Semi Conducting &amp Magnetic Materials Week 3 Feb 7 2012

Semi-conducting & Magnetic Materials
MT41016
Prof S. B. Sant Department of Metallurgical & Materials Engineering IIT Kharagpur

Emission of light Electron excited state reverts back to lower energy state.
Happens with emission of photons (light) & phonons (heat). Luminescence If this occurs in nanoseconds fluorescence If microseconds or milliseconds phosphorescence
Photoluminescence photons impinge on a material remits light at lower energy Electroluminescence emission of light as a consequence of electric field Cathodoluminescence light emission by the showering of electrons of high energy.

Stimulated Emission - LASER Light Amplification by Stimulated Emission of Radiation E2 E1
h 21
Two energy levels, E1 and E2 Higher energy level more electrons Assume electrons made to stay some time at that level. E1 emitting a photon In time, one of them, will E2 with energy h 21 This photon might stimulate another electron to E2 E1 The photons can be in phase coherent emission - Avalanche effect Highly Intense Monochromatic Strongly Collimated How Optical Pumping external light absorption Xe flashlamps pulse lasers

Stimulated Emission - LASER
Device current ~ 5 mA at ~ 3V Input power ~ 15 mW, 33%-95% (L.D.) Power density ~ 300-600 W/cm2 Sunlight intensity ? ~100 mW/cm2
2 major Designs for Laser Diodes

Energy Bands in Crystalscontd.

Energy Bands in Crystalscontd. pn junction
Electrons drift and diffuse across a junction between unlike materials

Energy Bands in Crystalscontd. pn junction C.B.
V.B.
C.B.
V.B.
Difference in Fermi Energies before contact establishes a band bending edge and a contact potential Vbi after contact.

Band diagrams for (a) n-type whose surface is negatively charged (b) p-type whose surface is positively charged. Assume that the surface of an n-type SC has somehow been negatively charged will repel the free electrons near the surface leaving +vely charged holes behind. Any electron that drifts towards the surface feels this repelling force. Far fewer free electrons at surface compared to the interior depletion region is a potential barrier for electrons.

Metal-Semiconductor junctions
Need to know: How do electrons flow on making contact. Fermi energies of electrons in both. Work Function, measures position of Fermi Energy w.r.t vacuum level (lowest energy to raise electron to escape from surface) well-defined constant for metals. It also measures Fermi level for Semiconductors varies with doping ! But, CB & VB Edges, w.r.t. vacuum, do not depend much on doping better choices. Therefore, Electron Affinity, s is used. defined as CBE relative to vacuum level Challenge: Experiments determine WF but, SC is doped need to convert to doping-independent Electron Affinity, s - difficult debate papers!!!

Doping-independent values good for tables device design, but, doping must be known to understand device performance! Let us then assume that actual Fermi level of the Semiconductor & Metal are precisely know leave the determination to Experiments!
When contact is made between a Semiconductor & Metal - electrons flow depending on the respective Fermi Levels. The flow can lead to Depletion or Enhancement of the majority carriers. Four possible situations to consider.

Work Function of Metal
Low
High
n-type
p-type
Doped Semiconductor
What does High & Low Work Function of a Metal mean? All it means is whether the Fermi Levels of the Metal lies above or below the Fermi Level of the Semiconductor Before Contact is made. Let us look at the Four possible situations.

Metal-Semiconductor contacts
M Semi M Semi
M Semi M Semi
After contact: Two produce Ohmic contacts (metallization) while the other two produce Schottky or rectifying contacts (now replaced by p-n diodes)

Ohmic contacts (metallization).
I V
Ohms Law
M Semi M Semi
M Semi M Semi
Electron Flow Into n-type semiconductor or Out of p-type Increases Majority carrier concentration of the semiconductor - increases conductivity of the Semiconductor near the junction - Ohmic contacts (metallization). Electrons flow from Metal into SC Difficult to find correct metals with appropriate WF for Wide-Band Gap Semiconductors

Band diagrams for metal & n-type semiconductor (a) before contact (b) After contact. M > S. Potential barrier: Heavy lines. is Electron Affinity.

M Semi M Semi
M Semi M Semi
Electron Flow: When charge flowing Into the semiconductor is opposite sign as the majority carriers type, the majority carriers are depleted near the junction forming a resistive depletion layer. - An applied bias voltage appears across this relatively insulating depleted region induces current flow.

Band diagrams for metal & p-type semiconductor (a) before contact (b) After contact. M < S.

Band Edge Diagrams for Biased Junctions

http://www.iue.tuwien.ac.at/phd/ayalew/node54.html

Biasing-Metal-Semiconductor contacts Schottky Diodes n-type SC
http://www.iue.tuwien.ac.at/phd/ayalew/node54.html

Band diagrams for (a) n-type whose surface is negatively charged (b) p-type whose surface is positively charged

Band diagrams for metal & n-type semiconductor (a) before contact (b) After contact.

Band diagrams for metal & p-type semiconductor (a) before contact (b) After contact.

Work Function of Metals
Element Aluminum Beryllium Cadmium Calcium Carbon Cesium Cobalt Copper Gold Iron Lead Work Function (eV) 4.08 5.0 4.07 2.9 4.81 2.1 5.0 4.7 5.1 4.5 4.14 Element Magnesium Mercury Nickel Niobium Potassium Platinum Selenium Silver Sodium Uranium Zinc Work Function (eV) 3.68 4.5 5.01 4.3 2.3 6.35 5.11 4.73 2.28 3.6 4.3

(a) before contact (b) After contact.

Metal-Semiconductor Contacts Electron Affinity, s 6H-SiC: 3.5 eV 3C-SiC: 4.0 eV 4H-SiC: 4.17 eV

Metal-Semiconductor Contacts Electron Affinity, s 6H-SiC: 3.5 eV 3C-SiC: 4.0 eV 4H-SiC: 4.17 eV
Assignment: Find appropriate metal contact to form (a) Ohmic contacts and (b) Schottky contacts on n-type and p-type 6H-SiC 3C-SiC 4H-SiC Provide calculations to justify the selection. Due: Feb 12, 2009

Crystal Growth

Crystal Growth

Thin Films
What is a "thin film" ? thin = less than about one micron ( 10,000 Angstroms, 1000 nm) film = layer of material on a substrate (if no substrate, it is a "foil") Applications: microelectronics - electrical conductors, electrical barriers, diffusion barriers . . . magnetic sensors - sense I, B or changes in them gas sensors, SAW devices tailored materials - layer very thin films to develop materials with new properties optics - anti-reflection coatings corrosion protection wear resistance Special Properties of Thin Films: different from bulk materials Thin films may be: not fully dense under stress different defect structures from bulk quasi - two dimensional (very thin films) strongly influenced by surface and interface effects This will change electrical, magnetic, optical, thermal, and mechanical properties.

Thin Films
Typical steps in making thin films: 1.emission of particles from source ( heat, high voltage . . .) 2.transport of particles to substrate (free vs. directed) 3.condensation of particles on substrate (how do they condense ?) Simple model:
How do the variables effect film structure and properties ?

Thin Films
What physics is in all this ? thermodynamics and kinetics phase transition - gas condenses to solid nucleation growth kinetics activated processes desorption diffusion allowed processes and allowed phases solid state physics crystallography defects bonding electricity and magnetism optics conductivity - resistivity magnetic properties mechanics stresses in films friction and wear

Thin Films
Classification of Defects in Crystalline solids Polycrystalline solid - contains several crystalline regions which are randomly oriented
Most crystalline materials have many defects. Some (like Silicon) can be grown with relatively few defects. Easiest way of determining nature of thin films is by X-ray diffraction. Intensity peaks arise from lattice planes that satisfy Braggs law:
= 2d . sin

Thin Films
Three types of defects: 1. Planar defects - grain boundaries interfaces between two single crystal regions of different orientation
atoms at grain boundaries tend to be loosely bound => more reactive (corrosion) and accelerated diffusion along grain boundaries typical grain sizes: 0.01 mm - 100 mm (micron) How many atoms in a solid are at grain boundaries ?

Thin Films
Rough model:
Assume grains are all cubes with sides of length l l = grain size a = atomic lattice parameter n = number of atoms in one row of the grain then, l = na
What would be the result for spherical grains of diameter, l ? for l = 0.1 micron (1000 Angstroms) and a = 3 Angstroms about 10 atoms out of 1000 are at grain boundaries (1 %)

Thin Films
Number of grain boundaries in film (grain size) depends on deposition rate and substrate temperature. generally: lower T => smaller grains => many boundaries higher T => larger grains => fewer boundaries grain size is often proportional to film thickness (thinner films tend to have smaller grains) 2. line defects - dislocations example: edge dislocation - from inserting an extra row of atoms distorts lattice => stresses (compression and tension) very common: often 1010 - 1012 dislocations/ cm2 in films form from: film growth process dislocations in substrate continuing into film contamination on substrate

Thin Films
3. point defects self interstitial - extra atom vacancy - missing atom substitutional impurity - impurity atom in lattice interstitial impurity - impurity atom not in regular lattice site
In principle you can eliminate all of these except vacancies

Thin Films
Vacancies arise from thermodynamics (entropy)
fraction of vacancies (f)
f =e
E f / k BT
where kB = Boltzmann's constant = 1.381 x 10-23 J/K typically Ef is about 1 eV at room temperature, f is about 10-17 point defects often arise from fast deposition low substrate temperatures => no time for atoms to move to crystal lattice sites

Thin Films
Surface Roughness Films always have some statistical distribution of thickness across the film
in the worst case:
d = d
generally observed less roughness

Crystal Growth

Crystal Growth
Si crystal growth Starting material is ? Sand (SiO2) reduced in an arc furnace with coal 98%Si Powdered raw Si reacted with HCl acid forming trichlorosilane Si + HCl SiHCl3 + H2 This is fractionally distilled to purify and then reduced with H2. SiHCl3 + H2 Si + 3HCl Polycrystalline

Crystal Growth
(a) Czochralski (b) Float zone (c) Bridgman (d) 12-inch Si single crystal

Crystal Growth (a)Czochralski Si melted in SiO2 crucible inside a graphite crucible. Seed single crystal held on a rod, touches the melt& slowly lifted 1 mm/min Crucible & rod rotate in opposite Direction 50 rpm Vacuum or protective atmosphere.

Crystal Growth

Crystal Growth
(a)Czochralski Si melted in SiO2 crucible inside a graphite crucible. Seed single crystal held on a rod, touches the melt& slowly lifted 1 mm/min Crucible & rod rotate in opposite direction 50 rpm Vacuum or protective atmosphere.

Crystal Growth (b) Float-zone Polysilicon rod with a seed crystal at the end is put in a vacuum chamber. A ring type induction furnace slowly moves along the length melting solidifying small portions from the bottom up single crystal high purity.

Crystal Growth

Single Crystal Growth
Floating Zone Method

Higher purity Oxygen content <1016 atoms/cm3 Higher resistivity 200 cm Reverse voltage > 750-1000V Mechanically weaker
Czochralski Method
~1018 atoms/cm3 50 cm Majority of IC - # of temp steps in Si wafer processing
Dopants: n-type use PH3, for p-type B2H6

Crystal Growth
(c)Bridgman method rarely for Si, but for GaAs. Polycrystalline material melted in a Si3N4 coated graphite or quartz Crucible inside a sealed quartz tube. Traveling furnace, 2 temperature zones, gradually melts the seed single crystal and the poly extra arsenic in low temperature zone

Crystal Growth (c)Bridgman method rarely for Si, but for GaAs. Polycrystalline material melted in a Si3N4 coated graphite or quartz Crucible inside a sealed quartz tube. Traveling furnace, 2 temperature zones, gradually melts the seed single crystal and the poly extra arsenic in low temperature zone

Crystal Growth
Liquid Encapsulate Czochralski Growth

Crystal Growth

Crystal Growth

Crystal Growth

Crystal Growth

Thin Film Growth
Single Crystal - Epitaxy Molecular Beam Epitaxy (MBE) Chemical Vapour Deposition (CVD) - LPCVD, APCVD, PECVD Metal-Organic Chemical Vapour Deposition (MOCVD)
Poly-Crystal Magnetron Sputtering Pulsed Laser Deposition (PLD) Ion Beam Deposition (IBD) amorphous or fine grains? Atomic Layer Deposition (ALD) amorphous or fine grains?

Crystal Growth
Molecular Beam Epitaxy (MBE)

Crystal Growth

Crystal Growth

Crystal Growth

Crystal Growth

Crystal Growth

Crystal Growth

Crystal Growth

Crystal Growth
Metal-Organic Chemical Vapour Deposition (MOCVD) Organo-Metallic Vapour Phase Epitaxy (OMVPE)

Crystal Growth
Metal-Organic Chemical Vapour Deposition (MOCVD)

Crystal Growth

Crystal Growth

Crystal Growth

Crystal Growth
Metal-Organic Chemical Vapour Deposition (MOCVD) (a) Emcore Veeco Turbo-disc (b) Thomas Swan showerhead (c) Aixtron planetary (d) EMF Vector flow reactor

Crystal Growth

Crystal Growth

Crystal Growth
Magnetron Sputtering

Crystal Growth
Magnetron Sputtering

Crystal Growth
Pulsed Laser Deposition (PLD)

Thin Film Growth
Veeco Ion Beam Deposition

Thin Film Growth

Semi Conducting &amp Magnetic Materials Week 3 Feb 7 2012

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Semi-conducting & Magnetic Materials

Prof S. B. Sant Department of Metallurgical & Materials Engineering IIT Kharagpur

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

2 major Designs for Laser Diodes

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Electrons drift and diffuse across a junction between unlike materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Band Edge Diagrams for Biased Junctions

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

(a) before contact (b) After contact.

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

How do the variables effect film structure and properties ?

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

In principle you can eliminate all of these except vacancies

Semi-conducting & Magnetic Materials

fraction of vacancies (f)

Semi-conducting & Magnetic Materials

in the worst case:

generally observed less roughness

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Floating Zone Method

Dopants: n-type use PH3, for p-type B2H6

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Semi-conducting & Magnetic Materials

Liquid Encapsulate Czochralski Growth