Crystal defects

Point Defects Foreign atom incorporated into the lattice Lattice Vacancy Impurity Substitutional Interstitial Frenkel Schottky defect
Vacancy

Substitutional

Frenkel

Schottky

Interstitial

Crystal defects
Line Defects(Dislocations)
Edge dislocation:
extra half-plane of atoms inserted in a crystal structure

Screw dislocation:
spiral planar ramp resulting from shear deformation

Crystal defects
Area Defects A large area discontinuity in the lattice Twinning Change in crystal orientation across the plane Stacking fault-Intrinsic,Extrinsic Stacking sequence of atomic layer is interrupted

Intrinsic

Extrinsic

Crystal defects
Volume Defects
Due to precipites of impurities

Steps In wafer Fabrication

Raw material(Quartzite) Metallurgical grade Si IC Design Mask Generation

Electronic grade Si

Clean room

Single crystal Si boule

Wafer clean

Si Wafer Wafer characterization/specification

Ready for process

CMOS Flow

Bipolar Flow

THE PURITY OF SILICON

The starting form of silicon, which manufacturers of devices and integrated circuits use, is a circular slice known as a wafer. These wafer diameters vary from 10-20 cms with maximum up to 30 cms. Silicon is found in abundance in nature as an oxide in sand and quartz. Silicon must be in Crystalline form Very pure Free of defects Uncontaminated.

Raw material(Quartzite)
Quartzite : mainly composed of quartz Quartz : SiO2

Quartz crystal

Step1: Metallurgical Grade Si from SiO2

Quartzite is heated with coke in an arc furnace at very high temperature(~1800oC)

SiO2 2C Si 2CO
Polycrystalline silicon MGS: Has Impurities like Fe , Al and Heavy metals at levels of several hundred to several thousand parts per million(ppm) Clean enough for making stainless steel

Unit cell of crystalline silicon

Poly crystalline silicon

Amorphous silicon

Crystalline

polycrystalline

amorphous

Step 2: Pulverized Si is treated with anhydrous HCl at3000 C to form tri-chloro Silane (SiHCl3)
EGS: level of impurities is in ppb 1 ppb=5*1013 cm-3 Reacting the MGS with dry HCl Triclorosilane : liquid with boiling point 32 deg C

Si 3HCl SiHCl 3 H 2

Step 3: Fractional distillation of SiHCl3 to remove unwanted impurities

Pure trichlorosilane

Impurities like FeCl3 have different boiling points Fractional distillation

Impurities

Step 4: Reduction of SiHCl3 in Hydrogen to form Electronic Grade Si

SiHCl 3 H 2 Si 3HCl
Reaction takes place in a reactor containing a resistance heated Si rod which serves as a nucleation point for deposition of Si High purity silicon polycrystalline

Starting Materials

Crystal Growth techniques

Crystal Growth from Liquid (Melt)

Verneuil (flame fusion) ~early 1900s Czochralski (pulling) ~1910s Kyropoulos (top seeding) ~1920s Bridgman (directional solidification) ~1940s Skull Melting ~1970s Laser-heated pedestal growth ~1990s Micropulling ~1990s Floating Zone (incl. image furnace) ~1990s

Bridgeman process

Bridgeman process
Simpler technique T-Vs Direction Seed end at lower temperature Seed crystal not molten Move the heater once charge is in molten The end in contact with the seed solidifies This event progresses Ampoule can also be moved in reverse direction Disadvantage :due to silicon expansion after solidification: dislocations due to contact

Czochralski Process

Czochralski Process
4-subsystems Furnace: Graphite chamber with gas inlets, outlets pumps to maintain pressure and opening for pull rod. Water cooling for quartz envelop Crucible: cup in which charge is kept , made of quartz, oxygen contamination, can be used only once Graphite susceptor in which crucible is placed, Graphite heater : Heating by RF or resistively Crystal pulling mechanism: Fixed seed crystal Pull rod to pull the seed up during crystal growth

Czochralski Process
Ambient control : Presence of oxygen leads to burning of graphite to carbon dioxide Also oxygen may react with silicon to form SiO2 So the chamber is evacuated Filled with inert gas like argon Pressure is atmospheric or some times lower Control System: microprocessor, sensors and outputs

Czochralski Process
EGS is broken into small pieces & placed in an quartz line graphite crucible The crucible is heated to slightly higher the melting point of Si After having set up the melt, a seed crystal ,attached to a holder and possessing the desired crystal orientation, is dipped into the melt Pulled up slowly and a small portion is allowed to Melt.

Czochralski Process
The melt in contact with the seed solidifies As the rod is pulled up a single crystal is obtained Care: prevent seed getting melt If thermal conditions and pull rate is not adjusted seed may melt Method is complicated , good quality crystals are obtained Generally the crystal is rotated slowly as it grows to provide uniform growth

Czochralski Process
To adjust the pull rod( pull rate) If the pull rod is pulled faster a single crystal may not be formed If it is done slowly even the seed may melt Heat transfer equation Latent heat of solidification Mass solidification rate Thermal conductivity of liquid Thermal gradient in the melt Area of isotherms in the melt Thermal conductivity of solid Thermal gradient in the solid Area of isotherms in the solid

dm dT dT L +KL A1=Ks A2 dt dx1 dx2

Czochralski Process
Pull Rate Assumption: thermal gradient in the melt is zero

dm dT L =Ks A2 dt dx2 dx dT L(A2 2 )=Ks A2 dt dx2 dT Ks dx dx2 = dt L

This is the maximum attainable pull rate

2: density

dx :Pull rate dt dx :Rate of change of volume A dt

Czochralski Process
Pull Rate Thermal gradient: + deg celsius Heat loss is entirely taken by latent heat

dm dx L(A2 2 ) Hi-Ho= L dt dt
L, : constant Pull rate and area of crystal formed are inversely related Larger the crystal , smaller is the pull rate

Czochralski Process
Cooling the crystal: 9500 C thermal defects Pull rate> 2mm/m: defects are less Larger crystal demands less pull rate It is easier to grow small crystals

Czochralski Process
Doping Adding impurities or dopants to the silicon melt to change its electronic properties At the solidification interface between the melt and the solid, there will be a certain distribution of impurities between the two phases. Distribution coefficient: Ratio of the concentration of impurity in the solid to the concentration in the liquid at equilibrium

Cs Kd CL

Czochralski Process
Most impurities : Kd<1 As crystal grows the impurities prefer to be in the melt For oxygen Kd>1 We have SiO2 in the crucible So chance of oxygen impurity is more This Oxygen in silica can have three possible effects 95% Donor like SiO4 Leads to formation of SiO4 Temperature(450-5000 C) O2 in interstitial sites(5-6.4X 1017 / cm3) : Improves yield since it is N type O2 >6.4X 1017 / cm3 : precipitates : beneficial if in bulk

Czochralski Process
Finished Crystal parts Wafer cutting

Czochralski Process

Czochralski Process

Wafers
Thin slice of semiconductor material, used in the fabrication of integrated circuits The wafer serves as the substrate for devices built in and over the wafer undergoes many fabrication process steps such as doping or ion implantation, etching, deposition of various materials, and photolithographic patterning. The single crystal ingot is mechanically processed to manufacture wafers Mechanically grinds the more or less cylindrical ingot into a perfect cylinder The crystal planes are identified using X-ray crystallography The Si cylinder is sawed into individual wafers

Ex:1)A silicon crystal is to be grown by czochralski method, and it is desired that the ingot contain 1016 phosphorous atoms/cm3 (a)What concentration of phosphorus atoms should the melt contain to give this impurity concentration in the crystal during the initial growth? For P in Si , Kd=0.35. (b) If the initial load of Si in the crucible is 5Kg, how many grams of phosphorus should be added? The atomic weight of phosphorus is 31.

Equation:

Cs Kd CL

Ans=2.86*1016 atoms /cm3

If the initial load of Si in the crucible is 5Kg, how many grams of phosphorus should be added? The atomic weight of phosphorus is 31. Find volume occupied by silicon Density of Si: 2.33 g/cm3 5 kg occupies 2.33*5000=2145.9227cm3 volume Find the no of phosphorus atoms in the melt = 2.86*1016 atoms /cm3 *2145.9227cm3 = 6.137*1019 atoms Find the Amount of phosphorus to be added 6.137*1019 atoms*31g/mole =3.1604*10-3 g of phosphorus 6.02*1023 atoms/mole

Ex: 2. A silicon ingot, which contain 1016 boron atoms/cm3 , is to be grown by the Czhochralski technique. What concentration of boron atoms should be in the melt to give the required concentration in the ingot? If the initial load of silicon in the crucible is 60kg, how many grams of boron (atomic weight 10.8) should be added? The density of molten silicon is 2.53 g/ cm3

Concentration of boron in the melt: 0.125* 1016 boron atoms/cm3 Amount of boron to be added: 5.3182mg

Crystal growth Techniques

Comparison CZ and Bridgeman processes Bridgeman process is simpler Crystal grown by Bridgeman process has a lot of defects

Crystals grown by CZ process is not perfect due to the oxygen content So we have to further purify this crystal if quality is importent

Floating Zone
To intentionally purify semiconductor material Arrangement Cooled silica envelop Gas Inlets and outlets Inert ambient Silicon bar and holder Seed Crystal RF coil(movable) Rod of high purity polycrystalline material(or bar ) is held in a chunk RF coil is used to locally melt the silicon bar

The part of silicon bar which is just in contact with the seed solidifies and attain the shape and orientation of seed
No crucible: no oxygen contamination

Repeat the passes to improve resistivity

Floating Zone

Floating Zone: modification

Core doping Start with doped polysilicon rod and deposit undoped poly rod on top to get desired concentration (process can be repeated) Pill doping Dopant inserted through small holes drilled on top Gas doping Gases such as PH3 or AsCl3 injected in the molten zone Transmutation doping (only for n-type doping) Isotope changed through exposure to neutrons

Comparison CZ-FZ
silicon that has lower contamination from FZ No crucible in FZ doping concentration is not uniform in FZ Not suitable for large diameter crystal silicon

Wafer cutting