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Transport phenomena.
0. General theory. Boltzmann equation
Definition: those phenomena determined by the movement of the free charge carriers (CC) influenced by
external (or internal!!) fields (electrical, magnetic, temperature/pressure gradients).
- Crystal separated from the environment thermodynamic equilibrium state (no particles/energy fluxes)
r
( )
f 0 k can be used
- Crystal in the presence of fields some energy transferred to free carriers some directed energy and/or
r r r
( )
charge fluxes may appear non thermodynamic equilibrium state f 0 k f k , r , t ( )
f0 may be modified as result of:
r r
- variation of the CC numbers in the volume element dr ( dr = dx dy dz ), described by position vector rr
(i.e. caused by diffusion or drift processes);
r r
- transition between the energy states characterized by k and k ' under influence of external fields
AND/OR
- variation of the CC numbers in a specific energetic state due to scattering mechanism (loosing energy)
df
f
f
Total time variation: is due to and
dt
total t
diff , field t
scatt .
df
f
f
In stationary state, = 0 so we must assume that (formally) = (*)
dt
total t
diff , field t
scatt .
Now, lets stop the external field(s). f f 0 only due to scattering. If the fields were not too strong, we can
f f - f0 t
assume that = - , having the solution ( f - f ) = ( f - f ) e -t
t
scatt . t 0 t 0 t =0
Scattering mechanisms
a onto ionized impurities
2e 2 m *1/ 2 E 3/ 2
tI = @ t E 3/ 2
2 0
e E
N I p Z 2e 4 ln
1+
1/ 3 2
N I Ze
(Z is the difference between valences of base and impurity atoms!!!)
m *2 e 2 1
b onto neutral impurities: t N =
20e h3 N n
(Nn neutral impurities concentration at a certain temperature (episode 2!!))
c onto lattice vibrations (phonons!!)
E -1/ 2
p 2h4 r v 2
acoustical t ac =
2 ( 2m *) E r2 N kT
3/ 2
N base atoms concentration, v speed of acoustic waves in crystal, r mass density, Er deformation
potential constant (does not matter whats this)
hw
optical t opt :
exp 0 - 1
kT
d ETC...(crystalline deffects (tD), surfaces ......)
t = aE - s
parameter a can depend onto temperature and s scattering exponent
Scattering mechanism s
ionized impurities 3/2
neutral impurities 0
acoustic phonons + 1/2
optical phonons 0
n
1 1 1 1 1 1 1
More scattering mechanisms acting simultaneous: = + + + + + ... =
t ef t N t I t ac t op t D j =1t j
In semiconductor physics the most important
1 1 1
= +
t ef t imp t latt
f r r r
f
h-1
E
( )
F gk E + v grr f =
t
scatt
General BOLTZMANN equation for non-equilibrium distribution function (Beq)
OR (for small deviation from equilibrium)
f r r r f - f0 f
h-1
E
( )
F gk E + v grr f = -
t
=- 1
t
r
( )
t k depends of f1 non-linear integro-differential equation which cannot be solved in general case
and, subsequent, coefficients of the transport phenomena (Hall, electrical conductivity, ..)
r r r r r r
Example: for electrical field, E and magnetic field, B F = -eE - ev B
f r r r r
f
eh-1
E
( )
-E - v B gkr E + v grr f =
t
(back)
scatt
1. ELECTRICAL CONDUCTION
1 kind of CC (e or h)
r r
Remember: for weak (?) electrical fields: j = s E , where s - electrical conductivity and current density (charge
passing in time unit through a unit of surface normal to the current direction): je = -neve ( ve see above!)
*******************************************************************************************
n = n( T )
s = s ( T )
m = m(T)
et e
1.1.1.1. Temperature dependence of the mobility ( me = ):
me
Low temperature domain weak thermal oscillations ionized impurities scattering prevails: m = AT 3/ 2
High temperature domain all impurity atoms are ionized lattice vibrations scattering: m = BT -3/ 2
T
1.1.1.2 Temperature dependence of CC concentration (see end of the episode 2)
I. INTRINSIC SEMICONDUCTORS
No impurity:
Eg
-
ni = NC NV e 2 kT Eg Eg
- -
(
s i = e NC NV Bn + B p T )
-3 / 2 2 kT
e = s 0 e 2kT , where s0 is not temperature dependent
-3 / 2
m = BT
2. Intermediate temperatures : ln s
n = N D = const. the dependence A
C2
E
1.2. Advanced level: relaxation time method (a little bit detailed calculus!!)
In brief:
Step 1: use Boltzmann equation (#Beq) in a particular case
Step 2: solving this eq. determine f
Step 3: deduce the expression for j and compare with Ohm law
STEP1
Consider homogeneous n-type semiconductor; spherical isoenergetic surfaces; presence of an weak electric field
applied as to E x = E , E y = 0 , E z = 0 Fx = -eE , Fy = 0 , Fz = 0
r r -1
f0 E f - f0
homogenous f is no r dependent v grr f 0 = 0 #Beq becomes h ( -eE ) =- and, with
E
kx te
E f f - f0
= hvx , we have h-1 0 ( -eE ) hv x = - wherefrom
kx E te
STEP 2
1
f0 f0 =
f = f 0 + et e v xE with E -
EF and, finally (some director cut here!!!) (Class/home-work 3)
E exp + 1
kT
f0 ( 1 - f0 )
f = f 0 - et e ( E ) vxE
kT
STEP 3
r r r r r f ( 1 - f0 )
calculate jex = -e ( ) ( ) ( )
N k f 0 - et e ( E ) vxE 0
N k f k vx dk x dk y dk z or jex = -e ( )
kT
vx dk x dk y dk z
( )
+
BUT f0(E) - even function of v (vx f0) is odd f0vx ( dk x dk y dk z ) = 0 (this is normal: no E no j)
-
r d kx d k y d kz
( )(
1 - N k d kx d k y d kz = ) 8p 3
(see Episode 1) and N C ( E ) dE = 2p ( 2me ) h -3 E1/ 2 dE (see Episode 2)
3/ 2
OR (noting C = 2p ( 2me )
3/ 2
h -3 )
2 - N C ( E ) dE = C E1/ 2 dE
r
( )(
Both 1 and 2 represent the same quantity N k d k x d k y d k z = NC ( E ) dE )
2 C e 2E
E 3/ 2 f 0 ( 1 - f 0 )
te ( E )
3 me kT
jex = dE (remember why & when between 0 and ????)
0
Its time for some tricks (see, for example, R.A. SMITH, Semiconductors, Cambridge University Press, 1980)
t e ( E ) E 3 / 2 f 0 dE
t e ( E ) E 3 / 2 f0 dE
E 3/ 2
f 0 dE
0 0 0
First, consider (*) or
and look. Clearly, the first
1/ 2 3/ 2 1/ 2
E f 0 dE
E f 0 dE
E f 0 dE
0 0 0
ratio is
te ( E) E
3/ 2
f 0 dE
te = 0
(**) some comments here!!!
3/ 2
E f 0 dE
0
-E
3
te ( E)
Third (putting all 6 blue stars together): E 3 / 2 f 0
dE = kT t e
E 1/ 2
f 0 dE
0
2 0
N C ( E ) f 0 dE with N C ( E ) dE = C E1/ 2dE (see above!)
Fourth: remember that n =
0
ne2 t e
Finally: jex = E
me
An interesting conclusion appear: comparing with Ohm law, jex = s eE , it is found that
ne 2 e te
se = te and mCe = !!!!!
me me
f 0 = 1 if E < E F f
Now, the trick: for degenerate semiconductors, (remember why!!!) 0 strongly changes
f 0 = 0 if E > E F E
2 C e 2E
f
for E EF (and 0 otherwise) jex = - t e ( EF ) EF3/ 2 0 dE or
3 me 0
E
2 C e 2E
jex = t e ( EF ) EF3/ 2
3 me
3 3/ 2 3
Finally, remember that n = 2p ( 2me )
3/ 2 -3
h EF or (see notation for C above) n = CEF3/ 2 and
2 2
enet e ( EF )
jex = E wherefrom
me
et e ( EF ) et e ( EF )
s e = en and me =
me me
(feel free to comments relations above and to think to the same cases for holes)
MOST GENERAL CASE: arbitrary shaped isoenergetic surfaces effective mass becomes a 6 component
At high impurity concentrations, electrons may jump from a neutral atom to an ionized one
without activation energy!! (especially at low temperatures)
U0 U0
x x
(a) (b)
U0
(a) no electric field: uright = uleft = u = u0 exp -
kT
a a
U 0 - qE 2 U 0 + qE 2
(b) with electric field: u 'right = u0 exp - and u 'left = u0 exp -
kT kT
(boring calculus)
N def q 2 a 2 U0 qa 2 U0
ionic conductivity: sL = n 0 exp - and ionic mobility: mL = n 0 exp
-
kT kT kT kT
local states
Eg
0
EV EF EC E EV EC E
(a) (b)
------------------------------------------------------------------------------------------------------------
2. CC TRANSPORT IN ELECTRIC AND MAGNETIC FIELDS
y
2.1. HALL EFFECT
0
x r L
FEe M1
2.1.1. Free electrons method z
+ + + + D+ + + +
r
a: n-type, spherical isoenergetic surfaces, ve r r b
FLe Ex
A B
constant relaxation time r
e
je r
U CD : I x Bz Ey r r
Ex + Ey
r r r C d
Lorentz force: FL = -ev x Bz
r r r M2
Electrostatic force: Fe = -eE y B
1
In stationary case: E y = E H FL = Fe E H = vx Bz and jx = - nevx E H = - jx Bz
ne
1 1
Hall coefficient: Re = - ; Rh = + ; (easy to find [ R ] = m3 / C ) Sign of R is the same as CC!!
ne pe
Ey
Hall angle: tg e = (see figure above!) Home/class-work: show that tge = me B (tip: use s definition)
Ex
r r
Re = - and Rh = + , where r Hall parameter (Hall factor) depend on scattering mechanism
ne pe
1 r mCe
Re = - (*) and s e = nemCe Re = - Re s e = r mCe m He = r mCe and m Hh = r mCh
ne se
Determining DEd
DEd -3/ 4 DEd
-
DEd
(*) r 1 r 1 1 2p me*kT
n = NC N d e 2 kT uur Re = - e 2 kT =- 2 e 2 kT
e NC N d e ND 2
h
OR
DEd
( )
DE d
( DE
) = f ( 1/ T ) is a
3/ 4
Re = CT -3/ 4e 2 kT ; C C ( T ) ReT
3/ 4
= Ce 2kT ln ReT 3/ 4 = C '+ d plot of ln ReT
2kT
straight line ..
j r r
r vh Also E y = Rjx B ; R = ?
Eey FLh
+ + + C + + + Please see the calculus in Annex2
y (SP2)!!
x r
B RESULTS only here!!
z
p mh2 - nme2 1 me p - nb 2 1
Rmix = or, by using b = R
(CC mobilitys ratio!!), mix =
( p m h + nm e ) e
2 mh ( p + nb ) 2 e
1 1- b
Particulate case: intrinsic semiconductors: n = p = ni Ri = (b</>1!!!)
ni e 1 + b
Determining Eg from temperature dependence of the Hall coefficient: see blackboard demonstration!!
c: Amazing case of high magnetic field regime: (Or, how to work for nothing!!!!?????)
If me B = 1 and/or mh B = 1 weak magnetic field (sometime, is used wt = 1 or w 2t 2 = 1 , with w/2p
cyclotronic resonance frequency see later)
Bx = 0 , B y = 0, Bz = B
eB
= we ,
For electric and magnetic fields oriented as above, and noting
E x 0; E y 0; E z = 0 me
g e
vex = - E x - we v y
me
g (1 a & b)
e
vey = - E y + we vx
me
By, solving this system, CC velocity components can be determined and, subsequently, j.
g g e 1
1. multiplying 1a with i and add to 1b: vex + i vey = -
me
(
E x + iE y - wei )
vex - vey (2)
i
g g g
2. introduce complex quantities Z = vex + ivey and Z = vex + i vey (3 a & b)
g e
3. Now, (2) is equivalent with Z + iwe Z = -
me
(
E x + iE y )
1 - e-iwet
4. Solution is Z = Z 0eiwet +
e
me
(
E x + iE y
iwe
) with Z 0 = vex 0 + ivey 0 (Z for t = 0)
5. This must be averaged over all values of free path (or time between collisions!!):
e te
Inserting blue Z and integrate vex + ivey = -
me
(
Ex + i E y
1 - iwet e
)
(some algebra dropped)
(E.H. PUTLEY, The Hall Effect in Semiconductor Physics, Dover Publications, New York, 1960;
R.A. SMITH, Semiconductors, Cambridge University Press, 1980;
H.F. WOLF, Semiconductors, Wiley-Interscience, New York, London, Sydney, Toronto, 1971.)
5.3. Problem: cannot compare real and imaginary parts!
5.4. Solution: multiplying an dividing with 1 + iwet e
jex jey
5.5. Taking into account that vex = - and vey = -
ne ne
jex =
ne 2 E x
te 2 2 -
( -wet eE x ) ( wet e ) j = ne2 t E = ne et e E = nem E
8. or ex e x x e x
me 1 + we t e 1 + we2t e2 me me
9. Finally: jex = s eE x !!! NOTHING NEW HERE !!!! Just Ohm law !!!
10. Now lets determine Hall coefficient, Re from general relationship E H = Re Bjex
Ey
10.1. From (*), E x = - ;
wet e
ne2 t e 1
10.2. Substituting in first pink relation: jex = - E y ( E y = EH )
- wet e
me 1 + we t e wet e
2 2
ne 2
eB j = - E
10.3. Finally (rember that = we ), ex eB H wherefrom
me me
me
1
10.4. Re = - !!! ALSO, NOTHING NEW HERE !!!! Same value as in case 2.1.1. above !!!!
ne
1
Equivalent for p-type semiconductors: Rh =
pe
Conclusion: for single conduction type semiconductors, magnetic field induction value is not important!!
Dont be disappointed! We acquired two useful pink relations!!! Lets use them to study
d: Mixed conduction case in strong magnetic field
1. Starting with the same two pink relations above for electrons:
ne2 t e wet e2 ne 2 t e wet e2
jex = 2 2 x E - 2 2
E y and jey = 2 2 y E + 2 2
Ex
me 1 + we t e 1 + we t e me 1 + we t e 1 + we t e
and similarly for holes
pe 2 t h wht h2 pe 2 t h wht h2
jhx = 2 2 Ex - 2 2
E y and jhy = 2 2 Ey + 2 2
Ex
mh 1 + wh t h 1 + wh t h mh 1 + wh t h 1 + wht h
2. continue introducing helpful notations:
ne 2 t e ne2 wet e2 pe2 th pe2 wht h2
Ae = ; De = ; Ah = ; Dh =
me 1 + we2t e2 me 1 + we2t e2 mh 1 + wh2t h2 mh 1 + wh2t h2
jex = AeE x - DeE y
jhx = AhE x - Dh E y
3. As result, and
jey = AeE y + DeE x jhy = AhE y + Dh E x
4. Total current densities are given by jx = jex + jhx and j y = jey + jhy OR
jx = ( Ae + Ah ) E x - ( De + Dh ) E y (*) and j y = ( Ae + Ah ) E y + ( De + Dh ) E x (**)
Ae + Ah
5. In stationary case, jy = 0 and E y = E H so, from (**), we obtain E x = - EH
De + Dh
( Ae + Ah ) 2 + ( De + Dh ) 2 E
6. Introducing this value in (*) and jx = - H OR
( De + Dh )
EH = -
( De + Dh ) jx
( Ae + Ah ) 2 + ( De + Dh ) 2
( De + Dh )
7. Compare with E H = Rm Bjx and find that BRm = -
( Ae + Ah ) 2 + ( De + Dh ) 2
8. Remember and use expressions for s, m, w, R, A and D (both for electrons and holes) to prove that
Rm =
( ) (
Res e2 1 + s h2 B 2 Rh2 + Rhs h2 1 + s e2 B 2 Re2 ) OR Rm =
( )
1 p - b n + b mh B ( p - n )
2 2 2 2
( s e + s h ) 2 + s e2s h2 B 2 ( Re + Rh ) 2 e ( p + bn ) 2 + b 2 mh2 B 2 ( p - n ) 2
(Chamber relations. See R.G. CHAMBERS, Proc. Phys. Soc., A65 (1952) 903.)
9. Conclusions:
for mixed conduction type semiconductors, in strong magnetic field, Hall
coefficient depends on B2 !!
( )
Moreover, for p - b n + b mh B ( p - n ) = 0 , Hall coefficient becomes 0 !!!
2 2 2 2
p - nb 2 1
In weak magnetic field ( m B = 1 ), Rm = (see far above!!)
( p + nb ) e
2
1
For very strong magnetic field, Rm @ const. (divide Rm with B2 )
e( p - n)
w eB
Corresponding frequency can be determined from uc = =
2p 2p m
w (and uc ) does not depend neither on particle velocity (kinetic energy) or trajectory radius!
If, in addition of static electric and magnetic fields, a variable high frequency electric field is applied, the moving
particle start to absorb energy and their trajectory radius grow as the field frequency is approaching to uc . Knowing
this frequency permit to determine the particle effective mass!!
WEAK or STRONG field can be classified comparing CC relaxation time with rotation period in magnetic field:
Weak: during relaxation time, t, no complete rotation is done.
Strong: during relaxation time, t, several rotations were done.
w eB t w eB t
These are equivalent with t= ? 1 (weak field) and t= = 1 (strong field)
2p m 2p 2p m 2p
et
Remember that m = .
m
2. Starting again with the pink equations above (we have not work just for nothing!!!)
ne 2 ne 2
jex = t eE x - wet e2E y
and
jey = t eE y + wet e2E x
me me
ne 2 ne2
4. Averaging these: jex = t e E x - we t e2 E y and jey = t e E y + we t e2 E x where
me me
2
t e ( E ) E 3/ 2 f 0 dE
te ( E)
E
3/ 2
f 0 dE
te = 0
and t e2 = 0
(see (**) at 1.2)
3/ 2 3/ 2
E f 0dE
E f 0 dE
0 0
2 2
2 te +w t2
5. Presuming again stationary conditions (jey = 0 and E y = E H ), jex = - ne e e E
H
me we t e2
2
2
2 me eB t e 1
6. Neglecting again we t e , finally E H = - 2 jex OR E H = - re B jex
ne me t e 2 ne
re
7. Compare with E H = Re Bjex Re = - with
ne
5 5
- 2s
t e2 2 2
re = 2
OR r = 2 (Hall factor/parameter)
te 5
-
2 s
Examples (see at the beginning):
3 5
s = 1/2 (lattice vibrations) r = 2 2 = 3p = 1,18
2
( 2)
8
315p
s = 3/2 (impurities) r = = 1,933
512
8. We must stop here!!! Ill be back if we have time!! (strong magnetic field, degenerate semiconductors,
multiple minima, non-spherical isoenergetic surfaces etc. lefted out !!!)
-----------------------------------------------------------------------------------------------------------------------------------
2.2. MAGNETORESISTIVE EFFECT
--------------------------------------------------------------------------------------------------------------------
f0 r r
r f - f0
Remeber Beq.? h-1 F gk E + v grr f 0 = - .
E t
Step 1: deducing non-equilibrium function
Insert temperature gradient in 1D case:
f0 f dT f - f0
-eE x vex + vex 0 =-
E T dx te
--------------------------------------------------------------------------------------------------------------------
3.2. THERMO-ELECTRIC EFFECTS
Definition: transport phenomena that appear in semiconductors under the influence of electrical
fields and temperature gradient
(a) in a semiconductor sample, in which a temperature gradient exist, a thermoelectric voltage can
appear
OR
(b) at the ends of a circuit made up from two (or more) different materials those junctions are
maintained at different temperatures, also a thermoelectric voltage appear
T2
T1 T2 <T1 B
A mV
mV B
T1
(a)
(b)
1. Ettingshausen effect: y
M2 T2 < T
electrons with ve = vem
x
cool electrons
In stationary case, E H = vem B - + +
r+ + + + +r +
z hot electrons
valuable only for mean value of r rF r r F r Ee
drift velocity (the same for all v e = v emFrEe v
r r F
e 2 < v em r Ler r
electrons/no distribution Le
r E x v e1 > vem FrEe j ex
function constant relaxation EH
time!!!). Otherwise, >>>>>>>
FLe
r M1 T1 > T
Definition: give your own B
dT
= -Pe B jex Guess what? Pe is Ettingshausen coefficient which can be simply written as
dy
2 t e2 t e E t 2 E t h2 t h E
me t e E and Ph = mh h (not dependent on CC type!!)
Pe = - -
ek t e 2 te
3 ek t h 2 th
3
2. Nernst effect:
Only excess carriers on L2 side in respect with L1 side y
x
were represented M2
z
+ + + + + + + +
dT
E y = QBz Q Nernst coefficient:
dx
L2
2 t e2 t e E L1
me t e E or Q = - rsk me and for holes
r
Qe = 2
- 3 e
Ey
eT t e te e
T1 < T r M1 T2 > T
2 t h2 t h E B
m h t h E
Qh = -
eT t h 2 th
3
3. Righi-Leduc effect:
y
dT dT M2 T4
= SBz x
cool electrons
dy dx hot electrons
z
dT
T1 T2 > T1
dy
S (R-L coefficient!) is given by L1 dT L2
2 2 2
nme2 t e E t e E t e2 2 t e2 E t e E dx
Se = - + -
Tek t e 2 te
4
te
3
r
M1 T3 > T4
or S = - nk 2 m 2Tr ( 5 - 4s + 2s )
2
and equivalent for holes..
e e
2ek
See again Annex 3 to find some values of the involved terms
End of episode 3