martes, 17 de julio de 2018

Sublimacion de Silicio y formacion de microporos.



1.1.1        Sublimacion de Silicio y formacion de microporos.

En experimentos de deposicion de SiC a 1200 oC se observe la formacion de poros sobre los cuales los films depositados formaban puentes, de modo que la superficie del film se observa continua y sin defectos
It has also been shown that SiC films grow owing to the  transition of the intermediate complex into SiC. The grown  film ‘hangs’ above the cavities like a bridge over a river or a house built on piles (see figure 9). Inside the cavities,the further nucleation of SiC takes place.

Theory and practice of SiC growth on Si and its applications to wide-gap semiconductor films
S A Kukushkin and A V Osipov
J. Phys. D: Appl. Phys. 47 (2014) 313001 (41pp)
Journal of Physics D: Applied Physics
doi:10.1088/0022-3727/47/31/313001

Figure 9. SEM photomicrographs of SiC films grown on a single-crystal Si surface. (a) A 3C-SiC film grown on a Si(1 1 1) surface inclined at 4◦ from the reference plane at the growth temperature T = 1300 ◦ C (the film ‘hangs’ over the cavities like a bridge). (b) A 4H-SiC film grown on a Si(1 0 0) surface at the growth temperature T = 1250 ◦ C with the clearly visible faceting of the pores. (c) A 3C-SiC film grown on the Si(1 1 1) surface inclined at 4◦ from the reference plane at the growth temperature T = 1200 ◦ C. (d) The same photo but enlarged.

1.2        2.3 Experimento. Deposición.


Se propone aplicar el procedimiento de reducción carbotermica de silice a filmes delgados de Carbono depositados sobre sustratos de SiO2.
Seuso como sustrato una placa de Silicio tipo p dopado con Boro, cubierta con Oxido de silicio obtenido por anneado a 600 oC. Se estima que el espesor de la capa de SiO2 es de 40 nanometros. Según investigaciones anteriores se ha encontrado que a pesar de la calidad amorfa del SiO2 obtenido térmicamente, parte de ella tiene estructura cristobalita y con parámetros de red extendidos , mayores de los esperados en un cristal de SiO2 con dicha estructura. (Apartado 1.2)

1.2.1        Determinacion teorica de grueso critico.

Según estudios anteriores , las dislocaciones se presentan cuando la energía elástica acumulada en el film debido al desfase en los parámetros de red es igual o mayor a la energía de las dislocaciones mismas, la energía elástica acumulada disminuye conforme aumenta el espesor del film y es cuando se comienzan a presentar las dislocaciones.
En la parte teorica de la disertación se explican las formulas aplicadas para determinar el grueso critico del film de SiC a obtener sobre SiO2, a fin de evitar la formación de dislocaciones y defectos volumétricos.
Cálculos que están en la libreta grande
La aplicación de estos cálculos al sustrato de SiO2 y al SiC que se desea obtener da como resultado un espesor critico de 2 nanometros. 
Se determina que para obtener un film de 2 nanometros de SiC, a partir de SiO2 y C se necesita depositar 4 nanometros deCarbono y proceder a la reducción carbotermica del SiO2 para obtener un film de SiC.
Con el objetivo de verificar el tiempo de reaccion calculado se decidio hacer tres muestras con filmes de carbono de diferentes gruesos .

1.2.2        2.3.1 medición de grueso de film en AFM.

Como prueba del metodo de deposición de Carbono (high frequency magnetrón sputtering) se hicieron ejemplares de diferentes gruesos , bajo diferentes tiempos de deposición.
Con ayuda del microscopio de fuerza atómica se determinó el grosor de los filmes y se estableció una relación entre el tiempo de deposicion  y el grueso obtenido del film. A fin de controlar el grueso del film, a través del tiempo de funcionamiento del magnetron.


2.2 reacción. Cinética de reacción.



1.1         2.2 reacción. Cinética de reacción.

En investigaciones anteriores, El proceso ha sido empleado exitosamente en la síntesis de SiC usando como elementos de entrada dióxido de silicio (cuarzo) y negro de humo, carbono amorfo. Los estudios termogravimétricos han demostrado que la reacción de formación de SiC y liberación de CO comienza a temperaturas tan bajas como 800 grados centígrados.

MET_54_3_579_582 SiO2plusC - SiC

1.1.1        2.2.1 reaccion en la superficie (SiO2 + C)


Carbothermal reduction is the primary chemical process practiced commercially for the synthesis of many ceramic materials, including SiC, The overall reduction reaction can be written as:
SiO2 (s) + 3C (s) = SiC (s) + 2CO (g)                                                           (1)
DG° = 598.18 - 0.3278 T (kJ)
The standard Gibbs free energy of the above reaction decreases with increasing temperature and becomes zero at 1525 °C. However, the reaction can take place at lower temperatures when the CO partial pressure is significantly lower than atmospheric pressure. It is generally accepted that SiC is synthesized through intermediate silicon monoxide (SiO) [2]:
C (s) + SiO2 (s) = SiO (g) + CO (g)                                                                  (2)
DG° = 668.07 - 0.3288 T (kJ)
SiO (g) + 2C (s) = SiC (s) + CO (g)                                                                  (3)
DG° = -78.89 + 0.0010 T (kJ)
The standard Gibbs free energy of Reaction (3) is negative in the examined temperature range (1000 to 2000 oC), therefore theoverall reaction of SiC formation is defined by the reaction of SiO formation. It is well established that the kinetics of carbothermal reduction of SiO2 is affected by temperature [3], molar SiO2/C ratio [4], carbon and SiO2 particle size [5], and initial bulk density [6]. The effect of gas atmosphere on the carbothermal reduction of silica has been studied to a lesser extent. The SiC formation will stop when the CO partial pressure in Reaction (1) reaches  the equilibrium value. CO has to diffuse out of the reactant mixture for further reaction to take place.
Carbothermal reduction of silica involves gaseous intermediate SiO. When the reduction of quartz is carried out in Ar, SiO is initially formed at the contact points of graphite and quartz particles following the solid-solid Reaction (2), and then SiO is further reacts with carbon to form SiC following Reaction (3). SiO can also be generated by Reaction (6) which, with the decrease in the contact area between quartz and graphite, becomes a major reaction for the SiO formation. CO2 formed in Reaction (6) is converted back to CO by Boudouard Reaction (7) which is highly favoured thermodynamically within the temperature range of isothermal reduction experi ments of this investigation.
SiO2 (s) + CO (g) = SiO (g) +CO2 (g)              (6)
C (s) + CO2 (g) = 2CO (g)                       (7)
Figure 7: CO evolution rate in the temperature programmed reduction of quartz in different gas atmospheres.
In the carbothermal reduction of SiO 2 in Ar, the conversion of quartz to SiC started at 1300 °C, and
was incomplete after 270 minutes at 1500 °C.

SYNTHESIS OF SILICON CARBIDE BY CARBOTHERMAL REDUCTION OF QUARTZ IN H2-Ar GAS MIXTURES
Xiang Li1, Guangqing Zhang1, Kai Tang2, Oleg Ostrovski3 and Ragnar Tronstad
The Fourteenth International Ferroalloys Congress Energy efficiency and environmental friendliness are the future of the global Ferroalloy industry May 31-June 4, 2015 Kiev, Ukraine pag.548
2 Lee, J.G., Miller, P.D., Cutler, I.B., Reactivity of solids. Plenum Press, 1976.
3 Moshtaghioun, B.M., Poyato, R., Cumbrera, F.L., Bernardi-Martin, de S., Monshi, A., Abbasi, M.H., Karimza-deh, F., Dominguez-Rodriguez, A.,Rapid carbothermic synthesis of silicon carbide nano powders by using mi-crowave heating. J. Eur. Ceram. Soc. 32(2012), pp. 1787–1794.
4 Agarwal, A., Pal,U., Influence of pellet composition and structure on carbothermic reduction of silica. Metall. Mater. Trans. B 30(1999), pp. 295–306.
5 Martello,D. E., Tranell, G. , Gaal, S., Raaness, O.S., Tang, K., Arnberg, L.,Study of pellets and lumps as raw materials in silicon production from quartz and silicon carbide. Metall. Mater. Trans. B 42( 2011), pp. 939–950.
6 Yao,J., Wang,H., Zhang,X., Zhu,W., Wei,J., Cheng, Y.B., Role of pores in the carbothermal reduction of carbonsilica nanocomposites into silicon carbide nanostructures. J. Phys. Chem. C 111(2007), pp. 636–641.

Dado que se escogio la ruta de carboreduccion a través de monóxido de silicio se tiene que tomar en cuenta que hay una segunda reacción que descompone el SiC en monóxido de silicio y CO.
SiO2(s) + C(s) → SiO(g) + CO(g);
SiO(g) + 2C(s)
→ SiC(s) + CO(g).
The second stage consists of reactions between silica with silicon carbide which form silicon monoxide and, where conditions permit, may also form silicon metal.
The major reaction during this stage is
2SiO
2(g) + SiC(s) → 3SiO(g) + CO(g).

Biernacki, J. J. and Wotzak, G. P. (1989), Stoichiometry of the C + SiO2 Reaction. Journal of the American Ceramic Society, 72: 122-129. doi:10.1111/j.1151-2916.1989.tb05964.x
Como ambos productos son gases se espera que no permanezcan en el film obtenido. Sino que se difundan y se liberen a la atmosfera.
Hay que detener el proceso de anneado antes de que todo el SiC obtenido se volatilice.



1.1.2        2.2.2REACCION en el sustrato Si+SiO2


En la interfaz del sustrato y el SiO2 sucede una reaccion que genera vapor de SiO

By generating SiO vapor from the silicon reduction of silica (SiO2 ) [28, 29, 32] as illustrated by equation (1.3).
Si (solid) + SiO2 (solid)
→ 2SiO (vapor) (1.3)
Moreover, some amount of silica (SiO2 ) was also found in the sample. It was
suggested that SiO vapor decomposed into SiO2 , according the following equation:
2 SiO (vapor)→ SiO2 (solid) + Si (2.2)
*SYNTHESIS AND CHARACTERIZATION OF a-SILICON CARBIDE NANOSTRUCTURES
Enagnon Thymour Legba  University of Kentucky, etleg0@engr.uky.edu
2.2 SYNTHESIS AND CHARACTERIZATION OF a-SILICON CARBIDE NANOSTRUCTURE.pdf
Recommended Citation
Legba, Enagnon Thymour, "SYNTHESIS AND CHARACTERIZATION OF a-SILICON CARBIDE NANOSTRUCTURES".
(2007). University of Kentucky Master's Theses. 494.



reduccion carbotermica del sílice



  1 SiO2 + C reduccion carbotermica del sílice

Silicon carbide (SiC) is a very attractive material for the fabrication of microelectronic and optoelectronic devices due to its wide bandgap, high thermal conductivity, excellent thermal and chemical stability and its resistance to radiation damage and electrical breakdown [1]. SiC has over 170 different polytypes [2]. The most common forms are 4H, 6H, known as the hexagonal (α-SiC) types, and the cubic 3C-SiC type [2-5]. Among the various polytypes, the 3C-SiC variety possesses unique properties, including a high electron mobility up to 1000 cm2/Vs and a consequent high saturation drift velocity. 

1.1        критическая толщина


Es importante la obtención de filmes de SiC de alta calidad y sencillez de obtención, ya que se puede aplicar en Celdas solares, sensores y componentes electrónicos.
Una problemática diferente es la cuestión de la deposición de filmes delgados en sustratos apropiados de silicio, ya que habitualmente el error entre los parámetros de red del sustrato y de los Filmes de SiC supera el 15%, provocando tensiones tendientes a liberarse  mas alla del grueso critico del film como dislocaciones.  
Crystallographic defects give rise to residual stresses in the crystals. The stresses can occur through a variety of mechanisms in SiC crystals.
Se propone el uso de buffer layer de SiO2, térmicamente obtenido en la superficie del Silicio por anneado a 600 oC , lo que permitiría , al mismo tiempo , la reaccion entre Carbono y sílice , mientras que las tensiones residuales en el film serian menores, dado el menor desfase en los parámetros de red del SiO2 y el C.

1.2         2.2 El SiO2 obtenido por anneado de placas de Silicio.



ECS Journal of Solid State Science and Technology, 4 (8) N96-N98 (2015)
Structural Analyses of Thin SiO2 Films Formed by Thermal Oxidation of Atomically Flat Si Surface by Using Synchrotron Radiation X-Ray Characterization
Kohki Nagata, Atsushi Ogura, Ichiro Hirosawa, Tomoyuki Suwa, Akinobu Teramoto, Takeo Hattori, and Tadahiro Ohmid.

Thin SiO2 films were fabricated on the Si (001) substrate.
thermal oxidation was carried out in a pure oxygen atmosphere with three different temperatures. We prepared a SiO2 sample grown with an 800◦ C process for 82 min, with a 900◦ C process for 13 min and with an 1100◦ C process for 30 sec. These thicknesses of SiO2 films were approximately 7 nm.

Figure 3a shows the GIXRD profiles obtained for the SiO2 film formed in the highly pure oxygen atmosphere at 900◦ C. A sharp diffraction peak at 2θ = 17.6◦ was apparently observed with a broad amorphous peak. In addition, a weak diffraction peak at 2θ = 28.0◦ was also observed in single logarithmic plot of intensity which emphasize weak peak (Fig. 3b). The difference in the azimuthal angle between the two peaks was approximately 18◦ , which confirms that the peaks correspond to the (110) and (120) diffractions of the alpha-cristobalite. These results indicate that the thin SiO2 film has a partially crystalline structure with an amorphous component and that the crystalline structure maintained a preferential orientation. The alpha-cristobalite-like structure in bulk region of thick SiO2 film has also been reported in previous research.7 Cristobalite-like structure take over crystalline periodicity of crystalline Si after oxidation process. It was considered that homogeneous oxidation reaction should be essential to maintain the partially crystalline structure.
In addition, in-plane lattice constants estimated from diffraction angles indicated a = b = 5.7 Å. They were larger than those of conventional alpha-cristobalite,25 implying the crystalline-like structure in thin SiO2 film was distorted isotropically. These results indicated that an alpha-cristobalite-like structure was formed by reflecting the crystalline structure of the Si substrate.
La presencia de cristobalita deformada ha sido identificada en otros trabajos.
The atomic arrangement is essentially the same as that of the B-cristobalite structure of the cubic system, except that it is tetragonally deformed: the lattice is elongated along the c axis so as to fit the lateral lattice spacing to that of the Si substrate [7] and to keep the bond distance between the Si and 0 at about 1.6 A.

1993 J. Phys.: Condens. Matter 5 6525
X-ray diffraction evidence for epitaxial microcrystallinity in thermally oxidized Si02 thin films on the Si(OO1) surface.
Isao Takahashi, Takayoshi Shimura and Jimpei Harada
Department of Applied Physics, Nagoya University, Chiiusa-ku, Nagoya 46461, Japan