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Chapter 2

D. K. Schroder, Semiconductor materials and device characterization


3rd edition, 2006

Carrier and Doping Density


Wonjae Kim
16. 11. 2012

S-16.4123 Postgraduate course in Electron Physics

Outline
1. Introduction

2. Electrical measurement for determining doping and carrier densities


Capacitance-Voltage (C-V)
Current Voltage (I-V)
Hall effect
3. Optical techniques
Plasma Resonance
Free carrier absorption

Infrared Spectroscopy
Photoluminescence (PL)
4. Other analysis
Secondary Ion Mass spectrometry
Rutherford Backscattering
5. Summery

Introduction
Are carrier density and doping density identical ?
At thermal equilibrium
Intrinsic
(no impurities)

Donor impurities
(n ND)

Acceptor impurities
(p NA)
Band diagram, Density of state, Fermi-Dirac distribution, carrier density [1]

Introduction
Carrier density doping density

In case of frozen or thermally intrinsic

Electron density as a function of temperature for Si [1]

Introduction
In empirical measurement (or analysis),
Carrier density = Doping density (uniformly doped)
Carrier density Doping density (non-uniformly doped)

What are the methods for determining the carrier and doping densities?
Electrical methods (~carrier density)
Capacitance-Voltage, Current- Voltage, Spreading Resistance, Hall measurement ..
Optical methods (~ identification of impurities)
Plasma Resonance, Free carrier absorption, infrared spectroscopy,
Photoluminescence (PL) ..

Others (~ doping density)


Secondary ion mass spectroscopy (SIMS), Rutherford Backscattering (RBS)..

I. Electrical methods
1. Capacitance-Voltage measurement
Reverse-biased barriers (Schottky barrier, pn-junction)
MOS-Capacitance
Mercury probe contact
Electrochemical C-V profiler (ECV)
2. Current-Voltage measurement
MOSFET Substrate voltage-Gate voltage
MOSFET Threshold voltage
Spreading Resistance Probe (SRP)
3. Hall measurement

Electrical method

Capacitance-Voltage method
Differential Capacitance

(Parallel plate capacitor)

A reversed-biased Schottky diode and the doping


density (NA) and carrier density (p) profile [2]

Electrical method

Capacitance-Voltage method
Differential Capacitance-Voltage profiling
C-V and (1/C2) V Curves
1/C2 V curve is preferred to identify the
uniformity of carrier density
(discontinuity at around 3 V )

C-V and (1/C2)-V curves of pp+Si, p(x)-W profile [2]

Electrical method

Capacitance-Voltage method
Deviation of major carrier density from doping density
Schottky diode

Carrier density Doping density


(at zero-biased junction)
Due to diffusion (some of the holes diffuse from the highly
doped region to the lowly doped region) and drift

Determination of deviation
Zero-biased junction

Reverse-biased junction [2]

Deviation of majority carrier density from the doping


density is governed by the extrinsic Debye length

*Deviation is larger with abrupt junction (steeper doping gradient)

Debye length
A distance that mobile charge carriers (e.g. electrons) screen out electric fields.

Measurement deviation
Capacitance id determined by the movement of majority
carriers
Majority carrier distribution Doping density profile
( Apparent density) when abrupt spatial change (doping
density step) occurs within one Debye length (<1LD)
Majority carrier density Doping density profile when more
gradual density step (>1LD)
Charge distribution from electric field at a plate with a
dielectric medium [3]

Certainly would expect that the concentration varies


smoothly within a certain distance, and this distance
we call Debye length.

Electrical method

Capacitance-Voltage method
Heterojunction semiconductor
C-V measurement to determine the band
offsets
The doping densities profiles are determined
from the slope m1 and m2.
Cpl is related to the thickness of the narrow
band, and Vpl is related to the band offset

*C-V curve yields an apparent (or effective) electron


density n* (differ from true electron and doping
density) due to the steep junction step (< LD)

Doping (carrier) density plot of n-GaAs/N-Al0.3Ga0.7As


heterojunction (N>n) [2]

Electrical method

Capacitance-Voltage method
Depletion approximation (for uniformly doped substrate)

neglecting minor carriers


assuming total depletion of majority carrier in space charge region to a depth W
Perfect charge neutrality beyond W

Differential Capacitance-Voltage profiling


The charges that actually move in response to the ac voltage are the mobile holes, not
acceptor.
Therefore, differential C-V profiling technique determines the carrier densities

Electrical method

Capacitance-Voltage method
MOS-C capacitor
From Poissons equation
VG

COX
CS

S, inv = surface potential in strong inversion 2F


(F = the energy difference between EF and Ei)

CS = KS0A / W

C2F = Capacitance at VT

R = Cinv / Cox

Band diagram and carrier distribution of MOS [1]

Electrical method

Capacitance-Voltage method
MOS-C capacitor

No depth dependent doping profile can be expressed


Depth-doping profile may be measured by gradually
immersing the wafer in an etch

Doping (carrier) density versus Cinv / Cox as a function of


oxide thickness for the SiO2 / Si system at T = 300K [2]

Electrical method

Capacitance-Voltage method
Poly-si gate MOSFET

MOSFET connection and measured C-V curve [2]

When VG > VT
From C/COX,
ND ( = 5 x 1019 cm-3) at tOX (= 10 nm) is estimated.
Limited to strong inversion since gate oxide may breaks down

Electrical method

Capacitance-Voltage method

Maximum-Minimum MOS-C capacitance measurement


Measure the maximum high-frequency capacitance in strong
accumulation
Measure the minimum high-frequency capacitance in strong
inversion

C-V curve for MOS-C [2]

Max-Min capacitance method yields the average doping


density over the space charge region width in strong
inversion

Electrical method

Capacitance-Voltage method
Mercury Probe Contacts

No depth dependent doping profile can be expressed


No metal contacts on substrate are required
No mechanical damage to the surface of substrate
However, leakage current through junction can limit for
accurate measuring -> Thin oxide layer (~ 3nm) is used

Schematic of Mercury prove [4]

Electrochemical C-V profiler (ECV)

To use capacitance of an electrolyte-semiconductor


Schottky contact
Depth profiling is carrying out by electrolytically
etching the surface (no depth limitation)
However, it is destructive

Schematic of ECV [2]

Electrical method

Current-Voltage method
For doping density profile, C-V measurement on large-diameter device is effectively
valid, but not on small geometry MOSFETs due to extremely small capacitance.

MOSFET Substrate voltage - gate voltage


MOSFET is biased in its linear region by a low drain-source
voltage (VDS)
Constant VDS, constant I1 through the operation amplifier are
applied
When VGS is changed, op amp adjusts its output voltage (VBS)
Space charge region under the gate is extended by the VBS
Inversion charge density is constant (approximated by VDS)
op amp

Electrical method

Current-Voltage method
MOSFET Threshold Voltage
Threshold voltage is measured as a function of substrate bias

[ = (2qKs0NA)1/2 / Cox , VSB = VS VB ]


[F = Energy difference between EF and Ei]
[F = (kT/q)ln (NA/ni)]

Measure VT as a function of VSB (changing VSB)


Plot VT versus (2F + VSB)1/2 using 2F = 0.6 V
Take the slope () and find NA
With NA find a new F, and repeat plotting VT versus (2F + VSB)1/2

Electrical method

Current-Voltage method
Spreading Resistance

Commonly used for Si


Two spreading resistance probes are stepped along the beveled surface
The spreading resistance is measured as a function of sample depth
Doping density profile is calculated from the measured resistance profile.
Very high resolution profiles generated

[Park systems, Nanotechnology solution partners, p149] [5]


Dopant density profiles determined by various methods for MOSFET [2]

Electrical method

Hall-effect (Hall measurement)


Accurate measurement for Carrier density, resistivity, Mobility is available

By Lorentz force

qEy = -qvxBz
Jp = qpvx = qpEx (= qp)
Ey = (Jp/qp)Bz = RHJpBz = RH(I/A)Bz
dEy = VH

(RH 1/qp)
Ey = VH/w = RH(I/A)Bz
RH = dVH / IBz

II. Optical methods


1. Plasma Resonance
2. Free Carrier Absorption
3. Infrared Spectroscopy
4. Photoluminescence (PL)

Optical method

Plasma Resonance
Optical reflection coefficient is defined by

n = reflective index
k = /4 ( is the absorption coefficient)

Semiconductor

R approaches unity (maximum) when photon frequency approaches the plasma


resonance frequency (p= c/ p) ; when insident p

*Surface plasmon resonance frequency


The frequency of light photons matches the natural frequency of surface electrons

However, it is very difficult to define p in practice.


Therefore, min ( at reflective minimum higher wavelength; min < p) is used for
determining carrier density utilizing empirical relation ship as,

Optical method

Free carrier absorption


Free carrier absorption
A carrier is excited from a filled state to an
unoccupied state (in the same band) by absorbing a
photons (h < EG) => Free carrier absorption

Free carrier absorption coefficient for holes,


[Nature Photonics 4, 511 - 517 (2010)] [6]

Fit for high density (~ 1017 cm-3)

But difficult for lower density due


to too low absorption coefficient

c velocity of light
n reflective index
m* effective electron mess
carrier mobility

By fitting curves to experimental Si,

Optical method

Infrared Spectroscopy
Optical absorption process with h < (EG ED) at low
temperature
i) Electrons can be excited from the ground state to conduction
band -> broad absorption continuum.
ii) Electrons can be exited from the ground state to one of
several excited states -> producing sharp lines in spectrum

Only useful for low doping densities


Method is simple but requires low temperature
Energy band diagram of semiconductor containing donors
[2]

h < EG

IR spectrum of donor impurities for n-Si measured at T ~ 12 K [2]

h > EG

Optical method

Photoluminescence (PL)
Photoluminescence process

i) Absorption -> Re-radiation (Excitation to higher state->


returning to lower state by recombining electron-hole pairs)
ii) Radiative emission intensity is proportional to impurity
density

Identification of impurity is precise

[Nature Photonics 4, 511 - 517 (2010)] [6]

But, density measurement is not easy due to


non-radiative recombination which is
dissipated to phonons
Measuring both the intrinsic and extrinsic PL
peaks
Using the ratio as XTO / ITO which is
proportional to the doping density
XTO : transverse optical phonon of doping elements PL intensity
peak (X = B or P)
ITO : transverse optical phonon of intrinsic PL intensity peak

PL intensity ratio versus doping density for B and P [2]

Mechanical bombardment method

Secondary Ion Mass Spectrometry (SIMS)

[Institute of complex materials, Dressden] [7]

[Geochemical instrumentation and analysis] [8]

Removal of material using ion-beam sputtering


Analysis of sputtered species (only ionized) by passing through an energy
filter and mass spectrometer (converted to impurity density)
Secondary ions are monitored by time (time converted to depth)

Mechanical bombardment method

Secondary Ion Mass Spectrometry (SIMS)

p+(B)/p(B)-Si

n+(As)/p(B)-Si

Profiles obtained with the ECV and SIMS [2]

Very powerful for analysis of impurities (straightforward)


High sensitivity for elements, but not as high as electrical or optical methods

Detecting densities ~ 1014 cm-3, depth ~ 1-5 nm


But destructive for the surface

Mechanical bombardment method

Rutherford Backscattering (RBS)


Rutherford Backscattering
Detecting backscattering light ions from incident
light ions (usually monoenergetic He ions of 1 3
MeV) by a surface barrier detector
Most useful for heavy elements in a light matrix,
for example, As in Si or Te in GaAs
Whereas, difficult for B in Si and Si in GaAs due to
losing He energy from interaction with heavy ions
(e.g., As).

[SPIRIT, www.spirit-ion.eu] [9]

No scattering occurs from ions lighter than probe


ions
Sensitivity is low compared to SRP and SIMS
The lowest detection ~ 1014 cm-3
Depth profiling ~ 2-5 nm

Non-destructive quantitative technique


Boron densities. (1.5 MeV He+ is used for Rutherford backscattering
spectrometry) [10]

Summary
Electrical method
C-V measurement, I-V measurement, SRP, Hall-effect
- Determining carrier density (profile)
- Simple method, Accurate measurement, Non-destructive

Optical method
Plasma resonance, Free carrier absorption, Infrared Spectroscopy, Photoluminescence
- Identification of doping
- Non-destructive

Mechanical bombardment method


Secondary Ion Spectroscopy (SIMS), Rutherford Backscattering (RBS)
- Highly straight-forward to determining doping density
- Destructive

References
[1] S. M. Sze, Semiconductor Deivce, Physics and Technology, Wiley
[2] D. K. Schroder, Semiconductor materials and device characterization, 3rd edition, 2006
[3] CAU, Christian-Albrechts-Universitt (http://www.tf.uni-kiel.de)
[4] The solid film, 516, 89178925 (2008)
[5] Park systems, Nanotechnology solution partners, p149
[6] Nature Photonics 4, 511 - 517 (2010)
[7] Institute of complex materials, Dressden
[8] Geochemical instrumentation and analysis
[9] SPIRIT, www.spirit-ion.eu
[10] Physical Review B, 56, 1393 (1997)