Colloids and Surfaces A: Physicochem. Eng.

Aspects 384 (2011) 8089

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Two-dimensional arrangement of monodisperse ZnO particles with
LangmuirBlodgett technique
N. brahm
a
, D. Seb ok
a
, Sz. Papp
b
, L. K orsi
b
, I. Dkny
a,b,
a
University of Szeged, Department of Physical Chemistry and Materials Science, H-6720, Szeged, Aradi vt. 1, Hungary
b
Supramolecular and Nanostructured Materials Research Group of The Hungarian Academy of Sciences, H-6720, Szeged, Aradi vt. 1., Hungary
a r t i c l e i n f o
Article history:
Received 31 January 2011
Received in revised form6 March 2011
Accepted 8 March 2011
Available online 16 March 2011
Keywords:
ZnO
LangmuirBlodgett
Interference
Photonic band gap
Photoluminescence
a b s t r a c t
Monodisperse, spherical ZnO particles with different sizes were synthesized in diethylene glycol. Particles
were characterized by means of TEM and SEM images, XRD, nitrogen adsorptiondesorption isotherms
and small angle X-ray scattering methods. The ZnO nanoparticles were used to prepare Langmuir-lms
(at the air/water interface) and LangmuirBlodgett lms (on solid supports). Langmuir-lms were char-
acterized by surface pressure vs. surface area isotherms. Single and multilayer LangmuirBlodgett lms
were prepared for optical interference, photonic band gap and photoluminescence investigation. We
improved our previous optical interference model, special features of ordered lms of uniform spheri-
cal particles were integrated into the model to calculate effective refractive index and thickness of the
lms. Photonic band gap of single layer was determined from transmittance spectra and lm parameters
were calculated such as effective refractive index of the lm and volume fraction of partilces in the lm.
Photoluminescence measurements showed correspondence between primary crystallite size of particles
and the wavelength of photoluminescence emission maxima.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Monodisperse particles have great importance in fabrication
of highly ordered nanostructured materials and photonic crystals.
The well-ordered structure provides good control over the desired
properties of the material. Several synthesis methods are available
for the preparation of ZnO nanomaterials [13], but only a few
methods result in monodisperse, spherical colloid particles, which
is essential for several applications. Preparation of uniform ZnO
particles in aqueous media was used by Chittofrati and Matijevic
[4], Zhong and Matijevic [5], Jiang et al. [6] and a microemulsion
method was used by Masashi et al. [7].
Polyol-mediated preparation of metallic and metal-oxide par-
ticles in the micrometer and submicrometer size range was
reported to result in uniform, spherical particles with narrow
size-distribution [810]. Jezequel et al. [11] reported rst time
about preparation of monodisperse spheres of ZnO particles of
200400nm in diameter in diethylene glycol (DEG) media. They
investigated the effect of several parameters, such as water con-
centration, nature of the solvent, salt concentration, maximum

Corresponding author at: Supramolecular and Nanostructured Materials

ResearchGroupof TheHungarianAcademyof Sciences, Universityof Szeged, H-6720
Szeged, Aradi vt. 1, Hungary. Tel.: +36 62 544210; fax: +36 62 544042.
E-mail address: i.dekany@chem.u-szeged.hu (I. Dkny).
reaction temperature and heating rate, as well. They found that the
presence of water is essential in the formation of ZnO, the optimal
result was obtained with the molar ratio H
2
O/Zn=2 (accordingly
Zn(CH
3
COO)
2
2H
2
Ois used for the synthesis). DEGwas proved to
be the best solvent for the formation of spherical particles, while
maximumsalt concentration of 0.18mol/L was observed for parti-
cles in the submicrometer size range. Heating rate was reported to
be the key parameter for tuning the size of the particles. Seelig et al.
[12] described a two-step reaction process for ZnO formation in
diethylene glycol. In the rst step a polydisperse sol was prepared,
andafter centrifugationsome aliquot of the supernatant was added
tothe reactionmixture inthe secondstep. Theywere able tocontrol
the particle diameter in the range of 100600nmwith the amount
of primary supernatant added. Tay et al. [13] investigated the
formation mechanism of ZnO particles during the DEG-mediated
synthesis. Their researches showed that particle growth occurs by
the aggregation of nano-entities, which are individually unstable.
Spherical conguration of the aggregated sub-units is believed to
be the minimumof the surface free energy, therefore the greatest
stability.
Uniform colloidal particles are usually prepared for optical,
especially for photonic crystal applications. Numerous tehniques
have been developed to fabricate different periodic, ordered
structures including lithographic techniques [14], optical inter-
ference methods [15], and colloidal self-assembly: sedimentation
[12], spin-coating [16], dip-coating [17], convective self-assembly
0927-7757/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2011.03.025
N. brahmet al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 8089 81
[18] and LangmuirBlodgett technique [19]. Self-assembly based
techniques reqire high quality building blocks, namely the
nanoparticles must be monodisperse and spherical in shape to
achieve really a goodquality photonic material. LangmuirBlodgett
(LB) technique is a relatively simple and cheap method for the per-
paration of ordered structures. The colloidal crystal is obtained by
the consecutive deposition of single layers of the uniform build-
ing blocks. High quality photonic crystals can be fabricated by the
LB technique from different sized silica particles [19,20]. Prepara-
tion of LB- lms of ZnO particles was reported by Naszalyi et al.
[21,22], they fabricated complex LB-lms with introducing silica
layers between ZnO layers and invesitgated the optical properties,
photocatalytical activity and mechanical stability of the lms.
The aim of our work was to synthesize monodisperse, spheri-
cal ZnO colloidal particles with various sizes in autoclave, prepare
LB lms and characterize the optical interference, photonic band
gap and photoluminescence properties of the lms. We present
the investigation of ZnO particles with TEMand SEMimages, XRD,
BET and SAXS techniques. The preparation and characterization of
Langmuir-lms at theair/water interfacearedetailed. Investigation
of LangmuirBlodgett lms on solid supports with SEM, UVvis
spectroscopic and photoluminescence methods are also demon-
strated.
2. Experimental
2.1. Preparation of ZnO particles
Particle synthesis was carriedout by the methodof Jezequel [11]
with some modications. Particles were prepared in an autoclave
(Parr, 5500) at atmospheric conditions. 1.1g (in case of 234nmand
457nmZnO particles) or 2.2g (in case of 301nmand 349nmZnO
particles) zinc acetate dihydrate (Fluka, a.r.) and 100ml of diethy-
lene glycol (Molar Chemicals, purum) were put into the autoclave,
one valve was opened for air, and settings were as follows: tem-
perature: 160

C; heating rate: 3.5

C/min; stirrer: 400rpm. The

reaction mixture was heated to 160

C, maintained 1h and then

cooled down in half an hour. The resultant white sol was stored at
roomtemperature.
Powder samples were obtained by repeated centrifugation and
redispersion in ethanol (Molar Chemicals, a.r.). After the third
washing cycle the supernatant was discarded and the particles
were dried in air at 105

C for 12h.
2.2. Preparation of Langmuir and LangmuirBlodgett lms
Langmuir lms at the air/water interface and LB lms on solid
(glass, quartz, Si wafer) substrates were prepared in a Kibron
MicroTroughS Langmuir-trough. Spreading sols were obtained
by mixing the original sol with chloroform (SigmaAldrich,
Chromasolv

, 99.9%) in the volume ratio 1:1. Surface pressure

() vs. surface area (A) compression isotherms were recorded at a
compression speed of 815mm
2
/min. Solid substrates for LB lms
were cleaned in fresh piranha solution (at least 1h) and rinsed with
deionized water before lmpreparation. Films were withdrawn at
constant pressure (=10mN/m), only in the upstroke direction.
2.3. Characterization of ZnO particles
Size and size-distribution function of ZnO particles were
determined from TEM pictures (Hitachi S-4700 eld electron
microscope, transmission mode). Samples were prepared on
carbon-coated copper grids fromthe compressed Langmuir lmat
the air/water interface. Size distribution was calculated by mea-
suring the diameter of at least 150 particles. Scanning electron
microscopic pictures (Hitachi S-4700 eld electron microscope)
were taken to observe the suface morphology of the particles.
XRD measurement of powder samples were carried out to charac-
terize the crystal structure of the particles and to determine the
primary crystallite size. XRD measurements were performed on
Philips PW 1830 diffractometer using Cu K radiation at a volt-
age of 40kV and a current of 35mA. Scherrer equation was used
to determine average crystallite diameter from half width of the
diffraction peaks: d=(k)/(cos), where d is the mean crystallite
sizeof thepowder, is thewavelengthof CuK, is thefull widthat
half-maximum, is the Bragg diffraction angle and k is a constant.
N
2
adsorptiondesorption isotherms (Micrometrics, Gemini 2375)
were measured to calculte BET surface area and porosity of pow-
der samples. Small angle X-ray scattering (SAXS) measurements
of powder samples were taken on a Philips PW1820 diffractome-
ter, CuK
(
radiation (( =0.154nm) being used at 40kV and 30mA.
The primary beamwas directed through a Ni-lter into a compact
Kratkycamera, type KCEC/3. The beamwidthandits thickness were
15mm and 40m, respectively. The measurements were done in
vacuum atmosphere. The powdered sample was placed in a sam-
ple holder with thickness of 0.5mm. The intensity of the scattered
radiation was measured by a position sensitive detector (PDS 50M)
controlled by ASA software, in an angle range of 2=0.058

.
Absorption intensities (As, Ab) were determined by the so-called
moving slit method. The I (h) scattering function measured in the
Kratky camera has to be normalized and then background scat-
tering has to be taken into consideration, in order to be able to
determine structural parameters.
2.4. Characterization of Langmuir and LangmuirBlodgett lms
Surface pressure vs. surface area isoterms were evaluated by
determining the collapse pressure (
c
), collapse area (A
c
) and the
contact cross-sectional area (A
k
) of the particles (see Fig. 4a.). One
can calculate the area occupied by one single particle (A
1
) in the
Langmuir-lmusing the following equation [22]:
A
1
=
A
k
N
=
A
k
d
3

p
6m
(1)
where N is the number of particles in the Langmuir-lm, m is the
mass of the particles in the lm, d is the mean particle diameter
and
p
is the density of particles. As a comparison it is possible
to calculate the theoretically expected area for one particle with
the area of the hexagon including the particle (A
H
), which can be
expressed as follows [22]:
A
H
=

3
2
d
2
(2)
Structure of the multilayered LangmuirBlodgett lms and par-
ticle ordering was studied by a eld emission scanning electron
microscope (Hitachi S-4700). For the investigation of the opti-
cal and photonic properties transmittance spectra (Ocean Optics
USB4000) were measured during the preparation of multilayered
lms on glass slides after each deposited layer. Reectance spec-
tra were recorded with an Ocean Optics (Ocean Optics USB4000)
spectrophotometer equipped with a goniometer with ber optic
attachment. Reection was investigated with polychromatic, non-
polarized light at incident angle of 45

. Photoluminescence (PL)
measurements of quartz supported lms were performed with a
Horiba Jobin Yvon FluoroMax-4 uorescence spectrometer using
350nm excitation wavelength. The measurement layout was set
to an incident angle of =30

for the excitation source, the direc-

tion of the detection of the emitted ligth was =60

( is the angle
between the ligth and the surface normal).
82 N. brahmet al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 8089
Fig. 1. (a)(d) TEMimages of ZnO particles, mean particle diameter is marked on the pictures, (e) SEMimage and f. TEMimage of 234nmZnO particles demonstrating the
surface structure of particles.
3. Results and discussion
3.1. Nanoparticle synthesis
Preparation of ZnOcolloidal particles was described by Jezequel
et al. [11] in a one-step reaction. Seelig et al. [12] tried to reproduce
their method, but they could not make monodisperse particles in
one step, so they developed their two-step method. We tried to
synthesize the ZnO particles by adapting the method of Seelig, but
the result was a bidisperse sol. We decided to achieve monodis-
perse particles in an autoclave, where the temperature and the
heating rate can be controlled accurately. The synthesis was suc-
Fig. 2. Size-distribution functions of ZnO colloidal spheres calculated fromparticle
diameter values resulting fromTEM.
cesfull in one step after nding the right parameters. The key is that
the autoclave must be opened to air, otherwise the particles grow
up to a few m in diameter. Ashtaputre et al. [23] carried out the
preparation of ZnO particles in autoclave, they used high pressure,
added some water to the reaction mixture and obtained 15m
doughnut-shaped particles.
3.2. Particle characterization
TEMpictures (Fig. 1ad.) were taken to determine the size and
size-distribution (Fig. 2) of particles synthesized in the autoclave.
The images show that particles are spherical in shape and all the
sols containparticles withnarrowsize-distribution(standarddevi-
ation is less than 5%). SEMpicture of 234nmZnO particles (Fig. 1e)
was taken to demonstrate the particle morphology and synthe-
sis mechanism: the particles were formed by the aggregation of
colloidal sub-units, which results in a rough surface and remark-
able particle porosity. The results of the obtained data from TEM,
XRD, andBET measurements for the different sizedZnOspheres are
collected in Table 1 XRD diffraction pattern (Fig. 3a) exhibits the
characteristic peaks of hexagonal wurtzit crystal structure (JCPDS
Table 1
Characterization of ZnO particles with TEM, XRD and N
2
adsorptiondesorption
methods.
d (nm) 23411 30112 34914 45716
d
primary
(nm) 9.7 14.5 12.3 9.6
a
S
BET (m
2
/g) 57 66 79 71
pT (g/cm) 3.83 3.54 3.41 3.63
p (%) 32 37 39 35
N 10,389 6620 16,904 77,238
N. brahmet al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 8089 83
Fig. 3. (a) XRD diffractograms, (b) N
2
adsorption and desorption isotherms and (c)
poresize distribution function for the different sized ZnO powder samples.
36-1451, markedinFig. 3a). Crystallite size determinedfromScher-
rer equation based on line broadening reveals that the particles
were formed by the aggregation of well crystallized 914nm pri-
mary particles. N
2
adsorptiondesorption isotherms (Fig. 3b.) were
measured to evaluate BET surface area, particle density and poros-
ity of particles (calculated values are collected in Table 1.). The pore
size distribution (Fig. 3c.) shows that particles have mesopores.
The high value of particle porosity originates fromthe aggregation
type growth mechanism. It is possible to calculate the approximate
number of primary crystallites for one particle if we suppose that
primary cristallites are spherical in shape and the volume fraction
of primary cristallites in one particle is 0.74 (this value is used for
hexagonally close packed systems). The number of primary crys-
Fig. 4. (a) Surface pressure () vs. surface area (A) isotherms of different sized ZnO
particles, (b) series of isotherms of 301nmZnOparticles with different spread mass.
tallites (N) can be expressed as follows:
N =
V 0.74
V
primary
=
r
3
0.74
r
primary
3
(3)
where V is the volume of one particle, V
primary
is the volume of one
primary crystallite, r is the radius of particles and r
primary
is the
radius of primary crystallites (obtained fromXRD). The results are
collected in Table 1. The number of primary crystallites in case of
different particle sizes are quite diverse, which can be due to the
different tendencies of primary crystallite size and particle size.
Theparameters determinedfromSAXSmeasurements werecol-
lected in Table 2. Mass fractal dimension (D
m
, 1D
m
3) describes
the porosity of the sample: if D
m
=1, the sample has very high
porosity, it consists of almost only pores, if D
m
=3 the sample is
compact, it has no pores. The D
m
value of our samples is around
2.52.7, in case of 457nmZnOparticles it is 1.85. The higher poros-
ity result does not agree with the nitrogen adsorptiondesorption
results (see a
s
BET
values in Table 1). The reason for this can be the
presence of closedpores of the particles whichare not accessible for
N
2
molecules. Surface fractal dimension (D
s
, 2D
s
3) describes
the structure of the surface of the sample: if D
s
=2 the surface is
smooth, if D
s
=3the surface is veryroughandfragmented. Our sam-
ples have D
s
value between 2.3 and 2.5. The specic surface area
(S
p
) determined by SAXS is much higher than the results obtained
with BET method, which can be due to closed particle porosity.
The tendency of S
p
values for different sized ZnO particles agrees
well with D
m
values, 457nm ZnO particles have higher porosity
84 N. brahmet al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 8089
Fig. 5. LangmuirBlodgett lms of 234nm, 301nm, 349nmand 457nmZnO particles: top viewof single layers (scale bar equals to 5m).
Table 2
SAXS parameters determined for the different sized ZnO samples.
d (nm) 234nm 301nm 349nm 457nm
Dm
a
2.5 2.7 2.7 1.85
Ds
b
2.3 2.5 2.4 2.4
Kp (Cps/nm
3
)
c
43.2 42.1 38.7 41.58
M
1
(Cps/nm
2
)
d
177 1145 191 642
Kp/M
1
0.244 0.193 0.202 141
S/V (nm
2
/nm
3
)
e
0.244 0.192 0.201 0.29
SP (m
2
/g)
f
115 92 105 142
lc (nm)
g
11.3 10.5 10.8 9.05
L
1
(nm)
h
11.9 14.7 10.4 8.96
L
2
(nm)
i
23.0 29.0 27.6 19.12
a
Mass fractal dimension.
b
Surface fractal dimension.
c
Porod constant.
d
First moment of the scatterig function.
e
Relative inner surface.
f
Specic surface area.
g
Correlation length (inhomogenity length for the entire powder sample).
h
Inhomogenity length for phase 1.
i
Inhomogenity length for phase 2.
than others which involves the highest mass fractal dimension
and specic surface area. The inhomogenity length for ZnO phase
(L
1
) in the samples is in the order of 10nm. These values corre-
spond well with the primary crystallite size resulted from XRD
measurements (d
primary
in Table 1). Inhomogenity length for air
phase (L
2
) is higher than the pore sizes determined fromnitrogen
adsorptiondesorption measurements. These two values should
not be equal, because the inhonogenity length includes the air
between the particles beside the pores.
3.3. Langmuir-lmpreparation, characterization
Formationof 2Darrays of ZnOparticles at the air/water interface
was characterizedthroughLangmuir-balance experiments. Surface
pressure () vs. surface area (A) isotherms were recorded to inves-
tigate the behaviour of the particles at the interface. Fig. 4a shows
A isotherms of different sized ZnO particles and the determi-
nation of the collapse pressure (
c
), collapse area (A
c
) and the
contact cross-sectional area (A
k
). Table 3 contains the results for
the different samples. Isotherms of different sized ZnO particle
lms have almost the same shape: after a well-dened, steeply
rising part comes collapse and the surface pressure is further
increasing but with a smaller gradient. Theoretical (A
H
) and exper-
imental (A
1
) calculations (Eqs. (1) and (2)) of the area for one
particle in the Langmuir-lm were compared for different sized
ZnO particles (Table 3). The good agreement of the results mean
well ordered, close packed particles at the air/water interface. A
series of A isotherms were measured in case of 301nm ZnO
particles with different spread amount (Fig. 4b). Contact cross-
sectional area (A
k
) was determined fromthe isotherm, Fig. 4b inset
shows the A
k
values as a function of the spread mass of ZnO. The
Table 3
Parameters determined fromLangmuir balance experiments.
d (nm)
c
(mN/m) Ac (mm
2
/mg) A
k
(mm
2
/mg) A
1
(nm
2
/db) AH (nm
2
/db)
234nm 30.3 1646 1964 5.0510
4
4.7410
4
301nm 26.5 1493 1664 8.4110
4
7.8510
4
349nm 29.1 1238 1377 1.0610
5
1.051
5
457nm 30.5 910 1047 1.910
5
1.8110
5
N. brahmet al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 8089 85
Fig. 6. UVvis transmittance spectra of multilayered lms of 234nmZnO.
linear dependence reveals goodcontrol over the measurement pro-
cess.
3.4. Structure of LangmuirBlodgett lms (SEM)
Single layered LangmuirBlodgett lms were prepared on
Si wafer substrate to investigate particle ordering in the solid
supported lms. Fig. 5 contains pictures of single layer lms
of different sized ZnO particles. It can be seen that particles
form a single layer, no aggregated or collapsed domains can
be found. Particle ordering is very good but not perfect, the
layers are consisting of hcp ordered domains. We can further
establish that larger particles are easier to assemble in ordered
structure.
3.5. Optical and photoluminescence characterization of
LangmuirBlodgett lms
LangmuirBlodgett lms of our ZnO particles show different
interesting features. Multilayered lms of 234nm ZnO particles
were characterized by transmittance and reectance measure-
ments. Film preparation was followed by transmittance measure-
ment after each deposited layer. The spectra recorded in case of
15 layers is collected in Fig. 6. The decrease in transmittance and
the appearance of reection with increasing layer thickness can be
observed.
Optical interference properties of our lms were studied by
reectance measurements. We have established a simple opti-
cal model based on the interference on plane parallel plates for
the theoretical calculation of reection intensity. The essentials
of the method is nding the optimal values of the parameters
of our model in order to achieve the best t for the experimen-
tally recorded spectra. Our model considers particle characteristics
(average diameter, porosity, refractive index) and lm proper-
ties (particleparticle distance, lm thickness, effective refractive
index), as well. Details of calculation regarding on the reectance
intensity is published in our previous work [24]. The model of
that work was extended with the special calculation possibilities of
ordered lms of monodispersed colloid spheres, which covers the
precise determination of lmparameters, such as particleparticle
distance, lmthickness and volume fraction of the particles in the
lm.
Fig. 7. Schematic representation of the parameters used in our optical model.
The initial step of our method is to calculate the refractive index
of particles (n
p
) with LorentzLorenz equation [25]:
n
2
p
1
n
2
p
+2
=

i
f
i
n
2
i
1
n
2
i
+2
= f
ZnO
n
2
ZnO
1
n
2
ZnO
+2
(4)
where n
ZnO
is the bulk refractive index of ZnO, f
ZnO
is the volume
fraction of ZnO in one single particle. The wavelength dependent
bulk refractive index of ZnO was calculated with an analytical for-
mula [24]:
n
ZnO
=
a +b

2
where a and b are constants (a =1.84, b=26,667), is the wave-
length of the light. The volume fraction of ZnOin one single particle
(f
ZnO
) can be expressed as a function of the porosity:
f
ZnO
=
(100 p)
100
(5)
where p is particle porosity in %. Thickness of the lm (H) can be
calculated as follows [25]:
H = d +(k 1)
_
d
2

D
2
3
(6)
where d is the average diameter of the particles, k is the number of
layers andDis the distance betweenthe centre of twoneighbouring
particle in the lm(Fig. 7.)
If we assume hexagonally close packed order in the lm, the
volume fraction of the particles in the lm (f
p
) can be expressed
with the following equation:
f
p
=
kd
3

3D
2
H
(7)
The effective refractive indexof the lm(n
eff
) canbe determined
with LorentzLorenz equation:
n
2
eff
1
n
2
eff
+2
= f
p
n
2
p
1
n
2
p
+2
(8)
The reection intensity (I
R
) is proportional to the following
expression (the details of the deduction were published previously
[24]):
I
R
a
2
_
r
2
+2rr

(1 r
2
) cos
4n
eff
H cos

+r
2
(1 r
2
)
2
_
(9)
where a is the amplitude of the incident ray, r and r

are ampli-
tudes of reections on the air/lmand lm/substrate interfaces,
86 N. brahmet al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 8089
Fig. 8. (a) Measured and tted reectance spectra of multilayered
LangmuirBlodgett lms of 234nmZnO particles, (b) effective refractive indices of
lms resulted fromoptical tting.
is the angle of refraction and is the wavelength of the light. The
amplitudes of reections can be calculated [24]:
r =
_
n
eff
n
air
n
eff
+n
air
_
2
(10)
r

=
_
n
s
n
eff
n
s
+n
eff
_
2
(11)
Results of optical interference calculation of multilayered lms
of 234nm ZnO particles are demonstrated in Fig. 8. Fig. 8a shows
the measured and the corresponding tted reectance spectra and
Fig. 8b includes effective refractive indices as a function of wave-
length at different layer numbers. The calculated spectra for the
single layer has good t for the experimental curve in a wide wave-
length region (400850nm). The lower limit of wavelength is
around 400nm, because ZnO has increasing absorbance belowthis
value. For thedoublelayer it is alsoawidewavelengthregionwhere
the tting is appropriate (400800nm). Calculations in case of
lms consisting of three or more layers have accepable results in
Table 4
Filmthickness (H) and particle volume fraction (fp) values resulted fromthe optical
calculations at different layer numbers (k).
k 1 2 3 4 5
H (nm) 234 409 586 764 940
fP 0.4475 0.5202 0.5562 0.5735 0.5822
Fig. 9. Transmittance spectra of single layer LangmuirBlodgett lms of 301nm,
349nmand 457nmZnO particles.
a much more narrow interval (430570nm). Accordingly, only
the results regarding these wavelength intervals can be accepted.
The effective refractive indices show an increasing tendency with
increasing layer numbers. The explanation of this is the increas-
ing volume fraction of ZnO particles in the lm: particles sit in the
gaps of the former layer. Filmthickness (H) and volume fraction(f
p
)
values are collected in Table 4. Our model gives excellent results
for single and double layers, but less convenient for higher layer
numbers. More reasons can be responsible for it: the rst and most
serious factor is that the absorbance of the lm is enhanced with
increasing layer numbers due to the increasing amount of ZnO. On
the other hand the small defects in the lm structure accumulate
at increased layer numbers and results in less ordered structures
which cannot be described perfectly with our model. At this point
we should mention that the disadvantage of the incomplete order
of the particles can be probably overcome with other techniques.
Self-assemby of the particles with other methods (for example the
convective self-assembly [18]) could result in almost perfect crys-
tals if hitting on the optimal parameters of the lm formation. It
would be interesting to test our model for such a well-ordered
crystal. Considering all the observations we can conclude that the
applied model describes the samples well, the calculations particu-
larly for lower layer numbers engage properly for the experimental
results.
Single layer LangmuirBlodgett lms of 301nm, 349nm and
452nmZnO particles were characterized by UVvis transmittance
measurement (Fig. 9). First and second order photonic band gap
(PBG) positions of the different sized ZnO samples are marked in
Table 5
Results of photonic band gap calculation: rst order photonic band gap (
max,1
), second order photonic band gap (
max,2
), effective refractive index of lm(n
eff
), bulk refractive
index of ZnO (n
ZnO, bulk
), porosity of particles (p), volume fraction of particles in the lm(fp) and interparticle distance in the monolayer (D).
d (nm)
max,l
(nm)

max,2
(nm)
n
eff
n
ZnO, bulk
(at
max,2
)
p (%) np fp D (nm)
301mn 719 408 1.355 2.000 36.72 1.633 0.563 312
349 mn 820 460 1.318 1.966 39.18 1.688 0.541 369
457 mn 598 1.309 1.915 35.13 1.594 0.522 492
N. brahmet al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 8089 87
the gure andlistedinTable 5. The rst order PBGis at longer wave-
lengths than900nmincase of 457nmparticles, soit cannot be seen
in the spectra. Theoretically expected wavelengths of the potonic
band gaps of the lms can be calculated by two simple equations
[26]:

max,1
= 2 Ln
eff
(12)

max,2
= Ln
eff
(13)
where
max,1
and
max,2
are the rst and second order photonic
stop band positions, L is the lattice parameter and n
eff
is the effec-
tive refractive index of the lm. The lattice parameter for single
layers is the thickness of the lm. In our case the lm thickness is
equal to the particle diameter. It can be seen from Eqs. (12) and
(13) that the wavelength of the rst order PBG is twice the wave-
length of the second order PBG. Transmittance spectra of our lms
indicate different relationship, the rst order PBG appears at lower
wavelengths thanexpectedfromthe value of the secondorder PBG.
The reason for this is not yet clear.
Effective refractive indices of lms were calculated fromsecond
order photonic band gap positions (these n
eff
values correspond to
the wavelength of the second order maxima). Several methods can
be found in the literature for the calculation of refractive indices,
for photonic crystal materials it is often used to be calculated as the
weighted average of the compounds of the lm, and the weight is
the volume fraction [26]:
n
eff
= f
p
n
p
+f
air
n
air
(14)
where f
p
and n
p
are the volume fraction and refractive index of
the particles, f
air
and n
air
are the same parameters for the air. This
method can be extended to calculate the refractive index of parti-
cles.
n
p
= f
ZnO
n
ZnO
+f
air
n
air
(15)
Table 5 contains the bulk refractive indices of ZnO at the corre-
sponding wavelengths (
max,2
), porosity of particles (p), calculated
particle refractive indices (with Eqs. (5) and (15)). At this point
effective refractive indices resulted from the measured transmit-
tance spectra can be used to determine the volume fraction of the
particles (Eq. (14)) and the interparticle distance (Eq. (7), consider-
ing that H=d) in the lm. Table 5 contains the results.
Photoluminescence (PL) properties of the different sized ZnO
particles were studied by measuring the emision of the quartz sup-
ported single layer LangmuirBlodgett lms. Fig. 10a demonstrates
the recordedemissionintensities as a functionof the wavelengthin
caseof 350nmexcitationsource. Astrongandwidevisibleemission
appears around 570nm, and a weak, sharp UV emission at 390nm.
Usualy nanostructured ZnO materials exhibit UV and visible emis-
sion. The UV emission is due to the radiative recombination of
photogenerated excitons, the origin of the visible part of the emis-
sion is not completely understood yet, it is related to surface states
and defects in the crystal structure (mostly connected with oxigen
vacancies) [27,28]. The weak, sharp UVemission appears at 390nm
in case of all samples. The position of the visible emission peak is
shifted for different samples. Since our particles are composed of
primary crystallites, it is evident to look for a relationship between
theprimarycrystallitesizeandthePLemisionfeatures (wavelength
andintensity). Figs. 10bandc showthe wavelengthandintensity of
the visible emissionas a functionof pimary cristallite size (obtained
from XRD). We obtained that increasing primary crystallite size
results in red shift in the emission maxima and decrease in emis-
sion intensity, which agrees well with earlier results [29]. We have
to consider the effect of the photonic structure on the photolumi-
nescence emission. It is known that photonic stop band lowers the
intensity of the emission if the wavelengths are overlapping. In our
case all the emissions are positioned around 570nm. This emission
Fig. 10. (a) PL spectra of quartz supported single layer LangmuirBlodgett lms of
ZnO particles with various sizes, dependence of (b) PL emission wavelength and (c)
intensity on primary crystallite size (the solid lines are guide to the eyes).
cannot be compared with he PBG wavelengths determined from
Fig. 9, because these values are obtained at =0

incident angle (
is the angle to the surface normal). Since photoluminescence emis-
sion has angular dependence in case of photonic crystals [30] we
have to calculate the photonic band gap corresponding to =60

with the following equations [30]:

max,2
= L
_
n
2
eff
sin
2
(16)

max,1
= 2L
_
n
2
eff
sin
2
(17)
88 N. brahmet al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 8089
where is the angle to the surface normal. As a result for =60

the
rst order band gaps for 301nm, 349nmand 457nmZnO particles
arerespectively594nm, 651nmand842nm, thesecondorder band
gaps are 297nm, 326nm and 421nm. It is clear that none of the
second order band gaps overlap with the PL emission. Only the
rst order band gap of the lm of 301nm ZnO particles is close
to the emission maxima and this sample has the lowest emission
intensity. We suppose that this is mainly due to particle size effect
and not the effect of the PBG, because the rst order stop bands
are much weaker and wider dispersed than the second order stop
bands.
4. Conclusions
We have synthesized monodispersed, spherical ZnO particles
in autoclave in diethylene glycol media adapting the method
of Jezequel et al. [11]. The size and size-distribution of parti-
cles was determined from TEM images, surface structure was
demonstrated with SEM and TEM pictures, particle features such
as primary cristallite size, specic surface area, porosity, den-
sity and several SAXS parameters were determined by XRD,
N
2
adsorptiondesorption and SAXS measurements. Langmuir-
lms at the air water interface were prepared and characterized
with surface pressure and surface area isotherms. Solid sup-
ported LangmuirBlodgett lms were prepared and characterized
regarding optical interference, photonic band gap and photolu-
minescence. We have improved our former optical model (based
on interference on plane parallel plates) for the calculation of
reectance intensity as a function of wavelength. Fitting for the
measured spectra provided effective refractive index and thickness
of lms.
Acknowledgement
The authors are very thankfull for the nantial support of the
Hungarian Scientic Fund (OTKA) Nr. K 73307 and NK 73672. The
Project named MOP-4.2.1/B-09/1/KONV-2010-0005 Creating
the Centre of Excellence at the University of Szeged is supported
by the European Union and co-nanced by the European Regional
Fund.
Appendix A.
Calculationmethods for small angle X-rayscattering bydisperse
systems [3134]:
When X-rays are scattered by colloidal particles due to differ-
ences in electron density caused by inhomogeneities, the intensity
of scattered radiation is a function of the angle of scattering ()
and the scattering vector (h):
I(h) =
2
(0)V
_

0
4r
2

0
(r)
sin hr
hr
dr (18)
where V is the volume of the systemin which X-rays are scattered
by electrons. Inthe above equationthe value of
2
(0) canbe dened
in the following way [3133]:

2
(0) =
1
V
_

0
(
e
(r)
e
)
2
d
3
r (19)
where
e
(r) is the local electron density at a given point (r) and
e
is the average electron density. When the concept of electron den-
sity uctuation is introduced: (r) =
e
(r)
e
, then the correlation
function in Eq. (18) can be given:

0
(r) =

2
(r)

2
(0)
(20)
The correlation function contains signicant information on the
geometry and structural arrangement of the scattering particles.
Thefollowingrelationshipholds for thetailingregionof thescat-
tering function, where hR>1 (the so-called Porod-range) [3439]:
I(h) =
2
(0) 2
S
h
4
(21)
where S is the surface area of the particles. The relative specic
surface area of the particles (relative to unit volume V) is [3335]:
S
V
=
limI(h) h
4
h
Q
=
K
p
Q
(22)
where Kp is the tail end constant.
The specic surface area is:
S
p
=
S/V 10
3
d
(23)
where d (gcm
3
) is the density of the disperse system.
Correlation length can also be calculated directly fromthe scat-
tering function, in case if the following integrations are known
[3639]:
l
c
=
_

0
I(h)hdh
Q
(24)
From the middle section of the scattering curve the fractal
dimension of the particles can be determined [36] in the case if
the scattering curve is linear in the relatively wide range of h: log I
(h) =p log h. Fromthe value of the tangent p, the surface fractal D
s
is calculated by the relationship D
s
=p+5, the value of which has to
fall within the range of 2D
s
3.
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