Nonlinear optical properties of highly oriented polydiacetylene evaporated films

T. Kanetake, K. Ishikawa, T. Hasegawa, and T. KodaK. Takeda and M. HasegawaK. Kubodera and H. Kobayashi

Citation: Appl. Phys. Lett. 54, 2287 (1989); doi: 10.1063/1.101104

View online: http://dx.doi.org/10.1063/1.101104
View Table of Contents: http://aip.scitation.org/toc/apl/54/23
Published by the American Institute of Physics
Nonlinear optical properties of highly oriented polycUacetylene evaporated
films
T. Kanetake, Ko Ishikawa, T. Hasegawa, and To Koda
Department 0/ Applied Physics. Ulliuersity o/Tokyo. Tokyo 113. Japan
K. Takeda and M. Hasegawa
Departmem a/Synthetic ChemL~try, University of Tokyo. Tokyo] 13, Japan
K. Kubodera and H. Kobayashi
NTT Optoelectronics Laboratories, Atsugi. Kanagawa 243-03. Japan

(Received 9 January 1989; accepted for publication 21 March 1989)

Third-order harmonic generation has been measured on highly oriented polydiacetylcne
(PDA) films prepared by the vacuum deposition method. Experimental values of the third-
order electric susceptibility XIJ ) measured for pumping laser polarized parallel to the polymer
chain show a sharp three-photon resonance to the IE" exciton in PDA. Potential usefulness of
these highly oriented PDA evaporated films in nonlinear optical applications is suggested.

The nonlinear optical (NLO) properties of conjugated
polymer polydiacetylenes (PDAs) are currently attracting
interest because of the fairly large third-order electric sus-
ceptibility Xi:') and the very fast NLO response time. I Due to
the possible interest in NLO applications, third-order NLO
properties have been extensively studied in PDA films of
various forms, including shear-melt-grown thin crystals,2
Langmuir-Blodgett films,:; solvent-cast films,4 and vacuum-
deposited films. 5 •6 A severe problem with these films is the
large light scattering loss due to their irregular structure. In
order to minimize this effect, it is necessary to produce high-
ly oriented films of good optical quality. We have attempted
to fulfill this requirement by using a specific vacuum depo-
sition technique. 7 In this letter we report on the NLO prop-
erties of these highly oriented PDA films. Some of the pre-
liminary results on these films have already been reported. 6
Polydiacetylene monomers were used as the startiIlg
=
materials. These have the form of R~C= C~C C-R, where
R represents the substitutional side group
(CH z ) III U{ CH 2 ) 11 .. i CH 3' Here, U stands for the urethane
group OCONH, which is known to stabilize the planar
structure of a polymer by forming an intramolecular hydro-
gen bond network between adjacent side groups. The ther-
mal and photochemical properties of these monomers are
very dependent on the values of m and n, that is, on the
length of alkyl chains in t he side group (this is described in
detail elsewhere).x Such chemical flexibility enables us to
discover which monomer materials are suitable for film fab-
rication. In the present study, we report on the results ob-
tained 011 PDA films prepared using monomers with m = 4
and n =.= 3,4,5. There PDAs are abbreviated as PDA-C~UCti
(11 = 3,4,5).
The first step in film fabrication was the vacuum depo-
sition of a thin monomer layer (of about 10 nm thickness)
upon a glass substrate. The deposition temperature was
around 120°C and the deposition rate was approximately 50
nm/h. After photopolymerization ofthis layer using 365 nm
light filtered from a Hg discharge lamp, the surface of the
layer was repeatedly rubbed with a soft silicone cloth along a
specific direction. This rubbing process is envisaged to cause
mechanical alignment of the polymer fibrils on the treated
substrate, which are otherwise irregularly arranged. A
thicker monomer layer of about roo nm thickness was then
deposited onto this substrate. After photo polymerization,
the resultant PDA lUms showed it high degree of optical
anisotropy, with an optical density ratio of around 30
between the directions of poiarization parallel and perpen-
dicular to the rubbing direction.
Measurements of the third-harmonic generation
(THG) were made on the vacuum-deposited PDA films,
using an optical system composed of a Q-switched Nd:Y AG
laser and a dye laser, details of which are described else-
where.'·') The PDA films, either oriented or unoriented,
were mounted on the rotable tip of a goniometer so that the
films could be rotated around the vertical axis perpendicular
to the impinging laser beam. The polarization of the laser
light in this case was paranel to the rotation axis. The dura-
tion of the laser pulse was 5.5111' with a repetition rate of 10
Hz and the power density was, in most cases, set at about 80
MW Icm 2 • Degradation of PDA films by the laser irradia-
tion was observed when the power density exceeded 130
MW fcrn". All measurements were made in the air at room
temperature.
For the experimental evaluation of the third-order elec-
tric susceptibility ill, the THO intensities (as a function of
the rotation angle e of the goniometer) were measured on
the PDA fLlms. A fused silica plate was used as a standard.
Some caution was necessary in the measurements to prevent
the NLO effect of the environmental air. 10 When we used a
focusing lens of focal length greater than 80 mm, the THG
intensities from a I-mm-thick silica plate Ll'l
(SiO]) = 2.8X 10- 14 esu at 1.9 {Lmj were found to be con-
siderably dependent on the air pressure
[xt'i(air) = 1.8)< 10 17 esu at 1 atm and 1.9 pm]. However,
when a 50 mm focal length lens was used, the THG intensity
of the silica plate was confirmed to be essentially indepen-
dent of the air pressure. Thus, all measurements were made
in air using a 50 mm focusing lens. Experimental i 3l values

2287 Appl. Phys. Lett. 54 (23), 5 June, 989 0003-6951/89/232287-03$01.00 Co) i 989 American Institute of Physics 22B7
 x 104 the laser light. As seen in Figs. 1(a) and 1(b), the THO
(a) Orient ..d Rim (E,,)
~. 5 intensities are nearly four orders of magnitude larger for the
11) parallel polarization than for the perpendicular one. The
'.V".
corresponding X<3! values were estimated to be 2.9 X 10- !()
0.5 ....:-. :\~:~~.\
esu and 0.03 X 10 -10 esu for the parallel and perpendicular
3 (b) Oriented Film (E~) polarizations, respectively. The ,\)3)( II) value is, to some ex-
tent, dependent on the film quality and the thickness. The
maximum value found for a pumping wavelength of 1.90 pm
was about 5 X 10 - to esu. [Strictly, the XU )( II) values should
?: be corrected for the self-absorption of the THG light in the
.~
., x'0
I
3 (c) Uncriented Film
film as discussed later.] However, the THG intensities in the
.E 3
unoriented film rFig. 1 (c) ] were found to be independent of
2
the direction of polarization, giving the isotropic average :to)
X
value of 1.0>< 10- 10 esu. The ratio of Ll )IX(3) ( II) is about
0.34, which is close to <cos 4 ¢) = 3/8, with ¢ being the angle
between a conjugated polymer chain and the electric vector
of the polarized laser light. This indicates that the polymer
chains in the unoriented film are randomly oriented within
- 60 -40 - 20 0 20 40 60
the plane paranel to the substrate. Detailed studies of the
film structure confirmed this result. I I
Incidence Angle e (/ deg )
The i 31 values fOT three kinds of PDA-C4 UC"
FIG. 1. Relativc THG intensities vs rotation angle fi around a vertical axis
at 1.90 flm pumping ill the air at room temperatnre, (a) and (b) for an (n = 3,4,5) films at 1.90 llYn excitation are listed in Table 1.
oriented polydiacetylcne (PDA-C,UC,) t1lm (109 11m thick) ill the polar- Previously, Tomaru et al. have reported the anisotropic i'l
ization direction parallel and perpendicular to the oriented axis, respective- values in an oriented PDA film, X i3l ( II ) = 0.11 and
ly, (c) for an ulIllrientcd PDA-C,UC, evaporated lilm (108 nm thick), Cd) X,l)(l) <0.01, both in thc units of 10- 10 esu. 5 The present
fe)f a i-mm-thick glass substrate.
X(31 values are more than ten times larger than their result.
Possible reasons for the large i 3 ) values in the present study
of PDA films were evaluated from the observed relative
are proposed to be due to the high degree of photopolymeri-
THG intensities and the film thickness using the following
zation and to the longer conjugation length of polymers in
relation'-J;
the present samples. In Table 1, it is noticed that the X(3!( II)
2 I \ l/' 21/(3)'0
I
(1) value becomes larger as the number of 11 decreases from 5 to
rr ( J ~)"""' )
=::;.- ---) -

I ,{, I
Here I is the thickness of the PDA tHm, which is assumed to
be much smaller than I he coherence length, J) and arc
the third-order susceptibility and coherence length of the
standard fused silica glass, respectively, and I and I ~,cab are
peak THG intensities in the fringe patterns of the PDA film
and silica, respectively.
The relative THG intensities for 1.90 {-tm excitation are
plotted in Fig. 1 as a function of the rotation angle (J for an
oriented PDA-C., U Col film ( 109 nm thick) in Figs. 1 (a) and
1 (b), an uiloriented PDA-C4 UC 4 film (108 nm thick) in
Fig. 1 (c), and for a I-mm-thick glass substrate in "Fig. 1 Cd).
The oriented film shows anisotropy in the polarized absorp-
tion, whose anisotropic ratio is as large as 30. The THO
intensities were also found to be strongly dependent on the
relative direction of the oriented axis to the polarization of
3. The present data arc, however, insufficient to conclude if
such a trend is intrinsic.
'e.' In the measurements mentioned above, the pumping
wavelength was fixed at 1.90 pm. The corresponding photon
energy is 0.65 eV, which is just resonant to the three-photon
transition to the I B" exciton at 1. 95 e V (see Fig. 2). There-
fore, there must exist a significant resonant enhancement
effect in the THG process. In order to investigate this effect,
we have made THG measurements on an oriented PDA-
C. U C 4 film in the wavelength region L5~2.1 pm of the
pumping laser. The resulting THG emission covers the pho-
ton energy region 1.8 to 2.5 eV, where a strong absorption
due to the IS" exciton and its vibronic side bands is observed.
Therefore, the observed THG intensities should be corrected
for the internal attenuation of the THG field in the film. A
theoretical treatment of the attenuation effect for the har-

TABLE I. Third-order electric susceptibility x''' of the urethane-based polydiacetylcne (PDA) evaporated films at 1.90,um pumping. The X'" values are not
corrected for the self-absorption effect in the films. The side group C,Ue,,: - (CH,).OCONH(CH,)" ,CH, .

Thickness ,( 10 '" esu)

Sample Structure (Al isotropic parallel pcrpemllcular

I'DA-C.UC, unoriented 550 1.8

oriented 530 3.8 0.2
PDA-c,ue, unorientcd lOgO 1.03
oriented 1090 2.9 0.03
PDA-C,UC, utloricnted 1200 0.94
oriented 1100 2.1 ()'o8

2288 Appl. Phys. Lett., Vol. 54, No. 23. 5 June 1989 Kanetake et at. 2288
 PHOTON ENERGY leV
0.5 0.6 0.7 0.8 0.9
x n
2 the THG emission by the vibronic excitons, since the data
15 1.8 2.1 v. 2.7
PHOTON ENERGY leV
FiG. 2. Chain direction components of the complex refractive indices;
nOCl» (broken line). K(3I!» (solid Iinc), and the third-order electric sus-
ceptibility I.1'O'! (open circles) of a highly oriented polydiacctylene (PDA-
C 4 U C.) film ( 100 nrn thick) at room temperature. Photon energies in the
lower abscissa are for n,K( 3M) spectra and THO emissions, and those in the
upper abscissa are for the pumping laser beam polarized parallel to the ori-
ented axis of film.
monic fields in the PDA fUm has been reported by Kajzar
and Messier. 3 Based on a similar assumption, we have exam-
ined the normal propagation of the pumping field at (u and
the third-harmonic field at 3m in the three-layer structure
composed of a transparent glass substrate, an absorptive
PDA film with complex refractive index h( = n + iK) and
thickness 1, and the air. The theoretical procedure is straight-
forward, and we get the following expression for the correct-
ed li')1 in terms of the experimental li])1 given by Eq_ (1)
and correction factors which should be taken into account in
the resonant case:
I.
X
011 '''JlT
= IXL'lfIc,p Iii,t", -1- n;",
l'
I ommendations are much appreciated.
ll",,, + I
(l::.kl)l + (al/2f
X ( 1 + exp( - al) - 2 exp(- al/2) cos(Akl)
Here, a (3&) = 6WK ( 30> ) / c is the absorption constant of the
film, l::.k is the wave vector mismatch between the fundamen-
tal and harmonic light in the film, and n~,,) ( = 1.46) is re-
fractive index of standard silica, In order to evaluate the
ix( 31 1corr values, we need the values of n,K( 36)). They were
determined from the absorption constants, property correct-
cd for the reflection loss, and a standard Kramers-Kronig
analysis on the same film used for the THG measurements.
This correction factor is approximately 3.4 at a pumping
wavelength of 1.9 !-lm, but it depends on the film thickness.
The results for 11'13) Icorr (open circles) and n ,K( 3il») (solid
and broken curves) are plotted in Fig. 2. [Note that the
photon energy scale in the lower abscissa is for the n,K( 30) )
spectra and THG emission, and the upper abscissa is scaled
for the photon energy of the pumping laser. ]
There are several notable features in the experimental
X(3) spectrum shown in Fig. 2. One of these is the prominent
peak at 0.65 eV which is obviously due to the three-photon
2289 Appl. Phys. Lett., Vol. 54, No. 23, 5 June 1989
resonance with the IB" exciton peak at 1.95 eV. The peak X{31
value reaches to about 1.7 X 10' 9 esu at the exciton absorp-
tion peak. Another feature is the sharp decrease in X(3) in the
region above 2.0 eV followed by a minimum at around 2.15
eV. This minimum cannot be attributed to the absorption of
have already been corrected for this effect. It is conduded,
therefore, that the THG process in the PDA film is dominat-
ed by the three-photon resonance effect with the 0-0 IBu
exciton, and that resonance with higher vibronic side bands
plays only a minor role. At energies greater than that mini-
mum, the magnitude of X<3) increases again and seems to
exhibit a second peak at around 2.4 eV. Since this energy is
dose to the one-electron band gap, predicted from the pho-
toconductivity spectra in PDA crystals (the blue form), this
second peak may be tentatively attributed to three-photon
resonance with the free-carrier generation process. How-
ever, since the present data are not sufficient as yet to reveal
the X(.1) spectrum above this second peak, we remain cau-
tious.
In conclusion, we have shown that highly oriented PDA
films made by a vacuum deposition method exhibit remark-
ably good NLO properties which are almost comparable to
those reported on PDA-PTS single crystals. 12 An important
advantage of the present PDA films is the feasibility offabri-
eating a low-loss waveguide structure using a conventional
vacuum deposition technique. Towards this goal, we are
now making accurate evaluations of the optical refractive
indices, light scattering loss factor, and other relevant opti-
cal parameters required for waveguide design.
This work has been carried out with a close collabora-
tion with Professor Y. Tokura and S. Koshihara, Depart-
ment of Physics, University of Tokyo, whose innovative rec-
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