Chapter 3 :

Second order
Non Linear Optics
-
3 waves interactions
 Part 1 :
The second order
non linear
susceptiblity

NL (2 )
P ( ω 3 ) =ε o . χ ( ω3 =ω 1+ω2 ) . Ei ( ω 1 ) . E k ( ω2 )
j jik
First simplication :

- the functions used in the Fourier series represent physical parameters, so they must be real
- yet, wl could be positive or negative in the equations :
- it’s just a matter of choice of the positive orientation
- it has not particular physical signification

Þ +/- terms are conjugated and follow :

In the case of a 2nd order NL interaction, e

Second simplification : ABDP relations

If we consider again only the 2nd order interaction,

when the three pulsations w1, w2 and w3 are simultaneously existing in the medium,
the following three relations could be obtained and are equivalent :

The elements of the tensors [c(2) (w1)], [c(2) (w2)], [c(2) (w3)] are linked by the

Armstrong, Bloembergen, Ducuing and Pershan (ABDP) relations [ref BLOEMBERGEN]

Third simplification : Kleinman’s relations [ref Kleinman]

- when the fields are far from the absorption bands, the tensor elements are not dependant with
the pulsation

- and if we consider the creation of w3, there is no difference between polarizing w1 and w2
according to i and k, or according to k and i

 It follows that the indexes could be written in any order

c(2)jik = c(2)kji = c(2)ijk = c(2)ikj = c(2)kij = c(2)jki

 The number of necessary elements for a tensor of rank 3 decreases from 27 to 18

 Easier : contraction of the two last indexes j,k in one new index j

j = xx = 1 j = yz = zy = 4 the 3rd rank tensor could be represented

j = yy = 2 j = xz = zx = 5  by a « simple » 3x6 matrix with elements cij
j = zz = 3 j = xy = yx = 6
where i  [1, 2, 3] and j  [1, …, 6]

[c(2)] =

Adding symmetry properties :

18  10 maximum non zero elements in the 2nd order susceptibility tensor

 Main case :

( )
𝐄 𝐱 ( 𝛚 𝟏 ) . 𝐄 𝐱 ( 𝛚𝟐 )
𝐄 𝐲 ( 𝛚 𝟏 ) . 𝐄 𝐲 ( 𝛚 𝟐)

( )[ ]
𝐍𝐋
𝐏 𝐱 ( 𝛚𝟑 ) 𝛘 𝟏𝟏 𝛘 𝟏𝟐 𝛘 𝟏𝟑 𝛘 𝟏𝟒 𝛘 𝟑𝟏 𝛘 𝟐𝟏
𝐄 𝐳 ( 𝛚 𝟏 ) . 𝐄𝐳 ( 𝛚𝟐 )
( 𝛚𝟑 ) = 𝛘 𝟐𝟏 𝛘 𝟏𝟐 .
𝐍𝐋
𝐏 𝐲 𝛘 𝟐𝟐 𝛘 𝟐𝟑 𝛘 𝟑𝟐 𝛘 𝟏𝟒
𝐄𝐲 ( 𝛚𝟏 ) .𝐄 𝐳 ( 𝛚 𝟐 ) +𝐄𝐳 ( 𝛚 𝟏 ) . 𝐄 𝐲 ( 𝛚𝟐 )
𝐏 𝐍𝐋
𝐳 ( 𝛚𝟑 ) 𝛘 𝟑𝟏 𝛘 𝟑𝟐 𝛘 𝟑𝟑 𝛘 𝟐𝟑 𝛘 𝟏𝟑 𝛘 𝟏𝟒
𝐄𝐳 ( 𝛚𝟏 ) .𝐄 𝐱 ( 𝛚 𝟐 ) +𝐄 𝐱 ( 𝛚𝟏 ) . 𝐄𝐳 ( 𝛚𝟐 )
𝐄𝐱 ( 𝛚 𝟏 ) .𝐄 𝐲 ( 𝛚 𝟐 ) +𝐄 𝐲 ( 𝛚 𝟏) . 𝐄𝐱 ( 𝛚𝟐 )

Consider now the different symmetry classes for cristalline media :

Centrosymmetric classes

All moduli vanish

Triclinic - Class 1
Number of non zero moduli
 Monoclinic - Class 2 (2//y - standard) Monoclinic - Class 2 (2 // z)

Monoclinic - Class m (m  y - standard) Monoclinic - Class m (m  z)

Orthorhombic - Class 222 Orthorhombic - Class mm2

Tetragonal - Class 4 or 4mm Tetragonal - Class

Tetragonal – Class 422 ou 2m

Idem centrosymmetric class,
all moduli vanish
 Cubic - Class Cubic - Class 432
Idem centrosymmetric class,
all moduli vanish

Trigonal - Class 3 Trigonal - Class 32 Ex : quartz

Trigonal - Class 3m (m x - standard) Trigonal - Class 3m (m  y)

Hexagonal - Class 6 or 6mm Hexagonal - Class Hexagonal – Class 622

Idem
4 or 4mm

Hexagonal - Class m2 (m  x – standard) Hexagonal - Class m2 (m  y)

Idem 422 and
centrosymmetric class,
all moduli vanish
Several orders of magnitude

Generally, the NL coefficient dij (unit : pm/V) is used instead of cij cij= 2. dij

Materials dij values

Oriented polymeric materials (with d33 from 1 to 100 pm/V
dyes incorporated)
Inorganic crystals :
- KDP, quartz dij from 10 to 2000 pm/V
- LiNbO3, LiTaO3 dij from 0,5 to 50 pm/V

Oriented organic glasses d33 = 7 or 8 pm/V

Organic monocrystals d33 from 10 to 50 pm/V
Polyvinylic alchool (PVA) d33  41 pm/V
Polymeric liquid crystals (on d33 from 1 to 10 pm/V
polystyrene support)
Ferroelectric copolymers d33  1 pm/V
(PVDF-TrFE, PVDCN-Vac)
 First illustration : Second Harmonic Generation

w1 = w2 = w  w3 = 2w

( )
2
E x (ω )

( )[ ]
2
P NL E y (ω)
x (2 ω) χ 11(2 𝜔 ) χ 12 (2 𝜔) χ 13 (2 𝜔) χ 14 ( 2 𝜔) χ 31(2 𝜔) χ 21 (2 𝜔 ) 2
P NL = χ 21 (2 ω ) . E z (ω)
y (2 ω) χ 22 (2 ω) χ 23 (2 ω) χ 32 (2 ω ) χ 14 (2 ω) χ 12 (2 ω)
NL
χ 31 (2 ω ) χ 32 (2 ω) χ 33 (2 ω) χ 23 ( 2ω ) χ 13 (2 ω )
( )
χ 14 ( 2ω ) 2. E y ω . E z ω
( )
P z (2 ω)
2. E z ( ω ) . E x ( ω )
2. E x ( ω ) . E y ( ω )

The input wave (pump beam) reacts with itself.

Double pulsation wave (half wavelength) is generated inside the medium.
Ex : quartz crystal – symmetry class 32
=

Ex : oriented polymer – symmetry class mm (idem 6mm)

=
Training :
Exercise 1
Exercise 2 (part A)

Furthermore about SHG (won’t be done during the tutorial sessions):

CASE STUDY 1 - SHG Reflection and transmission - NL Brewster effect
CASE STUDY 2 - SHG Transmission - NL coefficients measurement