN)
Blue 450 < λ < 500 2.48 < ΔV < 3.7 Zinc selenide (ZnSe)
Indium gallium nitride (InGaN)
Synthetic sapphire, Silicon carbide (SiC) as substrate with or without epitaxy,
Silicon (Si) as substrate—under development (epitaxy on silicon is hard to control)
Violet 400 < λ < 450 2.76 < ΔV < 4.0 Indium gallium nitride (InGaN)
Ultraviolet λ < 400 3 < ΔV < 4.1 Indium gallium nitride (InGaN) (385-400 nm)
Diamond (235 nm)
Boron nitride (215 nm)
Aluminium nitride (AlN) (210 nm)
Aluminium gallium nitride (AlGaN)
Aluminium gallium indium nitride (AlGaInN)—down to 210 nm
Pink Multiple types ΔV ≈3.3 Blue with one or two phosphor layers,
yellow with red, orange or pink phosphor added afterwards,
white with pink plastic,
or white phosphors with pink pigment or dye over top.
Purple Multiple types 2.48 < ΔV < 3.7 Dual blue/red LEDs,
blue with red phosphor,
or white with purple plastic
White Broad spectrum 2.8 < ΔV < 4.2 Cool / Pure White: Blue/UV diode with yellow phosphor
Warm White: Blue diode with orange phosphor

Blue and ultraviolet

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) and 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. Two years later, in 1993, high-brightness blue LEDs were demonstrated again by Shuji Nakamura of Nichia Corporation using a gallium nitride growth process similar to Moustakas’s. Both Moustakas and Nakamura were issued separate patents, which confused the issue of who was the original inventor (partly because although Moustakas invented his first, Nakamura filed first). This new development revolutionized LED lighting, making high-power blue light sources practical, leading to the development of technologies like Blu-ray, as well as allowing the bright high-resolution screens of modern tablets and phones.

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 the blue LED. In 2015, a US court ruled that three companies (i.e. the litigants who had not previously settled out of court) that had licensed Nakamura’s patents for production in the United States had infringed Moustakas’s prior patent, and ordered them to pay licensing fees of not less than 13 million USD.

By the late 1990s, blue LEDs became widely available. They have an active region consisting of one or more InGaN quantum wells sandwiched between thicker layers of GaN, called cladding layers. By varying the relative In/Ga fraction in the InGaN quantum wells, the light emission can in theory be varied from violet to amber. Aluminium gallium nitride (AlGaN) of varying Al/Ga fraction can be used to manufacture the cladding and quantum well layers for ultraviolet LEDs, but these devices have not yet reached the level of efficiency and technological maturity of InGaN/GaN blue/green devices. If un-alloyed GaN is used in this case to form the active quantum well layers, the device emits near-ultraviolet light with a peak wavelength centred around 365 nm. Green LEDs manufactured from the InGaN/GaN system are far more efficient and brighter than green LEDs produced with non-nitride material systems, but practical devices still exhibit efficiency too low for high-brightness applications.

With nitrides containing aluminium, most often AlGaN and AlGaInN, even shorter wavelengths are achievable. Ultraviolet LEDs in a range of wavelengths are becoming available on the market. Near-UV emitters at wavelengths around 375–395 nm are already cheap and often encountered, for example, as black light lamp replacements for inspection of anti-counterfeiting UV watermarks in some documents and paper currencies. Shorter-wavelength diodes, while substantially more expensive, are commercially available for wavelengths down to 240 nm. As the photosensitivity of microorganisms approximately matches the absorption spectrum of DNA, with a peak at about 260 nm, UV LED emitting at 250–270 nm are expected in prospective disinfection and sterilization devices. Recent research has shown that commercially available UVA LEDs (365 nm) are already effective disinfection and sterilization devices. UV-C wavelengths were obtained in laboratories using aluminium nitride (210 nm), boron nitride (215 nm) and diamond (235 nm).

RGB

RGB LEDs consist of one red, one green, and one blue LED. By independently adjusting each of the three, RGB LEDs are capable of producing a wide color gamut. Unlike dedicated-color LEDs, however, these obviously do not produce pure wavelengths. Moreover, such modules as commercially available are often not optimized for smooth color mixing.

White

There are two primary ways of producing white light-emitting diodes (WLEDs), LEDs that generate high-intensity white light. One is to use individual LEDs that emit three primary colors—red, green, and blue—and then mix all the colors to form white light. The other is to use a phosphor material to convert monochromatic light from a blue or UV LED to broad-spectrum white light, much in the same way a fluorescent light bulb works. The ‘whiteness’ of the light produced is essentially engineered to suit the human eye. The yellow phosphor in LEDs is Cerium doped YAG crystal, in powder form and may be suspended in plastic, epoxy, synthetic rubber or silicone. Touching bare LEDs using synthetic rubber or silicone can damage the delicate wire bonds from LED to package or the LED itself, so they may be protected by a plastic or glass cover, such as in the LED flash in smartphones. It is this YAG phosphor which causes white LEDs without diffusers (such as those used in LED lamps and bulbs) to look yellow when off.

There are three main methods of mixing colors to produce white light from an LED:

  • blue LED + green LED + red LED (color mixing; can be used as backlighting for displays, extremely  poor for illumination due to gaps in spectrum)
  • near-UV or UV LED + RGB phosphor (an LED producing light with a wavelength shorter than blue’s is used to excite an RGB phosphor, a mixture of red, green, and blue phosphor)
  • blue LED + yellow phosphor (two complementary colors combine to form white light; more efficient than the first two methods and more commonly used)

Because of metamerism, it is possible to have quite different spectra that appear white. However, the appearance of objects illuminated by that light may vary as the spectrum varies, this is the issue of color rendition, quite separate from color temperature, where a really orange or cyan object could appear with the wrong color and much darker as the LED or phosphor does not emit the wavelength it reflects. The best color rendition CFL and LEDs use a mix of phosphors, resulting in less efficiency but better quality of light. Though incandescent halogen lamps have a more orange color temperature, they are still the best easily available artificial light sources in terms of color rendition.

RGB systems

White light can be formed by mixing differently colored lights; the most common method is to use red, green, and blue (RGB). Hence the method is called multicolor white LEDs (sometimes referred to as RGB LEDs). Because these need electronic circuits to control the blending and diffusion of different colors, and because the individual color LEDs typically have slightly different emission patterns (leading to variation of the color depending on direction) even if they are made as a single unit, these are seldom used to produce white lighting. Nonetheless, this method has many applications because of the flexibility of mixing different colors, and in principle, this mechanism also has higher quantum efficiency in producing white light.

There are several types of multicolor white LEDs: di-, tri-, and tetrachromatic white LEDs. Several key factors that play among these different methods include color stability, color rendering capability, and luminous efficacy. Often, higher efficiency means lower color rendering, presenting a trade-off between the luminous efficacy and color rendering. For example, the dichromatic white LEDs have the best luminous efficacy (120 lm/W), but the lowest color rendering capability. However, although tetrachromatic white LEDs have excellent color rendering capability, they often have poor luminous efficacy. Trichromatic white LEDs are in between, having both good luminous efficacy (>70 lm/W) and fair color rendering capability.

One of the challenges is the development of more efficient green LEDs. The theoretical maximum for green LEDs is 683 lumens per watt but as of 2010 few green LEDs exceed even 100 lumens per watt. The blue and red LEDs approach their theoretical limits.

Multicolor LEDs offer not merely another means to form white light but a new means to form light of different colors. Most perceivable colors can be formed by mixing different amounts of three primary colors. This allows precise dynamic color control. As more effort is devoted to investigating this method, multicolor LEDs should have profound influence on the fundamental method that we use to produce and control light color. However, before this type of LED can play a role on the market, several technical problems must be solved. These include that this type of LED’s emission power decays exponentially with rising temperature, resulting in a substantial change in color stability. Such problems inhibit and may preclude industrial use. Thus, many new package designs aimed at solving this problem have been proposed and their results are now being reproduced by researchers and scientists. However multicolor LEDs without phosphors can never provide good quality lighting because each LED is a narrow band source (see graph). LEDs without phosphor while a poorer solution for general lighting are the best solution for displays, either backlight of LCD, or direct LED based pixels.

Correlated color temperature (CCT) dimming for LED technology is regarded as a difficult task since LED binning, age and temperature drift effects of LEDs change the actual color value output. Feedback loop systems are used for example with color sensors, to actively monitor and control the color output of multiple color mixing LEDs.

Phosphor-based LEDs

This method involves coating LEDs of one color (mostly blue LEDs made of InGaN) with phosphors of different colors to form white light; the resultant LEDs are called phosphor-based or phosphor-converted white LEDs (pcLEDs). A fraction of the blue light undergoes the Stokes shift, which transforms it from shorter wavelengths to longer. Depending on the original LED’s color, various color phosphors are used. Using several phosphor layers of distinct colors broadens the emitted spectrum, effectively raising the color rendering index (CRI).

Phosphor-based LEDs have efficiency losses due to heat loss from the Stokes shift and also other phosphor-related issues. Their luminous efficacies compared to normal LEDs depend on the spectral distribution of the resultant light output and the original wavelength of the LED itself. For example, the luminous efficacy of a typical YAG yellow phosphor based white LED ranges from 3 to 5 times the luminous efficacy of the original blue LED because of the human eye’s greater sensitivity to yellow than to blue (as modeled in the luminosity function). Due to the simplicity of manufacturing, the phosphor method is still the most popular method for making high-intensity white LEDs. The design and production of a light source or light fixture using a monochrome emitter with phosphor conversion is simpler and cheaper than a complex RGB system, and the majority of high-intensity white LEDs presently on the market are manufactured using phosphor light conversion.

Among the challenges being faced to improve the efficiency of LED-based white light sources is the development of more efficient phosphors. As of 2010, the most efficient yellow phosphor is still the YAG phosphor, with less than 10% Stokes shift loss. Losses attributable to internal optical losses due to re-absorption in the LED chip and in the LED packaging itself account typically for another 10% to 30% of efficiency loss. Currently, in the area of phosphor LED development, much effort is being spent on optimizing these devices to higher light output and higher operation temperatures. For instance, the efficiency can be raised by adapting better package design or by using a more suitable type of phosphor. Conformal coating process is frequently used to address the issue of varying phosphor thickness.

Some phosphor-based white LEDs encapsulate InGaN blue LEDs inside phosphor-coated epoxy. Alternatively, the LED might be paired with a remote phosphor, a preformed polycarbonate piece coated with the phosphor material. Remote phosphors provide more diffuse light, which is desirable for many applications. Remote phosphor designs are also more tolerant of variations in the LED emissions spectrum. A common yellow phosphor material is cerium-doped yttrium aluminium garnet (Ce3+:YAG).

White LEDs can also be made by coating near-ultraviolet (NUV) LEDs with a mixture of high-efficiency europium-based phosphors that emit red and blue, plus copper and aluminium-doped zinc sulfide (ZnS:Cu, Al) that emits green. This is a method analogous to the way fluorescent lamps work. This method is less efficient than blue LEDs with YAG:Ce phosphor, as the Stokes shift is larger, so more energy is converted to heat, but yields light with better spectral characteristics, which render color better. Due to the higher radiative output of the ultraviolet LEDs than of the blue ones, both methods offer comparable brightness. A concern is that UV light may leak from a malfunctioning light source and cause harm to human eyes or skin.

Other white LEDs

Another method used to produce experimental white light LEDs used no phosphors at all and was based on homoepitaxially grown zinc selenide (ZnSe) on a ZnSe substrate that simultaneously emitted blue light from its active region and yellow light from the substrate.

A new style of wafers composed of gallium-nitride-on-silicon (GaN-on-Si) is being used to produce white LEDs using 200-mm silicon wafers. This avoids the typical costly sapphire substrate in relatively small 100- or 150-mm wafer sizes. The sapphire apparatus must be coupled with a mirror-like collector to reflect light that would otherwise be wasted. It is predicted that by 2020, 40% of all GaN LEDs will be made with GaN-on-Si. Manufacturing large sapphire material is difficult, while large silicon material is cheaper and more abundant. LED companies shifting from using sapphire to silicon should be a minimal investment.

Organic light-emitting diodes (OLEDs)

In an organic light-emitting diode (OLED), the electroluminescent material composing the emissive layer of the diode is an organic compound. The organic material is electrically conductive due to the delocalization of pi electrons caused by conjugation over all or part of the molecule, and the material therefore functions as an organic semiconductor. The organic materials can be small organic molecules in a crystalline phase, or polymers.

The potential advantages of OLEDs include thin, low-cost displays with a low driving voltage, wide viewing angle, and high contrast and color gamut. Polymer LEDs have the added benefit of printable and flexible displays. OLEDs have been used to make visual displays for portable electronic devices such as cellphones, digital cameras, and MP3 players while possible future uses include lighting and televisions.

Quantum-dot LEDs

Quantum dots (QD) are semiconductor nanocrystals with optical properties that let their emission color be tuned from the visible into the infrared spectrum. This allows quantum dot LEDs to create almost any color on the CIE diagram. This provides more color options and better color rendering than white LEDs since the emission spectrum is much narrower, characteristic of quantum confined states.

There are two types of schemes for QD excitation. One uses photo excitation with a primary light source LED (typically blue or UV LEDs are used). The other is direct electrical excitation first demonstrated by Alivisatos et al.

One example of the photo-excitation scheme is a method developed by Michael Bowers, at Vanderbilt University in Nashville, involving coating a blue LED with quantum dots that glow white in response to the blue light from the LED. This method emits a warm, yellowish-white light similar to that made by incandescent light bulbs. Quantum dots are also being considered for use in white light-emitting diodes in liquid crystal display (LCD) televisions.

In February 2011 scientists at PlasmaChem GmbH were able to synthesize quantum dots for LED applications and build a light converter on their basis, which was able to efficiently convert light from blue to any other color for many hundred hours. Such QDs can be used to emit visible or near infrared light of any wavelength being excited by light with a shorter wavelength.

The structure of QD-LEDs used for the electrical-excitation scheme is similar to basic design of OLEDs. A layer of quantum dots is sandwiched between layers of electron-transporting and hole-transporting materials. An applied electric field causes electrons and holes to move into the quantum dot layer and recombine forming an exciton that excites a QD. This scheme is commonly studied for quantum dot display. The tunability of emission wavelengths and narrow bandwidth is also beneficial as excitation sources for fluorescence imaging. Fluorescence near-field scanning optical microscopy (NSOM) utilizing an integrated QD-LED has been demonstrated.

In February 2008, a luminous efficacy of 300 lumens of visible light per watt of radiation (not per electrical watt) and warm-light emission was achieved by using nanocrystals.

Quote from Wikipedia.
Link: https://en.wikipedia.org/wiki/Light-emitting_diode

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