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Light Absorption for Photosynthesis

Photosynthesis depends upon the absorption of light by pigments in the leaves of plants. The most important of these is chlorophyll-a, but there are several accessory pigments that also contribute.

The measured rate of photosynthesis as a function of absorbed wavelength correlates well with the absorption frequencies of chlorophyll a, but makes it evident that there are some other contributors to the absorption.

The plot of the absorption spectra of the chlorophylls plus beta carotene correlates well with the observed photosynthetic output. The measure of photochemical efficiency is made by measuring the amount of oxygen produced by leaves following exposure to various wavelengths.

It is evident from these absorption and output plots that only the red and blue ends of the visible part of the electromagnetic spectrum are used by plants in photosynthesis. The reflection and transmission of the middle of the spectrum gives the leaves their green visual color. 


Light-dependent reactions

Light-dependent reactions of photosynthesis at the thylakoid membrane
Main article: Light-dependent reactions

In the light-dependent reactions, one molecule of the pigment chlorophyll absorbs one photon and loses one electron. This electron is passed to a modified form of chlorophyll called pheophytin, which passes the electron to a quinone molecule, starting the flow of electrons down an electron transport chain that leads to the ultimate reduction of NADP to NADPH. In addition, this creates a proton gradient (energy gradient) across the chloroplast membrane, which is used by ATP synthase in the synthesis of ATP. The chlorophyll molecule ultimately regains the electron it lost when a water molecule is spit in a process called photolysis, which releases a dioxygen (O2) molecule as a waste product.

The overall equation for the light-dependent reactions under the conditions of non-cyclic electron flow in green plants is:[24]

2 H2O + 2 NADP+ + 3 ADP + 3 Pi + light → 2 NADPH + 2 H+ + 3 ATP + O2

Not all wavelengths of light can support photosynthesis. The photosynthetic action spectrum depends on the type of accessory pigments present. For example, in green plants, the action spectrum resembles the absorption spectrum for chlorophylls and carotenoids with peaks for violet-blue and red light. In red algae, the action spectrum is blue-green light, which allows these algae to use the blue end of the spectrum to grow in the deeper waters that filter out the longer wavelengths (red light) used by above ground green plants. The non-absorbed part of the light spectrum is what gives photosynthetic organisms their color (e.g., green plants, red algae, purple bacteria) and is the least effective for photosynthesis in the respective organisms.

Z scheme

The "Z scheme"

In plants, light-dependent reactions occur in the thylakoid membranes of the chloroplasts where they drive the synthesis of ATP and NADPH. The light-dependent reactions are of two forms: cyclic and non-cyclic.

In the non-cyclic reaction, the photons are captured in the light-harvesting antenna complexes of photosystem II by chlorophyll and other accessory pigments (see diagram at right). The absorption of a photon by the antenna complex frees an electron by a process called photoinduced charge separation. The antenna system is at the core of the chlorophyll molecule of the photosystem II reaction center. That freed electron is transferred to the primary electron-acceptor molecule, pheophytin. As the electrons are shuttled through an electron transport chain (the so-called Z-scheme shown in the diagram), it initially functions to generate a chemiosmotic potential by pumping proton cations (H+) across the membrane and into the thylakoid space. An ATP synthase enzyme uses that chemiosmotic potential to make ATP during photophosphorylation, whereas NADPH is a product of the terminal redox reaction in the Z-scheme. The electron enters a chlorophyll molecule in Photosystem I. There it is further excited by the light absorbed by that photosystem. The electron is then passed along a chain of electron acceptors to which it transfers some of its energy. The energy delivered to the electron acceptors is used to move hydrogen ions across the thylakoid membrane into the lumen. The electron is eventually used to reduce the co-enzyme NADP with a H+ to NADPH (which has functions in the light-independent reaction); at that point, the path of that electron ends.

The cyclic reaction is similar to that of the non-cyclic, but differs in that it generates only ATP, and no reduced NADP (NADPH) is created. The cyclic reaction takes place only at photosystem I. Once the electron is displaced from the photosystem, the electron is passed down the electron acceptor molecules and returns to photosystem I, from where it was emitted, hence the name cyclic reaction.


Light-emitting diode From Wikipedia, the free encyclopedia Jump to: navigation, search "LED" redirects here. For other uses, see LED (disambiguation). This article needs additional citations for verification. Please help improve this article by adding citations to reliable sources. Unsourced material may be challenged and removed. (August 2015) Light-emitting diode RBG-LED.jpg Blue, green, and red LEDs in 5 mm diffused cases Type Passive, optoelectronic Working principle Electroluminescence Invented Oleg Losev (1927)[1] James R. Biard (1961)[2] Nick Holonyak (1962)[3] First production October 1962 Pin configuration Anode and cathode Electronic symbol LED symbol.svg Parts of an LED. Although unlabeled, the flat bottom surfaces of the anvil and post embedded inside the epoxy act as anchors, to prevent the conductors from being forcefully pulled out from mechanical strain or vibration. Modern LED retrofit with E27 screw in base A bulb-shaped modern retrofit LED lamp with aluminium heat sink, a light diffusing dome and E27 screw base, using a built-in power supply working on mains voltage A light-emitting diode (LED) is a two-lead semiconductor light source. It is a p–n junction diode, which emits light when activated.[4] When a suitable voltage is applied to the leads, electrons are able to recombine with electron holes within the device, releasing energy in the form of photons. This effect is called electroluminescence, and the color of the light (corresponding to the energy of the photon) is determined by the energy band gap of the semiconductor. An LED is often small in area (less than 1 mm2) and integrated optical components may be used to shape its radiation pattern.[5] Appearing as practical electronic components in 1962,[6] the earliest LEDs emitted low-intensity infrared light. Infrared LEDs are still frequently used as transmitting elements in remote-control circuits, such as those in remote controls for a wide variety of consumer electronics. The first visible-light LEDs were also of low intensity, and limited to red. Modern LEDs are available across the visible, ultraviolet, and infrared wavelengths, with very high brightness. Early LEDs were often used as indicator lamps for electronic devices, replacing small incandescent bulbs. They were soon packaged into numeric readouts in the form of seven-segment displays, and were commonly seen in digital clocks. Recent developments in LEDs permit them to be used in environmental and task lighting. LEDs have many advantages over incandescent light sources including lower energy consumption, longer lifetime, improved physical robustness, smaller size, and faster switching. Light-emitting diodes are now used in applications as diverse as aviation lighting, automotive headlamps, advertising, general lighting, traffic signals, camera flashes and lighted wallpaper. As of 2015, LEDs powerful enough for room lighting remain somewhat more expensive, and require more precise current and heat management, than compact fluorescent lamp sources of comparable output. LEDs have allowed new text, video displays, and sensors to be developed, while their high switching rates are also used in advanced communications technology.


Discoveries and early devices[edit]

Green electroluminescence from a point contact on a crystal of SiC recreates Round's original experiment from 1907.

Electroluminescence as a phenomenon was discovered in 1907 by the British experimenter H. J. Round of Marconi Labs, using a crystal of silicon carbide and a cat's-whisker detector.[7][8] Soviet inventor Oleg Losev reported creation of the first LED in 1927.[9] His research was distributed in Soviet, German and British scientific journals, but no practical use was made of the discovery for several decades.[10][11] Kurt Lehovec, Carl Accardo and Edward Jamgochian, explained these first light-emitting diodes in 1951 using an apparatus employing SiC crystals with a current source of battery or pulse generator and with a comparison to a variant, pure, crystal in 1953.[12][13]

Rubin Braunstein[14] of the Radio Corporation of America reported on infrared emission from gallium arsenide (GaAs) and other semiconductor alloys in 1955.[15] Braunstein observed infrared emission generated by simple diode structures using gallium antimonide (GaSb), GaAs, indium phosphide (InP), and silicon-germanium (SiGe) alloys at room temperature and at 77 Kelvin.

In 1957, Braunstein further demonstrated that the rudimentary devices could be used for non-radio communication across a short distance. As noted by Kroemer[16] Braunstein".. had set up a simple optical communications link: Music emerging from a record player was used via suitable electronics to modulate the forward current of a GaAs diode. The emitted light was detected by a PbS diode some distance away. This signal was fed into an audio amplifier, and played back by a loudspeaker. Intercepting the beam stopped the music. We had a great deal of fun playing with this setup." This setup presaged the use of LEDs for optical communication applications.

Diagram of a light emitting diode constructed on a zinc diffused area of gallium arsenide semi-insulating substrate

In September 1961, while working at Texas Instruments in Dallas, Texas, James R. Biard and Gary Pittman discovered near-infrared (900 nm) light emission from a tunnel diode they had constructed on a GaAs substrate.[6] By October 1961, they had demonstrated efficient light emission and signal coupling between a GaAs p-n junction light emitter and an electrically-isolated semiconductor photodetector.[17] On August 8, 1962, Biard and Pittman filed a patent titled "Semiconductor Radiant Diode" based on their findings, which described a zinc diffused p–n junction LED with a spaced cathode contact to allow for efficient emission of infrared light under forward bias. After establishing the priority of their work based on engineering notebooks predating submissions from G.E. Labs, RCA Research Labs, IBM Research Labs, Bell Labs, and Lincoln Lab at MIT, the U.S. patent office issued the two inventors the patent for the GaAs infrared (IR) light-emitting diode (U.S. Patent US3293513), the first practical LED.[6] Immediately after filing the patent, Texas Instruments (TI) began a project to manufacture infrared diodes. In October 1962, TI announced the first LED commercial product (the SNX-100), which employed a pure GaAs crystal to emit a 890 nm light output.[6] In October 1963, TI announced the first commercial hemispherical LED, the SNX-110.[18]

The first visible-spectrum (red) LED was developed in 1962 by Nick Holonyak, Jr., while working at General Electric Company. Holonyak first reported his LED in the journal Applied Physics Letters on the December 1, 1962.[19][20] M. George Craford,[21] a former graduate student of Holonyak, invented the first yellow LED and improved the brightness of red and red-orange LEDs by a factor of ten in 1972.[22] In 1976, T. P. Pearsall created the first high-brightness, high-efficiency LEDs for optical fiber telecommunications by inventing new semiconductor materials specifically adapted to optical fiber transmission wavelengths.[23]

Initial commercial development[edit]

The first commercial LEDs were commonly used as replacements for incandescent and neon indicator lamps, and in seven-segment displays,[24] first in expensive equipment such as laboratory and electronics test equipment, then later in such appliances as TVs, radios, telephones, calculators, as well as watches (see list of signal uses). Until 1968, visible and infrared LEDs were extremely costly, in the order of US$200 per unit, and so had little practical use.[25] The Monsanto Company was the first organization to mass-produce visible LEDs, using gallium arsenide phosphide (GaAsP) in 1968 to produce red LEDs suitable for indicators.[25] Hewlett Packard (HP) introduced LEDs in 1968, initially using GaAsP supplied by Monsanto. These red LEDs were bright enough only for use as indicators, as the light output was not enough to illuminate an area. Readouts in calculators were so small that plastic lenses were built over each digit to make them legible. Later, other colors became widely available and appeared in appliances and equipment. In the 1970s commercially successful LED devices at less than five cents each were produced by Fairchild Optoelectronics. These devices employed compound semiconductor chips fabricated with the planar process invented by Dr. Jean Hoerni at Fairchild Semiconductor.[26][27] The combination of planar processing for chip fabrication and innovative packaging methods enabled the team at Fairchild led by optoelectronics pioneer Thomas Brandt to achieve the needed cost reductions.[28] These methods continue to be used by LED producers.[29]

LED display of a TI-30 scientific calculator (ca. 1978), which uses plastic lenses to increase the visible digit size

Most LEDs were made in the very common 5 mm T1¾ and 3 mm T1 packages, but with rising power output, it has grown increasingly necessary to shed excess heat to maintain reliability,[30] so more complex packages have been adapted for efficient heat dissipation. Packages for state-of-the-art high-power LEDs bear little resemblance to early LEDs.

Blue LED[edit]

Blue LEDs were first developed by RCA in 1972.[31] SiC-types were first commercially sold in the United States by Cree in 1989.[32] However, neither of these initial blue LEDs were very bright.

The first high-brightness blue LED was demonstrated by Shuji Nakamura of Nichia Corporation in 1994 and was based on InGaN.[33][34] In parallel, Isamu Akasaki and Hiroshi Amano in Nagoya were working on developing the important GaN nucleation on sapphire substrates and the demonstration of p-type doping of GaN. Nakamura, Akasaki and Amano were awarded the 2014 Nobel prize in physics for their work.[35] 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[36] and 2002,[37] 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.[38]

White LEDs and the Illumination breakthrough[edit]

The attainment of high efficiency in blue LEDs was quickly followed by the development of the first white LED. In this device a Y
:Ce (known as "YAG") phosphor coating on the emitter absorbs some of the blue emission and produces yellow light through fluorescence. The combination of that yellow with remaining blue light appears white to the eye. However using different phosphors (fluorescent materials) it also became possible to instead produce green and red light through fluorescence. The resulting mixture of red, green and blue is not only perceived by humans as white light but is superior for illumination in terms of color rendering, whereas one cannot appreciate the color of red or green objects illuminated only by the yellow (and remaining blue) wavelengths from the YAG phosphor.

Illustration of Haitz's law, showing improvement in light output per LED over time, with a logarithmic scale on the vertical axis

The first white LEDs were expensive and inefficient. However, the light output of LEDs has increased exponentially, with a doubling occurring approximately every 36 months since the 1960s (similar to Moore's law). This trend is generally attributed to the parallel development of other semiconductor technologies and advances in optics[citation needed] and materials science, and has been called Haitz's law after Dr. Roland Haitz.[39]

The light output and efficiency of blue and near-ultraviolet LEDs rose as the cost of reliable devices fell: this led to the use of (relatively) high-power white-light LEDs for the purpose of illumination which are replacing incandescent and fluorescent lighting.[40][41]

White LEDs can now produce over 300 lumens per watt of electricity while lasting up to 100,000 hours.[42] Compared to incandescent bulbs, this amounts not only to a huge increase in electrical efficiency, but a similar or better prorated cost for the bulbs.

Working principle[edit]

The inner workings of an LED, showing circuit (top) and band diagram (bottom)

A P-N junction can convert absorbed light energy into a proportional electric current. The same process is reversed here (i.e. the P-N junction emits light when electrical energy is applied to it). This phenomenon is generally called electroluminescence, which can be defined as the emission of light from a semi-conductor under the influence of an electric field. The charge carriers recombine in a forward-biased P-N junction as the electrons cross from the N-region and recombine with the holes existing in the P-region. Free electrons are in the conduction band of energy levels, while holes are in the valence energy band. Thus the energy level of the holes will be lesser than the energy levels of the electrons. Some portion of the energy must be dissipated in order to recombine the electrons and the holes. This energy is emitted in the form of heat and light.

The electrons dissipate energy in the form of heat for silicon and germanium diodes but in gallium arsenide phosphide (GaAsP) and gallium phosphide (GaP) semiconductors, the electrons dissipate energy by emitting photons. If the semiconductor is translucent, the junction becomes the source of light as it is emitted, thus becoming a light-emitting diode, but when the junction is reverse biased no light will be produced by the LED and, on the contrary, the device may also be damaged.


I-V diagram for a diode. An LED will begin to emit light when more than 2 or 3 volts is applied to it.


The LED consists of a chip of semiconducting material doped with impurities to create a p-n junction. As in other diodes, current flows easily from the p-side, or anode, to the n-side, or cathode, but not in the reverse direction. Charge-carriers—electrons and holes—flow into the junction from electrodes with different voltages. When an electron meets a hole, it falls into a lower energy level and releases energy in the form of a photon.

The wavelength of the light emitted, and thus its color, depends on the band gap energy of the materials forming the p-n junction. In silicon or germanium diodes, the electrons and holes usually recombine by a non-radiative transition, which produces no optical emission, because these are indirect band gap materials. The materials used for the LED have a direct band gap with energies corresponding to near-infrared, visible, or near-ultraviolet light.

LED development began with infrared and red devices made with gallium arsenide. Advances in materials science have enabled making devices with ever-shorter wavelengths, emitting light in a variety of colors.

LEDs are usually built on an n-type substrate, with an electrode attached to the p-type layer deposited on its surface. P-type substrates, while less common, occur as well. Many commercial LEDs, especially GaN/InGaN, also use sapphire substrate.

Most materials used for LED production have very high refractive indices. This means that much of the light will be reflected back into the material at the material/air surface interface. Thus, light extraction in LEDs is an important aspect of LED production, subject to much research and development.

Refractive index[edit]

Idealized example of light emission cones in a semiconductor, for a single point-source emission zone. The left illustration is for a fully translucent wafer, while the right illustration shows the half-cones formed when the bottom layer is fully opaque. The light is actually emitted equally in all directions from the point-source, so the areas between the cones shows the large amount of trapped light energy that is wasted as heat.[43]
The light emission cones of a real LED wafer are far more complex than a single point-source light emission. The light emission zone is typically a two-dimensional plane between the wafers. Every atom across this plane has an individual set of emission cones. Drawing the billions of overlapping cones is impossible, so this is a simplified diagram showing the extents of all the emission cones combined. The larger side cones are clipped to show the interior features and reduce image complexity; they would extend to the opposite edges of the two-dimensional emission plane.

Bare uncoated semiconductors such as silicon exhibit a very high refractive index relative to open air, which prevents passage of photons arriving at sharp angles relative to the air-contacting surface of the semiconductor. This property affects both the light-emission efficiency of LEDs as well as the light-absorption efficiency of photovoltaic cells. The refractive index of silicon is 3.96 (at 590 nm),[44] while air is 1.0002926.[45]

In general, a flat-surface uncoated LED semiconductor chip will emit light only perpendicular to the semiconductor's surface, and a few degrees to the side, in a cone shape referred to as the light cone, cone of light,[46] or the escape cone.[43] The maximum angle of incidence is referred to as the critical angle. When this angle is exceeded, photons no longer escape the semiconductor but are instead reflected internally inside the semiconductor crystal as if it were a mirror.[43]

Internal reflections can escape through other crystalline faces, if the incidence angle is low enough and the crystal is sufficiently transparent to not re-absorb the photon emission. But for a simple square LED with 90-degree angled surfaces on all sides, the faces all act as equal angle mirrors. In this case most of the light can not escape and is lost as waste heat in the crystal.[43]

A convoluted chip surface with angled facets similar to a jewel or fresnel lens can increase light output by allowing light to be emitted perpendicular to the chip surface while far to the sides of the photon emission point.[47]

The ideal shape of a semiconductor with maximum light output would be a microsphere with the photon emission occurring at the exact center, with electrodes penetrating to the center to contact at the emission point. All light rays emanating from the center would be perpendicular to the entire surface of the sphere, resulting in no internal reflections. A hemispherical semiconductor would also work, with the flat back-surface serving as a mirror to back-scattered photons.[48]

Transition coatings[edit]

After the doping of the wafer, it is cut apart into individual dies. Each die is commonly called a chip.

Many LED semiconductor chips are encapsulated or potted in clear or colored molded plastic shells. The plastic shell has three purposes:

  1. Mounting the semiconductor chip in devices is easier to accomplish.
  2. The tiny fragile electrical wiring is physically supported and protected from damage.
  3. The plastic acts as a refractive intermediary between the relatively high-index semiconductor and low-index open air.[49]

The third feature helps to boost the light emission from the semiconductor by acting as a diffusing lens, allowing light to be emitted at a much higher angle of incidence from the light cone than the bare chip is able to emit alone.

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