Engineering of Microelectronic Devices

B-Doping
Lecture 2

D. G. Hasko
 Impurities and defects in silicon

Impurity on substitutional Silicon interstitial

site

Silicon vacancy or
Schottky defect
Silicon atom on
lattice site

Impurity
on interstitial site Frenkel defect
Solid Solubility Limits (after Trumbore)

Dopant needs to be on
lattice site (dissolved into
lattice) to be active.
High solubility occurs at
high temperatures,
but once dissolved, lattice
site occupancy state is
metastable.
Solid Solubility Limits (after Trumbore)

Industrially important
dopants.
Solid Solubility Limits (after Trumbore)

Heavy metal impurities

tend to have very
undesirable electrical
properties (eg traps
and recombination
centres).
 Dopant impurities for silicon

Dopant requirements:
low ionisation energy to ensure full activation.
high solubility to enable high doping levels.

Energy levels for important impurities in Si.

Element P As B Au

Energy (eV) 0.044 0.049 (0.065) 0.54(0.35)

Type n n p deep
 Dopant Concentration Nomenclature

Concentration (Atoms/cm3)

Dopant
Material < 1014 1014 to 1016 1016 to 1019 >1019
Type (Very Lightly Doped) (Lightly Doped) (Doped) (Heavily Doped)

Pentavalent n n-- n- n n+
-- - +
Trivalent p p p p p
 Dopant diffusion


Fick’s law
J = − D C ( x, t )
x
Where J is a flux of a position x and time t dependent
concentration with diffusion coefficient D.

  
C ( x, t ) = D C ( x )
This can be rewritten as

t x x
If D is independent of position

 This second order D.E. needs two

C = D C
2 boundary conditions for solution

t
 Dopant diffusion in silicon
Diffusion coefficient D depends on the diffusing species,
semiconductor material, temperature, etc.

Interstitial mediated
diffusion.

Substitutional mediated
diffusion (push-out).

Vacancy mediated
diffusion.

For impurity diffusion in silicon:-

Substitutional (dopant) P, As, B

Interstitial (recomb. cen.) Au
Diffusion Coefficient
 Fair’s vacancy model

Diffusion much easier when vacancies are present since impurity

can swap places with vacancy much more easily than with
another atom.
For moderate temperatures and impurity concentrations (<ni at
the diffusion temperature) the diffusivity usually takes a simple
form i.e.

 − Ea 
 
D = Do e  kT 

Account must also be taken of charge due to unsatisfied bonds.

 Diffusion coefficients of impurities in silicon

Vacancy mediated diffusion Ea ~ 3 - 4 eV

Interstitial mediated diffusion 0.6 -1.2 eV

B P
Do cm2/sec 0.76 3.85
Ea eV 3.46 3.66

Other factors affecting diffusion:

electric field effects due to concentration gradient of ionised

impurities.

bandgap narrowing at high impurity concentration leading to

modification of point defect density and diffusion.

solid solubility effects e.g. As clustering.

How are dopants introduced into semiconductor?

Three ways:
•Grown in when the crystal is formed (Czochralski growth
of substrate or during epitaxy).
•Diffused in during high temperature processing (during
epitaxy or oxidation or annealing).
•Ion implantation (industrially most important due to high
degree of control over implantation conditions).
 Chemical Vapour Deposition (CVD)

Radiant heater elements

Wafer

Gas
Gas inlet exhaust

Susceptor
Quartz furnace tube

Include dopant into gas stream (say AsH3).

 Chemical Vapour Deposition (CVD)

Dopant incorporation

Growing film
Frank-van de Merwe mode HCl SiCl2
H2

AsH3

Si
Substrate

Elevated temperature leads to high surface mobility

Silicon atoms move around until a suitable empty

lattice site is found.
 Autodoping
Dopant in gas Wafer

Gas
Gas inlet exhaust

Susceptor
Layer growth takes place at high temperature
Dopants diffuse to lower concentration regions Other dopant
sources
Pathway may be indirect (via gas stream)
Source may be unintended (susceptor or back
side of wafer)
 Autodoping

Dopant concentration
Desired doping profile
Doping in substrate close
to surface is reduced, due
to solid state out-diffusion
Doping in epitaxial layer
is increased, due to out-
diffusion and gas phase
autodoping
Depth

New surface Original surface

Effect of dopant diffusion is to reduce

concentration gradient
 Ion implanter

The ion source takes in gas (e.g. arsine) and produces ions
(As+, As2+ etc.), which are then accelerated through a large
voltage (usually >1kV) and mass selected to give a
monoenergetic (and single ion species) beam which is
scanned across the wafer.
 Ion implanter

This gives good control over:-

•dopant areal density through easy measurement of the deposited
charge.
•dopant position. The ion energy determines the range and so the
depth at which the ion comes to rest.
Ion implanter
 Ion implanter

Varian ion implanter

 Range and straggling

Ion loses energy by nuclear and This is a stochastic process

electronic scattering. so that there is variation in the
stopping distance for each
ion.

Average range Rp,

variation  Rp (in
both in-line and
transverse
directions).
 Boron ion implantation into silicon

By controlling the ion energy and flux, highly

controlled dopant distributions can be achieved
 Dopant distribution modelling

Assuming a Gaussian distribution for the stopped ions:

  
(
 − x−Rp )2 
  
N (x ) = 
 2 R p 2 
e
 (2 )2 R p 
1

where N(x) is the ion concentration at the depth x and  is the

number of ions incident per unit area on the substrate.
 Range and straggling of dopants in silicon
Rp (m)
 Rp (m)
1 B B P
P 0.1 As

As

0.1 0.01

0.002
10 100
0.01 Energy (keV)
10 100
Energy (keV)

Projected range Rp and straggle (standard

deviation)  Rp for common dopants in silicon.
 But distribution is not quite Gaussian!
Concentration cm-3
Boron implantation into silicon.
N(x) measured by Secondary
Ion Mass Spectrometry (SIMS).
Note log scale!
Normal implant into silicon.
Gaussian.
Difference!
But if lattice is disrupted first.

m
Depth
 Dopant distribution modelling

If the initial dopant distribution is very shallow (close to the surface) then
a simple relationship describes the diffusion of these impurities into the
semiconductor:

    − x2 
   
N (x ) =  1 
e  4 Dt 

 (Dt ) 2 

where t is the time spent diffusing at a temperature at which D is

the diffusion coefficient.
 Channelling

Apparent crystal packing depends on orientation.

Long pathways through crystal become available close to major crystal

planes.
Incident ion can travel much further before scattering.
Increase in range due to channeling.
.
Remedy: implant at angle to major plane,
remove crystallinity.
 Damage recovery and characterisation.

Implantation process causes lattice damage to substrate.

As ions lose energy by scattering, lattice atoms can be displaced, leading

to point defects.

If sufficient point defects are created, the lattice crystallinity is lost,

leading to highly modified band structure and electrical characteristics.

Furthermore, the incident ions do not end up at lattice sites, where they
need to be for the dopant to be active.

Finally, the damage and the presence of the inactive dopant impurities
leads to very high levels of strain in the semiconductor lattice.
 Damage recovery and characterisation.

This damage needs to be recovered by thermal annealing, which also

acts to activate the dopants.

By heating to a very high temperature (say about 1000C) the displaced

atoms are reordered using the substrate as a template.

During this process dopant atoms are incorporated into the lattice and so
become active (provided that the density does not exceed the solubility
limit).
 TEM characterisation

Defect structure may be seen by transmission electron microscopy TEM.

Cross-sectional dark field images (i.e. the silicon atoms in regular lattice
positions do not show up) showing areas of strain and defects as light
areas.
 TEM characterisation

Horizontal bright line across the top is the silicon surface.

Both samples were implanted with Silicon and then Boron.
The Silicon implant severely damages the lattice (but does not dope) so
that the subsequent Boron implant is not subject to channelling, which
would increase the junction depth.
Dopant concentration profile

Dopant concentration vs depth

measured using secondary ion mass
spectrometry (SIMS)
Samples implanted with Boron for
range of doses, then annealed.
For low dose, normal distribution.
Dopant concentration profile

Dopant concentration vs depth

measured using secondary ion mass
spectrometry (SIMS)
Samples implanted with Boron for
range of doses, then annealed.
For low dose, normal distribution.
For high dose (above solid solubility
limit) gaussian peak remains,
corresponding to original implant
remains, superposed on diffused
background.
 Sheet resistance

The sheet resistance Rs of a homogeneous layer of resistivity rho and

thickness t is


Rs =
t
Mobility (N) depends on carrier concentration N(z), which varies with
depth.
So that the sheet resistance of a doped layer is a weighted average.

1
Rs =
 N (z )e(N )dz
 Worked example

A dose of 1 1015 ions/cm2 of boron is implanted into a uniformly doped (1

1019/cm3) n-type wafer at an energy of 50keV.

Use the data from the projected range and straggle graphs to estimate the
peak density and the junction depth.

The density of boron ions as a function of depth is given by

  
(
 − x−Rp )2 
  
N (x ) = 
 2 R p 2 
e
 (2 )2 R p 
1
 Worked example
From the graph we see that Rp and  Rp are 0.2m and 0.06m
respectively for boron at 50kV.

The junction is formed where the implanted boron ion density falls to
the background donor density.

Converting into SI units and substituting into the equation gives

1 1025 = {1 1019/[ (2)0.5 0.06 10-6]} exp [-(x-0.2 10-6)2/{2 (0.06 10-6)2}]

where x is the unknown junction depth.

So that x=0.32m taking the positive root.

This result can be compared with the graph earlier.