lunes, 22 de marzo de 2010

El superconductor de alta temperatura más delgado: una capa monoatómica de un cuprato






Los cupratos están formados por capas alternas. ¿Cuántas capas planas son necesarias para observar la superconductividad? Sólo una. Un nuevo estudio experimental publicado en Science ha observado la superconductividad con una Tc de 32 K en una película "bicapa" con una sola capa metálica, dopada con zinc, LCZO, y una sola capa aislante, LCO. El dopado con zinc de toda la película de cuprato, elimina completamente la superconductividad. Cuando sólo se dopan ciertos planos, la temperatura crítica se reduce de 32 K a solo 18 K. Logvenov y sus colegas han dopado con zinc un solo plano de una "bicapa" y han observado que la Tc se mantiene en 32 K. Interpretan su experimento como que el origen de las superconductividad se encuentra en la capa monoatómica que hace de interface entre ambas capas de la bicapa, la metálica y la aislante. Han fabricado esta estructura utilizando la técnica de epitaxia por haces moleculares (MBE). El trabajo es un gran avance experimental que no sólo aporta gran información para los teóricos sino que además tendrá múltiples aplicaciones que requieren capas superconductoras ultradelgadas. El artículo técnico es G. Logvenov, A. Gozar, I. Bozovic, "High-Temperature Superconductivity in a Single Copper-Oxygen Plane," Science 5953: 699-702, 30 October 2009. Se han hecho eco de este artículo en "High-temperature superconductor goes super thin," Physics Today, Nov 2, 2009.
Estudiar si una sola capa de un cuprato puede ser superconductora es difícil porque una capa ultradelgada presenta defectos superficiales que reducen la temperatura crítica como la rugosidad superficial o la interdifusión de cationes con el substrato. En superconductores de la familia de los La-Sr-Cu-O, la temperatura crítica más alta observada en películas delgadas era de unos 10 K en películas formadas por 4 planos de óxido de cobre superconductores. En capas biatómicas de plomo se observó la superconductividad convencional (BCS) este año ("Superconductividad observada en capas biatómicas de plomo," 7 Mayo 2009).

Descubrir el secreto de la superconductividad de alta temperatura crítica le quita el sueño a muchos investigadores. Un fenómeno polifacético del que cada día descubrimos nuevas caras. Los cupratos están formados por capas alternas (los pnicturos también). Muchos teóricos piensan que el origen de la superconductividad de alta Tc está en dicha estructura en capas planas. Han dopado una a una las capas de una película ultradelgada de cuprato para obtener la estructura de la figura: con 6 capas metálicas (LSCO), una capa aislante LCO, una metálica LCZO y 4 aislantes (LCO). La adición de zinc a una capa de óxido de cobre reduce la Tc en dicha capa a sólo 18 K (dopar todas las capas, la destruye). El nuevo estudio ha mostrado la estructura superconductora más delgada conocida, con una sola capa con un grosor de 3 celdas unidad de la estructura cristalina que es superconductora con una temperatura de transición de 32 K. Un trabajo espectacular y necesario desde que se descubrió que algunos pnicturos son superconductores tridimensionales, a diferencia de los cupratos y el resto de los pnicturos. Cada día el secreto de los superconductores de alta Tc está más próximo.

Fuente: http://francisthemulenews.wordpress.com/2009/11/03/el-superconductor-de-alta-temperatura-mas-delgado-una-capa-monoatomica-de-un-cuprato/
Nombre: Franklin Quintero
Asignatura EES


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domingo, 21 de marzo de 2010

EPITAXIA DESDE LA FASE LÍQUIDA

Durante muchos años se han hecho investigaciones respecto a dispositivos semiconductores y sus comportamientos, los diversos procesos de crecimientos usados, pero el que nos interesa utilizar tiene varias ventajas frente a otros procesos de crecimiento y la más relevante es la calidad cristalográfica que se obtiene. 


El sistema a emplear es la Epitaxia desde la Fase Liquida (LPE). 

Este método de crecimiento actualmente se esta reivindicando puesto que varios laboratorios en el mundo han reportado crecimientos y la obtención de dispositivos optoelectrónicos en el rango del infrarrojo medio, con bastante éxito. Sin embargo, han soslayado estudios profundos en cuanto al crecimiento y caracterización de capas epitaxiales de aleaciones binarias, ternarias y cuaternarias obtenidas por esta técnica, y aun no ha quedado claro situaciones como la aparición del defecto nativo vacancia de Galio y Galio en sitio de Antimonio) defecto complejo que se comporta como impureza, principal responsable de la conductividad tipo p del Antimonuro de Galio, entre otras. En este método, la cristalización de las capas crecidas tiene lugar a partir de una solución saturada con un material semiconductor, en la que se utiliza un solvente previamente escogido. Para el crecimiento de capas epitaxiales semiconductoras de los grupos III-V y las soluciones sólidas que se obtienen ,con frecuencia se utiliza como solvente el G, In, Sb, y en algunos casos solventes neutrales como el Sn y Pb utilizar en calidad de solvente el Ga y el In. 

Estos elementos tienen temperaturas de fusión bajas, y además entran en la composición de las películas crecidas, por lo que la necesidad de introducir dopantes se reduce al mínimo. Tanto el Ga como el In tienen presión de vapor muy baja en el intervalo de temperatura que generalmente es utilizado en el proceso de crecimiento por el método de fase líquida. 

Además, estos dos elementos se pueden obtener muy puros y a las temperaturas usuales de crecimiento ni el Ga ni el In interaccionan con el grafito, material del cual están hechos generalmente los contenedores de las fases líquidas, cabe señalar que durante l proceso es necesario tener pendiente que todo sea de una forma cuidadosa para que el crecimiento se lleve de una forma exitosa, de lo contrario el experimento fallara, por ello hay que evitar a toda costa los contaminantes que puedan dañar nuestras muestras y nuestros reactivos más adelante describiré como es que se debe dar. 

Para llevar a cabo el proceso de epitaxia es necesario conocer el correspondiente diagrama de fase que determina la relación entre las composiciones de las fases líquida y sólida a diferentes temperaturas. 

Para los compuestos binarios III-V es característico el hecho de que a la composición de la fase sólida siempre le corresponde un 50% de átomos provenientes de cada grupo que forman el compuesto. Una fase sólida de composición constante a diferentes temperaturas puede encontrarse en estado de equilibrio con una fase líquida que represente una solución de un elemento del grupo V disuelto en un metal fundido del grupo III. 

Cuando esto sucede, la solubilidad del elemento del grupo V cambia con la temperatura; demás, a las temperaturas relativamente bajas que se utilizan en los crecimientos por fase líquida, las soluciones se encuentran bien homogenizadas, es decir, que la concentración el elemento del grupo V en la fase líquida es sólo de algunas unidades porcentuales. 

En el Centro de Investigación en Dispositivos Semiconductores se cuenta con un sistema de Epitaxia desde la fase Líquida en donde se llevan trabajos de tesis de doctorado y maestría. Actualmente se desarrollan diferentes proyectos de investigación para el crecimiento y caracterización e aleaciones semiconductoras ternarias AlxGal-xSb principalmente en la búsqueda de espesores nanométricos obtenidas a bajas temperaturas.

Fuente: http://www.cids.buap.mx/Infra/epitaxia/epitaxia.html
Nombre Franklin Quintero
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Epitaxia por haces moleculares

La epitaxia por haces moleculares es una técnica habitual en el crecimiento de heteroestructuras de semiconductores por la gran perfección cristalina que alcanza. Los haces moleculares inciden sobre un sustrato y diversas reacciones químicas ocasionan la deposición de monocapas sucesivas.

 


Epitaxia por haces moleculares

Mediante el adecuado control de las especies químicas de los haces se puede variar la composición de las capas epitaxiales. Los requerimientos técnicos son elevados pues se exige un perfecto control de la temperatura y vacío en la cámara de crecimiento. 
 


Cámara de crecimiento

Fuente: http://valbuena.fis.ucm.es/expint/html/dc/dc01/mbe.html
Nombre Franklin Quintero
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Epitaxia de Feixe Molecular

la Epitaxia de Haces Moleculares es una tecnologia crítica e imprescindible porque es el primer paso esencial que permite la fabricación de diversos dispositivos electrónicos y optoelectrónicos basados en semiconductores compuestos. Los materiales crecidos por MBE se utilizan en la investigación de semiconductores compuestos tales como el arseniuro de galio, fosfuro de indio, nitruros, aleaciones de silicio (SiGe, SiC), diamante, y otros materiales avanzados (óxidos, metales, ferroeléctricos, superconductores, etc), mientras que las obleas crecidas epitaxialmente por MBE se utilizan en la fabricación masiva de dispositivos micro- y optoelectrónicos comerciales, tales como circuitos integrados IC para microondas (MESFETs , PHEMTs and HBTs), o laseres bombeados y dispositivos VCSEL utilizados en las redes de fibra óptica.


Los dispositivos basados en semiconductores compuestos disponen de algunas prestaciones clave, incluyendo su capacidad de funcionar a altas frecuencias con muy bajo consumo de potencia, al mismo tiempo que generan menos ruido electrónico y menos distorsión que los productos basados en silicio. La tecnologia MBE es la preferida para muchos semiconductores compuestos utilizados en una creciente variedad de aplicaciones de alta tecnologia para comunicaciones inalámbricas y via satélite, redes de fibra óptica de gran velocidad, computadores, sistemas de defensa, y electrónica de consumo tales como adaptadores para servicios Internet y para reproductores de disco óptico (DVD, Blue Ray).
Obleas epitaxiadas y aplicaciones




Productos

Riber diseña, desarrolla, fabrica y comercializa un amplio rango de equipos de proceso MBE y productos relacionados tanto para la investigación de materiales semiconductores compuestos como en la producción masiva de obleas epitaxiadas. Riber también propone máquinas UHVCVD para la deposición CVD (chemical vapor deposition) en ultra alto vacío para I/D en técnicas de crecimiento epitaxial aplicadas a la fabricación de semiconductores compuestos basados en germanio-silicio.

Además de los sistemas MBE, se dispone de un amplio rango de componentes relacionados con la técnica MBE. Esto incluye células de efusión, "valved crackers", sistemas de control de flujo de gas e inyectores "valved", controladores de proceso así como componentes UHV tales bridas para sistemas de fuentes MBE, calefactores de sustrato, obturadores de flujo del haz, paneles criogénicos.

Servicios
Durante 25 years, Riber ha instalado mas de 450 sistemas mundialmente. El centro Customer Service proporciona un rápido servicio postventa y servicio de actualización para esta base de equipos instalados, estando soportado por 28 centros regionales de atención al cliente. Todos los centros incorporan personal experto en MBE y mantienen en stock piezas de repuesto. Riber ofrece soporte adicional a través de su propio Applications Laboratory, que está dedicado a la cualificación de componentes y accesorios MBE.
También se proporciona formación y soporte sobre crecimiento a los usuarios bajo la supervisión de licenciados altamente cualificados. Hoy en día Riber está jugando un papel destacado liderando el desarrollo y la promoción de la tecnología MBE a través de colaboraciones y proyectos I/D conjuntos con importantes socios a nivel mundial.

Fuente:http://www.semiconductor-today.com/news_items/2009/NOV/MIEUNI_271109.htm
Nombre Franklin Quintero
Asignatura EES


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MOVPE

MOVPE es el desafío más crítico en términos de gestión de gases de escape. La combinación de caudales del orden de litros por minuto de AsH3 y PH3, el predominio del hidrógeno y la alta deposición de fósforo blanco autoinflamable en las líneas de efluentes no es superada por ningún otro proceso utilizado en fábricas de semiconductores de silicio o compuestos


MOVPE
Características y ventajas
El reto especial que representa la aplicación de MOVPE se refleja en varias características exclusivas de la línea de productos absorbentes en lecho seco "CLEANSORB" de CS CLEAN SYSTEMS:
Todas las conexiones de gas están dentro de un módulo con extracción de aire
Todas las tuberías son de acero inoxidable
El sistema sigue funcionando durante cortes de energía
Detector de gas de referencia
Monitor de temperatura de matriz IR
Reoxidación (pasivación) de la columna absorbente
Miniabsorbente de derivación
Válvula de derivación automática
Enfriamiento forzado por columna de N2 ante sobrecalentamiento
Válvulas de entrada y salida que aíslan del proceso

Fuente: http://www.cscleansystems.com/applications_movpe.html?setlang=es-es&PHPSESSID=99c3abb1ccfb1a89f3142df0ceb5c17c
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Thickening aluminum nitride layers on sapphire substrates


Japan's Mie University has been investigating various ways to deposit thick layers of aluminum nitride (AlN) on sapphire substrates using hydride vapor phase epitaxy (HVPE) [Jiejun Wu et al, Appl. Phys. Express, vol.2, p.111004, 2009].
The research group believes AlN is promising as the basis for ultraviolet (UV) LEDs and high-electron-mobility transistors (HEMTs). UV radiation has important medical applications and, in combination with suitable phosphors, could be used as the driver of white-light modules. 
However, thick AlN layers are difficult to grow with the high quality that is needed for such applications. In the x-ray diffraction characterization of such layers, some peaks can have full-width at half maximum (FWHM) values of ~1000arcsec, indicating poor quality. 
In fact, the large FWHMs in AlN layers seem to arise from edge-type threading dislocations (TDs), as indicated by the asymmetric (10.2) and (10.0) planes giving rise to broad reflection peaks, while symmetric ones such as (00.2) can be as small as 100arcsec. Edge TDs have a far bigger impact on device performance compared with screw TDs.
Epitaxial lateral over-growth and related techniques have been used to decrease densities of TDs in both GaN and AlN layers. However, these techniques are complex and expensive. The Mie group therefore wants to develop simple methods for growing thick AlN layers.
As a preliminary to this, the researchers sought to understand the reasons for the dislocations. First, growing c-plane AlN on c-plane sapphire allows the initial islands of AlN crystal material to be twisted relative to each other. When these islands coalesce, edge TDs can occur (Figure 1, top). 
Growing c-plane AlN on a-plane sapphire (making the two c-axes perpendicular) reduces this twisting effect (Figure 1, bottom). While the tendency for neighboring AlN islands to have different out-of-plane tilts is increased, this can be controlled with suitable optimization of growth temperature and III/V element ratios.
Figure 1 (above): Schematics of twist and tilt variations between AlN islands grown on c-plane (a) and a-plane (b) sapphire.
The researchers also comment that a-plane sapphire has a smaller lattice mismatch with AlN and that easy cleavage along the r-plane would be convenient for the construction of laser diode facets.
The researchers used HVPE at low pressure (5kPa) to grow c-plane AlN on c-plane (00.1) and on a-plane (11.0) sapphire. The material sources were ammonia (NH3), Al and hydrogen chloride (HCl). The sapphire surface was prepared with a thermal clean in hydrogen for 10 minutes at 1150°C. The AlN was grown at 1350-1550°C. No buffers or interlayers were used. Optimized conditions for AlN growth varied for the different sapphire orientations: for (00.1)/c-plane sapphire, 1400°C with a V/III ratio of 200; for (11.0)/a-plane, 1500°C with the V/III ratio set at 600.
The resulting XRD measurements suggest a lower edge-type TD density for the a-plane sapphire growth, although the screw TD density increased somewhat. In particular, the asymmetric (10.2) and (10.0) peaks had FWHMs of 487 and 636arcsec, respectively, for the a-plane sapphire grown sample, while the c-plane sample recorded 752 and 927arcsec, respectively. The symmetric (00.2) reflection was 312arcsec for the a-plane sample, but only 176arcsec for the c-plane sample.
From these figures, the Mie group derives a rough estimate for edge and screw TD densities of 2.7x108 and 2.6x107/cm2, respectively, for the a-plane sample, and 5.8x108 and 8.1x106/cm2, respectively, for the c-plane sample. It was also found that the window for off-optimum growth while maintaining reasonable crystal structure was wider for the a-plane compared with c-plane growth.
The researchers also studied cracking effects in the AlN layer. They were able to maintain crack-free AlN growth on a-plane sapphire beyond 3.6μm thickness (Figure 2), while cracks appeared in material grown on c-plane sapphire at 1.8μm. Cracking did occur on a-plane sapphire with a 4μm-thick AlN layer, but the density of cracks (25.5/cm) was a factor of five lower than that for the 1.8μm layer on c-plane sapphire (145.9/cm).
















Figure 2: Optical microscope images of AlN grown on a-plane sapphire: crack-free 3.6μm layer (a), and cracking in a slightly thicker 4μm layer (b). On c-plane sapphire, a relatively thin 1.8μm layer exhibits cracks (c).
The a-plane sapphire sample showed cracks in only one direction, which the Mie researchers explain in terms of the larger thermal expansion coefficient of sapphire parallel to the c-axis, compared with the perpendicular direction.

Fuente: http://www.semiconductor-today.com/news_items/2009/NOV/MIEUNI_271109.htm
Nombre Franklin Quintero
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Metalorganic vapour phase epitaxy

(MOVPE) is a chemical vapour deposition method of epitaxial growth



of materials, especially compound semiconductor
Epitaxy
Epitaxy refers to the method of depositing a monocrystalline film on a monocrystalline substrate. The deposited film is denoted as epitaxial film or epitaxial layer. The term epitaxy comes from the Greek roots epi, meaning "above", and taxis, meaning "in ordered manner". It can be translated "to...

s from the surface reaction of organic compound
Compound semiconductor
A compound semiconductor is a semiconductor compound composed of elements from two or more different groups of the periodic table . For groups 13-15 ,...


s or metalorganics
Organic compound
An organic compound is any member of a large class of chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of compounds such as carbonates, simple oxides of carbon and cyanides, as well as the allotropes of carbon, are considered inorganic...


and metal hydrides containing the required chemical element
Metalorganics
Metalorganic compounds are a class of chemical compounds that contain metals and organic ligands. Metalorganic compounds are used extensively in materials science in applications such as metalorganic vapour phase epitaxy or sol-gel processing using alkoxides...


s. For example, indium phosphide could be grown in a reactor on a substrate by introducing Trimethylindium
Chemical element
A chemical element is a pure chemical substance consisting of one type of atom distinguished by its atomic number, which is the number of protons in its nucleus. The term is also used to refer to a pure chemical substance composed of atoms with the same number of protons.Common examples of elements...

((CH3)3In) and phosphine
Trimethylindium
Trimethylindium , In3, is the preferred metalorganic source of Indium for metalorganic vapour phase epitaxy of indium-containing compound semiconductors, such as InP, InAs, InN, InSb, GaInAs, InGaN, AlGaInP, AlInP, AlInGaNP etc. TMI is a white, crystalline and sublimable solid, with...


(PH3). Alternative names for this process include organometallic vapour phase epitaxy (OMVPE), metalorganic chemical vapour deposition (MOCVD) and organometallic chemical vapour deposition (OMCVD). Formation of the epitaxial layer occurs by final pyrolisis of the constituent chemicals at the substrate surface. In contrast to molecular beam epitaxy
Phosphine
Phosphine is the common name for phosphorus trihydride , also known by the IUPAC name phosphane and, occasionally, phosphamine. It is a colorless, flammable gas with a boiling point of −88 °C at standard pressure...


(MBE) the growth of crystals is by chemical reaction and not physical deposition. This takes place not in a vacuum
Molecular beam epitaxy
Molecular beam epitaxy , is one of several methods of depositing single crystals. It was invented in the late 1960s at Bell Telephone Laboratories by J. R. Arthur and Alfred Y. Cho.-Method:...


, but from the gas
Vacuum
In everyday usage, vacuum is a volume of space that is essentially empty of matter, such that its gaseous pressure is much less than atmospheric pressure. The word comes from the Latin term for "empty," but in reality, no volume of space can ever be perfectly empty...


phase at moderate pressure
Gas
This page is about the physical properties of gas as a state of matter. For the uses of gases, and other meanings, see Gas .A gas is one of four states of matter. Near absolute zero, a substance exists as a solid...


s (2 to 100 kPa
Pressure
Pressure is the force per unit area applied in a direction perpendicular to the surface of an object. Gauge pressure is the pressure relative to the local atmospheric or ambient pressure.- Definition :...


). As such this technique is preferred for the formation of devices incorporating thermodynamically metastable alloys. It has become the dominant process for the manufacture of laser diodes, solar cells, and LEDs
Pascal (unit)
The pascal is the SI derived unit of pressure, stress, Young's modulus and tensile strength. It is a measure of force per unit area, defined as one newton per square metre...


.
LEDS
LEDS can be initials for:* Law Enforcement Data System* Link Eleven Display System* Low Energy Dislocation Structure* Land Electronic Defence System * LEDs * Life-Events and Difficulties Schedule...


Reactor components

  • A reactor is a chamber made of a material that does not react with the chemicals being used. It must also withstand high temperatures. This chamber is composed by reactor walls, liner, a susceptor


    Susceptor
    A susceptor is a material used for its ability to absorb electromagnetic energy and convert it to heat . This energy is typically radiofrequency or microwave radiation used in industrial heating processes, and also occasionally in microwave cooking...
    Glass
    In general Glass refers to a solid, brittle, transparent material, commonly used for windows, bottles, or eyewear. Examples of glassy materials include, but are not limited to, soda-lime glass, borosilicate glass, acrylic glass, sugar glass, Muscovy-glass, or aluminium oxynitride. The term glass...
    Graphite
    The mineral graphite is one of the allotropes of carbon. It was named by Abraham Gottlob Werner in 1789 from the Greek γραφειν : "to draw/write", for its use in pencils, where it is commonly called lead, as distinguished from the actual metallic element lead...

    , gas injection units, and temperature control units. Usually, the reactor walls are made from stainless steel or quartz. To prevent over heating, cooling water must be flowing through the channels within the reactor walls. Special glass


    es, such as quartz or ceramic, are often used as the liner in the reactor chamber between the reactor wall and the susceptor. A substrate sits on a susceptor which is at a controlled temperature. The susceptor is made from a material resistant to the metalorganic compounds used; graphite


    is sometimes used. For growing nitrides and related materials, a special coating on the graphite susceptor is necessary to prevent corrosion by ammonia (NH3) gas.

  • Gas inlet and switching system. Gas is introduced via devices known as 'bubblers'. In a bubbler a carrier gas (usually nitrogen


    Nitrogen
    Nitrogen is a chemical element that has the symbol N and atomic number 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless and mostly inert diatomic gas at standard conditions, constituting 78% by volume of Earth's atmosphere.Many industrially important...
    Hydrogen
    Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. At standard temperature and pressure, hydrogen is a colorless, odorless, nonmetallic, tasteless, highly flammable diatomic gas with the molecular formula H2...
    Liquid
    Liquid is one of the principal states of matter. A liquid is a fluid that has the particles loose and can freely form a distinct surface at the boundaries of its bulk material. The surface is a free surface where the liquid is not constrained by a container....
    Temperature
    In physics, temperature is a physical property of a system that underlies the common notions of hot and cold; something that feels hotter generally has the higher temperature. Temperature is one of the principal parameters of thermodynamics...

    or hydrogen


    ) is bubbled through the metalorganic liquid


    , which picks up some metalorganic vapour and transports it to the reactor. The amount of metalorganic vapour transported depends on the rate of carrier gas flow and the bubbler temperature


    . Allowance must be made for saturated vapours.
  • Pressure maintenance system
  • Gas Exhaust and cleaning System. Toxic waste products must be converted to liquid or solid wastes for recycling (preferably) or disposal. Ideally processes will be designed to minimize the production of waste products.
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Nitride Semiconductors for High-Performance Blue and Green Light-Emitting Devices

Nitride Semiconductors for High-Performance Blue and Green Light-Emitting Devices

Most of the rapid developments in (AlIn)GaN alloy system technology have occurred within the past few years, and the technology is still moving at a fast pace. New performance records for light-emitting diodes and laser diodes are constantly being reported. This article highlights the progression of the development of the (AlIn)GaN alloy system and describes the fabrication and performance of some of the light-emitting devices that have been produced to date.
Since the invention of the incandescent electric lamp by Thomas Edison in 1879, there has been a drive for less expensive, more reliable, and brighter lighting sources. Massive industries have been created to produce filament and fluorescent lamps for interior applications, sodium-discharge lamps for streets, and neon signs for ever-popular exterior advertising. The most recent revolutionary lighting advancement is the light-emitting diode (LED). Initially demonstrated in 1962, the LED1 and its companion, the laser diode (LD),2,3 have been used in such diverse applications as optical-fiber communication networks, instrument-panel indicators, CD optical-storage technology, laser printers, and automobile tail lights and brake lights. Originally restricted to the color red, yellow, orange, and amber LEDs with light-emission efficiencies superior to incandescent lamps became commercially available by the early 1990s,4 spawning a market valued at well over $1 billion a year.5 That market is expected to undergo tremendous growth as LEDs continue to infiltrate the full-color outdoor display, traffic signal, and automotive interior and exterior lighting markets.
While the technological growth of red and yellow LEDs has been meteoric in the past decade, the push to extend operation into the short wavelength region of the visible spectrum (from green to violet) has proven very challenging. Although successful attempts to make LEDs and LDs with SiC and II-VI materials (e.g., ZnSe) have been made, the utility of such devices has been diminished by the very low efficiency in SiC diodes and the short device lifetimes in the II-VI materials due to the relative ease of defect formation. As a result, the III-V nitride materials with the wurtzite crystal structure (GaN, AlN, InN, and their alloys) have generated considerable interest for operation at these wavelengths. Since the electronic band structure for each of the nitride materials possesses a direct transition with a band gap energy ranging from 1.9 eV for InN, to 3.4 eV for GaN, to 6.2 eV for AlN at room temperature as well as a fairly high thermal conductivity, the (AlIn)GaN system has been explored in the areas of high-power and high-temperature electronic devices and short-wavelength (visible and ultraviolet) optoelectronic devices. (For an excellent review of relevant properties, consult Reference 6.)
Considerable efforts to produce and characterize the nitrides began in earnest more than 30 years ago at a number of notable research facilities, such as AT&T Bell Laboratories, IBM Thomas J. Watson Research Center, and RCA, because of the potential for producing surface acoustic wave devices, blue lasers, and LEDs. Most of these programs, however, were eventually canceled due to the inability to solve several key technological problems that hampered development. Since there was no suitable bulk-crystal technology for producing GaN substrates, epitaxy was done on highly lattice- and thermal-expansion-mismatched substrates such as silicon, gallium arsenide, and sapphire. The resulting heteroepitaxial films were invariably highly defected with ~1010 dislocations/cm2 and highly conducting as a result of defects and impurities. The films also exhibited poor surface morphology as a result of a nonoptimized growth approach. The high n-type background, coupled with the relatively deep ionization levels of common p-type impurities, resulted in an inability to grow p-type material and prevented the development of bipolar and injection-type devices. Despite these problems, the fabrication of metal-insulator-semiconductor LEDs was achieved, thus demonstrating the potential for this material system.7
It was not until the mid-1980s that these problems began to be overcome, due in large part to the efforts of Isamu Akasaki at Nagoya and Meijo Universities and a group led by Shuji Nakamura at Nichia Chemical Company. The use of thin, low-temperature AlN8 and, later, GaN9 buffer layers facilitated the growth of high-quality GaN films, specular and free of cracks, on sapphire substrates by metalorganic chemical vapor deposition (MOCVD). Simultaneously, remarkable improvements in the electrical and optical properties were demonstrated. Another monumental breakthrough was the first successful production of p-type GaN by low-energy electron-beam irradiation (LEEBI) of magnesium-doped GaN, which in the as-grown state exhibits high resistivity.10 As a result, the first GaN electroluminescent device based on a p-n junction was demonstrated. Subsequently, it was shown that magnesium-doped GaN could also be made conductive by thermal annealing in a N2 ambient at a temperature of about 600°C.11
These developments, along with the fact that light-generation processes in the nitride material seem unaffected by the high dislocation density commonly found in the epitaxial films, have allowed the demonstration and commercialization of high-brightness blue and green double heterostructure12 and single quantum well (SQW)13 LEDs in the past few years as well as the demonstration of the first violet (~420 nm) room-temperature, continuous-wave (CW) LD in 1996.14 When combined with the red, orange, and yellow LEDs and LDs, these breakthroughs set the stage for another photonic technology revolution.

EPITAXIAL GROWTH

Several techniques have been used for the epitaxial growth of III-V nitride semiconductors. Among these techniques, molecular-beam epitaxy and MOCVD have been the most popular, mainly due to their wide use in the fabrication of most III-V compound semiconductors. However, MOCVD may be more suitable for high-volume production for this material system for two reasons: higher throughput (lower cost) and demonstrated superior material quality.8,15-18
In an MOCVD process, the film is deposited through a chemical reaction occurring between metalorganic precursors and hydrides on a hot substrate surface. In the case of (AlIn)GaN crystal growth, TMGa, TMAl, and TMIn are normally used as group III precursors, while NH3 is used as a nitrogen source. GaN, for example, can be grown by introducing TMGa and NH3 simultaneously into the reaction chamber with a substrate, such as sapphire, heated to elevated temperatures (usually 800-1,000°C). Ternary compounds such as AlGaN and InGaN can be obtained by blending TMAl or TMIn simultaneously with TMGa. The solid composition is controlled by adjusting the gas-phase composition of the TMAl and TMGa or the TMIn and TMGa.
Although the MOCVD epitaxial growth principle is simple, researchers faced several challenges in the 1980s to achieve device-quality nitride thin films. One of the difficulties was that ammonia is a very stable molecule, and its cracking efficiency is low. In order to maintain the solid stoichiometry in the grown film, very high ammonia partial pressure in the growth ambient is required. Usually, a high volume of ammonia and a high growth temperature (enhancing thermal decomposition) are used in the growth process. However, when the growth ambient (usually a mixture of ammonia and hydrogen) consists of a high concentration of ammonia (normally 50%), physical properties of the ammonia will have a dominant effect on the flow dynamics in the reactor. This is not the case for the MOCVD growth of other III-V compounds such as GaAs or InP, where the concentrations of AsH3 and PH3 in the reactor are in the 0.01% range in a hydrogen ambient. Because ammonia has a higher density and a much lower thermal conductivity than hydrogen, the flow is apt to be turbulent (large Reynolds number). The situation becomes even worse at high growth temperatures where thermal convection can cause even more turbulent flow.
Figures 1a and 1b

In early 1990, Nakamura et al.16 reported a novel two-flow reactor design that addressed this problem (Figure 1). The source gases (main flow) were introduced parallel to the substrate surface similar to the conventional horizontal reactor. A second flow (subflow) consisting of equal amounts of N2 and H2was introduced from above, perpendicular to the substrate surface, to suppress any thermal convection arising from the heated substrate (1,000°C) and to bring the reactants toward the substrate surface. Without the subflow, the growth was not two-dimensional, and only GaN islands were formed.
A second problem for growing III-V nitride films is the lack of a suitable substrate that matches the lattice constant and thermal-expansion coefficient of the GaN films. In the mid-1980s, the Japanese research group led by Akasaki at Meijo University developed a two-step MOCVD process using a c-plane sapphire substrate. They grew a thin (200Å) AlN buffer layer at low temperature followed by a high-temperature thick layer of GaN.8 Mirror-like GaN films with improved optical and electrical properties were obtained. The use of the thin buffer layer was believed to enhance the two-dimensional nucleation so that a layer-by-layer growth mechanism could be achieved. In early 1990, Nakamura and coworkers at Nichia Chemical Company used a similar approach in which a GaN buffer layer was grown at low temperature.9 High-quality n-type GaN films were achieved with background carrier concentrations of 4 x 1016cm-3 and Hall mobilities around 600 cm2/V · s, despite high dislocation densities of 109-1010 cm2 in the films.
Heteroepitaxially grown GaN films on sapphire substrates contain high densities of structural line and planar defects. The structural properties of these layers have been extensively studied with transmission electron microscopy.19,20 Most dominant are threading dislocations that are nearly parallel to the c axis. Their density ranges between 108 dislocations/cm2 and 1010 dislocations/cm2 even after several micrometers of film growth.19 Depending on the substrate preparation, stacking faults and edge dislocations are present near the interface with the sapphire substrate.20 Inversion domain boundaries have also been reported for III-V nitrides in the literature.21 These structural defects are generated due to the small lattice constants of III-V nitrides resulting in a large lattice (~14%) and thermal-expansion-coefficient mismatch (~80%) with sapphire.19 In planar-view transmission electron micrographs taken several micrometers away from the GaN/sapphire interface, the threading dislocations tend to appear in cellular arrangements suggesting a columnar or cell-type structure of heteroepitaxial GaN films.
ontrary to other materials used for minority-carrier optoelectronic device applications, such as III-V arsenides or III-V phosphides, where dislocation densities above 104 cm-2 adversely affect the device performance, the realization of bright LEDs with long life is possible with III-V nitrides.13 It has been demonstrated that threading dislocations cross through the InGaN active layer of high-performance blue LEDs, which exhibit external quantum efficiencies as high as ~3% at 20 mA.22 It appears that dislocations in III-V nitrides are not associated with electrically active defects that would act as effective nonradiative recombination centers and effectively limit the lifetime of minority carriers.
For blue and green LEDs, InGaN films with high indium content are required. Nakamura and coworkers describe the growth of high-quality InGaN films23 by adjusting the growth rate and growth temperatures to optimize material quality and emission wavelength.
With all the building blocks available, high-efficiency commercial blue and green nitride-based LEDs are currently available from more than one source. The brightest devices use either a single or multiple quantum well structure (Figure 2). A typical complete device structure consists of a low-temperature deposited GaN or AlN buffer layer on c-plane sapphire, a 3-4 µm silicon-doped GaN layer, a SQW or multiple quantum well (MQW), a 1,000Å magnesium-doped AlGaN layer, and a 3,000Å magnesium-doped GaN layer.

N- AND P-DOPING OF III-NITRIDES

The formative stage of any semiconductor device technology requires the selection and characterization of dopants. Both impurities and native defects may act as donors or acceptors and affect the electrical conductivity of semiconductors. The species of dopant is chosen to best achieve the desired device performance, and controlled introduction of the dopant is required for reproducible characteristics. Undoped GaN films are usually n-type; contamination with silicon or oxygen, which act as donors, has been identified as the reason for this. Silicon and magnesium, which substitute for gallium in the GaN lattice, are the donor and acceptor of choice for doping III-V nitrides n- and p-type, respectively.24-26 However, all devices grown with techniques that use NH3 as a nitrogen source or that furnish a hydrogen-rich ambient, such as MOCVD, require an additional, deliberate processing step to electrically activate the acceptor dopant. These processes are either LEEBI10 or thermal annealing above 600°C in an N2 ambient.11,27 It has been shown that the formation of electrically inactive acceptor-hydrogen complexes during MOCVD growth is responsible for the observed low p-type doping efficiency in as-grown GaN.28 The LEEBI or heat treatment dissociates acceptor-hydrogen complexes and, thereby, electrically activates the acceptor dopants, as has been observed for other semiconductors (e.g., GaAs:Zn).29
The conventional Hall-effect technique is a well-established, powerful tool to investigate the electrical properties of shallow dopants in semiconductors, especially when performed over a range of temperatures. The analysis of the temperature dependence of the carrier concentration enables the determination of important dopant parameters, such as the concentration and thermal activation energy for dopant ionization, and the concentration of compensating donors or acceptors.30 Properties of silicon donors and magnesium acceptors in GaN have been investigated with variable-temperature Hall-effect measurements conducted in the temperature range of 100-700 K with a magnetic field of 12.5 kG or 17 kG. Combined with secondary ion mass spectrometry (SIMS) analysis, which yields quantitative silicon or magnesium profiles in the epitaxial films when calibrated with implantation standards, detailed properties of the dopants have been determined.
Results from variable-temperature Hall-effect measurements for n-type GaN are shown in Figure 3. Sample one was unintentionally doped, and samples two through five were silicon-doped. The electron concentrations are shown as functions of the reciprocal temperature, and the electron mobilities are shown as functions of temperature. The unintentionally doped GaN film exhibits the lowest electron concentration (~5 x 1016 cm-3, 300 K) and the highest electron mobility (~650 cm2/V s, 300 K). The silicon-doped samples show higher electron concentrations and lower electron mobilities. The silicon doping level was gradually increased from sample two to sample five. Consequently, the electron concentrations increase accordingly as determined by the Hall-effect measurements. Sample five shows an electron concentration of ~2 x 1019 cm-3, which is temperature independent. Such behavior is typically observed for degenerately doped semiconductors.
The peak mobilities for the n-type GaN samples shown in Figure 3 range from 135 cm2/V s (sample five, 300 K) to 1,450 cm2/V s (sample one, 130 K) and decrease with increasing electron concentration. The solid lines in Figure 3a are the result of a least-squares fit of the charge-neutrality condition30 to experimental n(T) data of samples one through four. The fit yields parameters for a shallow donor level that is dominant in the GaN films, and modeling yields activation energies for the shallow level of 16 meV (sample one), 14 meV (sample two), 12 meV (sample three), and 7 meV (sample four). The concentration of the shallow donor level is 6 x 1016 cm-3, 2.3 x 1017 cm-3, 7.4 x 1017 cm-3, and 7.9 x 1018 cm-3 in samples one through four, respectively.
The presence of a second donor level had to be assumed to model the temperature dependence of the electron concentrations of samples one through three. The activation energy for this donor level ranges from 32 meV to 37 meV and its concentration ranges from 3 x 1016 cm-3 to 6 x 1016 cm-3, independent of the silicon doping. It is possible that this is due to oxygen substituting for nitrogen in the GaN lattice acting as a donor.
Magnesium-doped GaN samples (samples six through eight) are shown in Figure 4. The p-type conductivity for all three samples was activated by thermal annealing. The hole concentration is shown as a function of reciprocal temperature, and the hole mobility is shown as a function of temperature. Sample six exhibits the highest hole concentration and the lowest hole mobility. At 300 K, the hole concentration is ~8 x 1017 cm-3 and the mobility is only ~3 cm2/V s. The analysis of the temperature dependence of the hole concentration at temperatures above 280 K using the charge-neutrality condition30 is consistent with the presence of a single acceptor with an activation energy of ~160 meV and a concentration of ~8 x 1019 cm-3 (solid line). The elemental magnesium concentration as determined by SIMS was found to be ~1 x 1020 cm-3. For magnesium-doped GaN, good agreement is typically found between the concentration of magnesium and the concentration of the dominant-acceptor level, the latter determined by analysis of the Hall-effect data. This indicates that most of the magnesium atoms are incorporated on gallium lattice sites and act as acceptors. For samples six and seven at temperatures below ~280 K, the temperature dependence of the hole concentration is not accurately described by the ionization of an acceptor due to hopping conduction via closely spaced acceptor states. For sample eight, however, the temperature dependence of the hole concentration can be described over the entire temperature range of the Hall-effect data. The analysis reveals that the acceptor concentration of sample eight is lower than in sample six. For samples seven and eight, the acceptor concentration is ~4 x 1019 cm-3 and ~2 x 1019 cm-3, respectively; the magnesium concentration as measured by SIMS was found to be ~5 x 1019 cm-3 and ~2 x 1019 cm-3, respectively, and the acceptor activation energies were found to be ~170 meV and 175 meV, respectively.

From the analysis of the Hall-effect data, the concentration of compensating donors was found to be greater than 1018 cm-3 for all of the magnesium-doped samples of Figure 4. Possible candidates for compensating donors are the nitrogen vacancy (VN) and substitutional oxygen (ON), the latter exhibiting a strong affinity to magnesium. However, the hole concentration is only marginally affected by the presence of compensation, since the acceptor concentration in magnesium-doped GaN is typically more than one order magnitude higher than that of compensating donors.
The hole mobility is adversely affected by both the presence of compensating donors and high concentrations of acceptors. The 300 K hole mobility for samples seven and eight are ~6 cm2/V s and 15 cm2/V s, respectively. The 300 K resistivity for all three magnesium-doped GaN films depicted in Figure 4 is ~3 W cm. Such a high resistivity constituted one of the main obstacles in achieving low forward voltages in GaN light emitters. The device problem is magnified by the difficulty in forming low-resistance ohmic contacts to magnesium-doped, p-type GaN.

LED FABRICATION TECHNIQUES

The brightest (AlIn)GaN LEDs are SQW or MQW p-n junctions grown on an electrically insulating sapphire substrate, as shown in Figure 2. Although some manufacturers use conducting SiC as the substrate for the (AlIn)GaN epitaxial growth [the lattice constant of SiC is, in fact, a better match to the (AlIn)GaN epitaxial films than sapphire], up to this point, the best devices have been produced using sapphire as the substrate. In addition, blue (AlIn)GaN solid-state lasers have been demonstrated by several groups.Nichia published the first observation of stimulated emission in a room-temperature (AlIn)GaN MQW violet LD under CW current injection in 1996 (Figure 5).14 Lifetimes of these lasers have recently been reported to exceed 100 hours.
In Figures 2 and 5, the electrical contacts to the p- and n-layers are both on the top surface of the device because of the insulating sapphire substrate. Because it is difficult to obtain highly-doped, conducting p-type GaN, the current does not spread laterally within the thin p-layers. Thus, the area of the contact to the p-layer has to be maximized to promote current spreading, which, in turn, maximizes light emission and minimizes turn-on voltage and series resistance. An important consequence for LEDs on sapphire is that since most of the light generated at the junction escapes the device through the top surface, the large-area p-contact has to be made as transparent as possible outside the area where electrical bond wires are attached. Other fabrication challenges include etching (AlIn)GaN (which has a hardness and chemical inertness resembling diamond) to expose the n-layer, etching or cleaving smooth laser facets through the highly-stressed and compositionally diverse active area, thinning the sapphire without breaking the wafer, and dividing the wafer into individual devices.
No practical or reliable wet etches for the (AlIn)GaN system have been found. Polycrystalline or damaged films can be etched very slowly in hot alkali or very hot phosphoric acid solutions. Dry plasma-etch techniques31 such as reactive ion etching, electron-cyclotron resonance (ECR), inductively coupled plasma (ICP), and chemically assisted ion-beam etching (CAIBE), however, are widely used. The etch chemistries are halogen-based, containing species such as Cl2, BCl3, or SiCl4. [Some of the published chemistries contain hydrogen, which can cause acceptor passivation in (AlIn) GaN.] Typical GaN etch rates range from 0.05-0.3 mm/min. Because of the requirements for making laser facets to control the etch profiles more accurately, high-density plasmas with low ion energies (e.g., ECR, ICP, and CAIBE) are being actively investigated. Recently, low-energy-electron-enhanced etching32 of GaN has shown promise, exhibiting chemical selectivity, superior planarization, excellent etch-rate control, and lack of damage under transmission electron microscopy inspection. However, these systems are not yet available commercially.

The best blue (AlIn)GaN LEDs currently have a typical forward voltage of 3.5-3.6V when driven by a current of 20 mA (corresponding to a current density of about 50A/cm2). The best laser threshold voltage and current reported to date are 5.5 V at 80 mA (3.6 kA/cm2).33 These numbers are relatively high. One would expect the forward voltage to correspond closely to the energy bandgap in the quantum wells, about 2.8-3.0V. Lower forward voltage characteristics are essential for improving laser output and lifetime. One key is improved ohmic contact to the p-type GaN. There is no published report of low-resistance ohmic contacts to p-type GaN, although leading manufacturers and some investigators34 come close to obtaining such behavior. It is also necessary to carefully choose the metals involved because of the high ionic content of the (AlIn)GaN bonds. Unlike what happens in covalent materials such as silicon, the work function of the metal deposited on p-GaN influences the metal-semiconductor barrier. The best p-contact candidates are the high work-function metals, such as Ni, Au, Pd, and Pt, because they yield low Schottky barrier heights.35
Figure 5
Another requirement for the p contact, as described earlier, is that it be transparent to light emission, which is accomplished by making it extremely thin to minimize absorption. AuNi films less than 0.03 µm thick are commonly used to obtain at least 50% light transmission at the wavelengths of interest. Metallizations suitable for commercial applications have additional requirements, such as superior adhesion to the semiconductor, good morphology, and excellent metallurgical reliability (low film stress, no intermetallic formation, corrosion resistance, thermal stability, etc.), which increase the challenge of finding a good system.
Ohmic contacts to n-type GaN are much easier to obtain than p-type ohmic contacts and do not have to be transparent. Many donors have low enough thermal-activation energies (22 meV for silicon)36 to be mostly ionized at room temperature, and it is easy to obtain high carrier concentrations. There are a number of publications on Schottky and ohmic contacts to n-type GaN.37 Most of the ohmic systems are based on aluminum or Ti/Al.38 Other interesting systems are indium-based,39 leading to InGaN formation after rapid thermal anneal through a solid-state reaction at the contact interface. The mechanism for ohmicity then relies on bandgap engineering arguments similar to the ones motivating the use of InGaAs layers on a GaAs surface to achieve barrierless current injection.40

LED CHARACTERIZATION AND PERFORMANCE

The first reports of p-n junction blue LEDs produced from the III-nitride materials system came in 199141 with a homojunction GaN LED emitting blue light around 430 nm at an output power of 42µW at 20 mA. This blue light emission was from an impurity transition related to the magnesium-dopant in the p-GaN layer. The performance was several times higher than the best commercially available SiC blue LEDs at the time. The first GaN/InGaN/GaN double heterostructure LEDs, reported in early 1993,42 showed improved output power to 125µW at an emission wavelength of 440 nm, corresponding to the energy bandgap of the InGaN active region. Later reports in 199323 described devices with output power of more than 1,000µW and reduced operating voltage of approximately 3.6 V.
The first commercial high-brightness candela-class blue LED products were released in late 1993 by Nichia Chemical Company and were described in the literature in early 1994.12 These commercial devices employed an intentional Zn-Si impurity complex in the InGaN active region to produce blue LEDs with a broad emission spectrum centered at 450 nm. The output power was as high as 1.5 mW, corresponding to an external quantum efficiency of 2.7% and a luminous efficiency of 2.1 lumens/watt. External quantum efficiency refers to the ratio of the number of photons produced to the electrical current crossing the pn-junction, in units of photons/electron. Luminous efficiency refers to the extent of the human-eye response per unit of input power to the LED. The human-eye response43 is greatest in the green spectral region and drops as the wavelength goes to the ultraviolet or infrared regions.
By changing the epitaxial growth process slightly it was possible to produce LEDs with emission into the blue-green spectral region around 490 nm. However, there were two significant issues with these Zn-Si codoped LEDs. First, the emission wavelength blue-shifted with increasing operating current, leading to a noticeable shift in color. Second, the blue-green LEDs had a distinct whitish appearance due to the broad emission spectrum.
The current variety of high-brightness blue44 and green45 LEDs were reported during 1995. This second generation of commercial III-V nitride LED products, based on a SQW structure, dramatically improved the efficiency and the color purity for blue-green and green LEDs. Reported output power values for 450 nm blue and 525 nm green LEDs are 4.8mW and 3.0mW, respectively, corresponding to luminous-efficiency values of approximately 3.0 lumens/watt and 22.0 lumens/watt, respectively. Nichia Chemical Company of Japan has commercialized LEDs with this SQW structure and produces devices with wavelengths of 470 nm blue, 495 nm blue-green, and 525 nm green with efficiencies that significantly exceed these reported values.46 The spectral width of these commercial LEDs is significantly narrower than the first generation Zn-Si codoped LEDs and, hence, results in a greatly improved color purity or saturation. However, the shift of color with increasing operating current remains a concern for this technology.
Figure 6
With the commercialization of InGaN quantum-well LEDs in the blue through green spectral regions, there now exists solid-state light sources spanning the entire visible spectral region. Figure 6 shows the luminous efficiency versus wavelength for the current state-of-the-art in commercially visible LEDs. High-brightness LEDs in the yellow-green through red-orange spectral region are commercially produced with the AlInGaP material system47 and in the red spectral region with the transparent-substrate AlGaAs material system.48 In addition, Figure 6 shows luminous-performance values for a number of conventional light sources and the human-eye response curve (CIE curve), which describes the theoretical limit for luminous efficiency. It is readily apparent that solid-state LEDs are rapidly encroaching upon the performance levels of traditional light sources and, in most cases, significantly exceed filtered filament-based light of a specific color.
Several major markets are being addressed with these newly developed solid-state light sources. Automobile exterior lighting has been moving rapidly to incorporate transparent-substrate AlInGaP technology into high-mount stop lights and into the full amber and red-orange taillight assembly. Full-color, outdoor, changeable message signs and full-motion video displays have been adopting (AlIn)GaN and AlInGaP technologies and will continue to proliferate as costs are reduced. Traffic-signal applications have begun to incorporate red AlInGaP and AlGaAs LEDs for stop lights and are moving toward incorporating amber and blue-green LEDs to produce a completely LED-based signal head. All of these markets are rapidly expanding and will provide enormous growth opportunities in the future.
Fuente:
Nombre Franklin Quintero
Asignatura EES


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