Tunable optical properties in atomic layer deposition grown ZnO thin films

Dipayan Pal, Aakash Mathur, and Ajaib SinghJaya SinghalAmartya SenguptaSurjendu DuttaStefan
ZollnerSudeshna Chattopadhyay

Citation: J. Vac. Sci. Technol. A 35, 01B108 (2017); doi: 10.1116/1.4967296

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Tunable optical properties in atomic layer deposition grown ZnO thin films
Dipayan Pal, Aakash Mathur, and Ajaib Singh
Discipline of Metallurgy Engineering and Materials Science, Indian Institute of Technology Indore,
Simrol, Indore 453552, India
Jaya Singhal
Centre for Biosciences and Biomedical Engineering, Indian Institute of Technology Indore, Simrol,
Indore 453552, India
Amartya Sengupta
Department of Physics, Indian Institute of Technology Delhi, Delhi 110016, India
Surjendu Dutta
Discipline of Physics, Indian Institute of Technology Indore, Indore 453552, India
Stefan Zollner
Department of Physics, New Mexico State University, Las Cruces, New Mexico 88003
Sudeshna Chattopadhyaya)
Discipline of Physics, Discipline of Metallurgy Engineering and Materials Science, Centre for Biosciences
and Biomedical Engineering, Indian Institute of Technology Indore, Simrol, Indore 453552, India
(Received 26 June 2016; accepted 24 October 2016; published 9 November 2016)
ZnO thin films with very low surface roughness and bulklike electron density were grown on Si
and SiO2 by atomic layer deposition. The real and imaginary parts of the complex dielectric
function of ZnO on Si show monotonically decreasing values with decreasing film thickness at and
below a threshold of about 20 nm. On the other hand, x-ray reflectivity results show that the elec-
tron density of our ZnO films is close to that of bulk ZnO and does not vary considerably with film
thickness. While the reduction of the dielectric function cannot be explained by the electron density
of our ZnO films, the Tanguy–Elliott amplitude prefactor governing the strength of optical inter-
band transitions can explain our results consistently through the lowering of the electron–hole over-
lap factor at the ZnO/Si interface. In the case of ZnO/Si, a staggered type-II (spatially indirect)
quantum well, holes are scattered into the Si substrate, causing a lowering of the electron–hole
overlap factor and thus the reduction of excitonic absorption, consequently a decrease in the real
and the imaginary parts of the dielectric function. This hypothesis was confirmed with ZnO films
grown on SiO2, where a thin type-I quantum well, consisting of a narrower-bandgap semiconductor
grown on a wider-bandgap (insulator) substrate, in which both the electron and the hole are con-
fined in the ZnO thin film, leads to an increase in the electron–hole overlap matrix element with
decreasing film thickness due to confinement, resulting in enhancement of the excitonic absorption
in thinner ZnO films on SiO2. VC 2016 American Vacuum Society.

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I. INTRODUCTION sensors,10 and nanogenerators.11 ZnO has also attracted a lot

In recent years, the optical properties of zinc oxide of interest for being used in hybrid solar cells because it is
(ZnO), a direct and wide band gap semiconductor (Eg  3.37 less toxic than many other II–VI semiconductors and is rela-
eV at room temperature) with large exciton binding energy tively easy to synthesize in large quantities with a variety of
(60 meV), have gained substantial interest for potential techniques.12 Furthermore, ZnO as an n-type semiconductor
applications in optoelectronics and photonics.1–3 The large with a wide band gap and a very good optical transmittance
exciton binding energy ensures efficient excitonic emission remains a potential candidate for an efficient cathode buffer
in ZnO at room temperature and even higher,4 which makes layer or a transparent electrode in the organic and hybrid
ZnO a promising material for short-wavelength optoelec- solar cells.12 In view of the above facts, tuning of the struc-
tronic devices, especially for ultraviolet light-emitting diodes tural and optical properties of ZnO films is highly important
and laser diodes.5 The thermal and chemical stabilities of and desired for optimal device performance.13 Studies
ZnO, along with its excellent optical/opto-electronic proper- showed that the thickness of ZnO films is a key parameter
ties,6 motivated extensive research for its use in a number of in photovoltaic devices where thicknesses below 300 nm
applications such as ultraviolet light emitters,6 thin film tran- are of specific interest in terms of optimization of device
sistors,7 solar cells,8 transparent conducting oxide,9 gas performance.11,14 The quantum size effects in ZnO nano-
structures, such as nanocrystals,15,16 quantum wells,17 nano-
a)
Electronic addresses: [email protected]; chattopadhyay.sudeshna@ rods,18,19 nanowires,20 quantum dots,21,22 etc., have been
gmail.com extensively investigated by many research groups. However,

01B108-1 J. Vac. Sci. Technol. A 35(1), Jan/Feb 2017 0734-2101/2017/35(1)/01B108/9/$30.00 C 2016 American Vacuum Society
V 01B108-1
01B108-2 Pal et al.: Tunable optical properties in ALD 01B108-2

few reports are available on the thickness dependence of achieved a growth rate of about 1.6 Å per cycle which is
properties of ZnO thin films.23–25 Experimentally, it has similar to the growth rate reported by the other groups.36,37
been observed that the quantum effects in ZnO thin films ZnO films with different thickness (5–70 nm) were grown
have become apparent in their optical properties specifically on Si and fused quartz (SiO2) substrates to explore the
in the dimensions of 20 nm or less.23–25 The systematic dependence of the optical properties on ZnO thickness and
quantitative thickness dependent study of the optical proper- substrate choice.
ties of ZnO thin films in this regime is highly important, and The crystalline structures of the as-grown ZnO films were
a convincing scientific explanation of the observed phenom- investigated by x-ray diffraction (XRD) with CuKa radiation
ena needs to be found. (k ¼ 1.54 Å) using a Rigaku SmartLab automated multipur-
In recent years, atomic layer deposition (ALD) has drawn pose x-ray diffractometer.
significant interest for growing ZnO thin films using sequen- The thickness of the films was estimated by using x-ray
tial, self-limiting surface reactions.26–29 Over other thin film reflectivity (XRR) measurements. X-ray reflectivity data of
deposition techniques, ALD offers several advantages such ZnO films were collected with CuKa radiation using a Rigaku
as excellent conformality, precise thickness control down SmartLab automated multipurpose x-ray diffractometer.
to atomic level, pinhole-free films, and high degree of repro- Specular reflectivity scans, i.e., scans in the plane containing
ducibility.30–32 Also, ALD grown ZnO thin films generally the incident beam and the normal to the sample surface, with
show n-type conductivity which makes it an important the incident angle hin equal to the scattering angle hsc, were
candidate for use as a transparent conductive oxide performed with hin varying from 0 to 3 . If q ¼ ks  ki is the
material.6,27,33 momentum transfer vector and ks and ki the scattered and inci-
Herein, we demonstrate the thickness induced change in dent x-ray wave vectors, respectively, then this geometry
optical properties of ALD-grown smooth, pinhole-free ZnO makes the components in the sample plane, qx ¼ qy ¼ 0, and
thin films on silicon (Si) and SiO2 substrates. We show the value of qz (¼ (4p/k) sin hin), the component normal to the
clearly that in thin ZnO films (at and below 20 nm), with sample surface, varies from 0 to 0.43 Å1. The reflectivity
decreasing film thickness, there is a significant drop in the data of ZnO films were analyzed by the Parratt formal-
real and imaginary parts of the dielectric function for ZnO/Si ism.38–42 This scheme recursively solves the Fresnel equa-
system. The reduction of the complex dielectric function is tions at each interface, i.e., the change in electron density (q)
explained by the Tanguy–Elliot amplitude prefactor through within any film. More precisely, in this method, we recur-
the effect of delocalization of holes in Si from ZnO at the sively solve the equation for the reflectance rn–1,n at the inter-
interface, which leads to the decrease in the overlap of elec- face between the nth and the (n  1)th layers, with the nth
tron and hole wave functions, thus the deconfinement of the layer having thickness dn and electron density qn, given as38
exciton, causing the drop in dielectric function.34,35 This  
hypothesis is consistent with the case of the ZnO/SiO2 sys- ðrn;nþ1 þ Fn1;n Þ
rn1;n ¼ expðiqz;n1 dn1 Þ ; (1)
tem, where both the electron and the hole are confined in the ð1 þ rn;nþ1 Fn1;n Þ
ZnO thin film, which leads to an increase in the electron–
hole overlap matrix element with decreasing film thickness, where
resulting in the enhancement of excitonic absorption in thin- ðqz;n1  qz;n Þ
ner ZnO films on SiO2. Fn1;n ¼ ; (2)
ðqz;n1 þ qz;n Þ
II. EXPERIMENT with
ZnO thin films were grown on silicon [Si (100)] and
fused quartz (SiO2) substrates at 200  C deposition tempera- qz;n ¼ ðq2z;0  q2c;n Þ1=2 : (3)
ture (or process temperature) using a BENEQ TFS-200
ALD reactor. Before loading the substrates into the ALD qz,0 is the z component (normal to the surface) of the momen-
reactor, all the substrates were ultrasonically cleaned in ace- tum transfer in vacuum or air, and q2c;n ¼ 16pqn re is the
tone and ethanol in sequence for 2 min, and then kept in critical value of qz for total external reflection for the nth
deionized (DI) water and finally dried in nitrogen (N2, layer. The constant re is the classical electron radius
99.999% purity). The precursors for zinc and oxygen were (¼2.8  106 nm). Equation (1) then yields the reflectivity as
diethyl zinc [DEZn, Zn(C2H5)2, Sigma-Aldrich] and DI
water, respectively. Nitrogen (N2, 99.999% purity) was used Rn1;n ¼ jrn1;n j2 : (4)
both as a carrier and the purging gas. The precursors were
This expression for reflectivity, valid for an ideally smooth
alternately introduced into the reactor using their intrinsic
interface, is then modified in the presence of the Gaussian
vapor pressures from external containers kept at 18  C. The
interface width or “roughness” (rn–1,n) as
reactor pressure during the growth was kept at 1.75 mbar.
One ALD reaction cycle consisted of a 0.2 s exposure to Rrough ðqz Þ ¼ Rðqz Þ exp ðqz 2 r2 Þ : (5)
DEZ, followed by a 0.75 s for N2 purge, a 0.2 s exposure to
H2O, and then another 0.75 s N2 purge. For the growth stud- The values of film thickness, electron density, and interface
ies, the number of ALD cycles ranged from 30 to 410. We width or roughness extracted from the best fit of reflectivity

J. Vac. Sci. Technol. A, Vol. 35, No. 1, Jan/Feb 2017

01B108-3 Pal et al.: Tunable optical properties in ALD 01B108-3

data using Eqs. (1)–(5) have constructed the electron density

profiles (EDPs), i.e., the electron density as a function of
film depth from the top for ZnO films, after convoluting the
profile with the interface widths.
The surface morphologies of ZnO films were examined
by field emission scanning electron microscopy (FESEM,
JEOL JSM-7600 F) and atomic force microscopy (AFM) in
the tapping mode using a Bruker Dimension icon with
ScanAsyst (Bruker, Santa Barbara, CA).
Spectroscopic ellipsometry (SE) measurements were
performed on ZnO thin films deposited on Si substrates with
an ellipsometer (J.A. Woollam, Co., Lincoln, NE, Model:
VASE) in the photon energy range of 0.8–6.5 eV at three
incident angles of 60 , 65 , and 70 , similar to the technique
described elsewhere.43 Ellipsometry techniques have been
extensively used to explore the optical properties of the ZnO
films, namely, complex dielectric function, absorption coef-
ficient, and band gap along with the film thickness and
roughness, using the WVASE (J.A. Woollam, Co.) software.
UV-VIS absorption spectra of ZnO films, deposited on
fused quartz substrates (SiO2), were measured using a UV-
VIS spectrophotometer in transmission mode (Perkin Elmer,
lambda-35) in the wavelength (k) range of 190–1100 nm.
The absorption coefficient a can be calculated from the
Beer-Lambert’s law as44

2:303  Abs ðkÞ

a¼ ; (6)
d
where d and Abs are the film thickness and film absorbance,
respectively.

III. RESULTS AND DISCUSSION

A. Thickness, electron density profile, FIG. 1. (Color online) (a) XRR for ZnO/Si with film thickness: (i) 5 nm, (ii)
and surface–interface roughness of ZnO 9 nm, (iii) 19 nm, and (iv) 38 nm; circles and lines represent experimental
films by x-ray reflectivity data and theoretical fit, respectively; and (b) corresponding extracted elec-
tron density (q) profile from XRR fits.
The XRR technique provides information about the film
thickness, the EDP, and the surface and interface roughness
observed for ZnO/Si systems. The thickness of our ALD-
of thin films. Figure 1(a) shows x-ray reflectivity data for
grown ZnO films ranges from about 5 to 70 nm. The growth
ZnO/Si samples with different ZnO film thickness, where
rate of ZnO determined with XRR from the deposited films
circles and lines represent experimental data and theoretical
on Si and SiO2 was about 1.6 Å/cycle (at 200  C), which is
fit, respectively. The x-ray reflectivity data have been fitted
in agreement with previous studies of ZnO growth by
by the well-known Parratt’s exact recursive method.38–42
ALD.36,37 Film thicknesses, corresponding growth parame-
X-ray reflectivity profile shows clear Kiessig fringes, and
ters, surface roughness, and other relevant parameters are
the corresponding extracted electron density indicates the
summarized in Table I.
formation of ZnO thin films with bulklike electron density,
on silicon (Si) substrates, with very low surface and interface
roughness. Figure 1(b) shows the representative EDPs (q) of B. Structure and morphology
the respective films extracted from XRR fits. Results show Figure 2(a) shows representative x-ray diffraction patterns
that the electron densities of ALD-grown ZnO films are of ZnO thin films of different thicknesses, grown on Si sub-
close to its bulk electron density, except that at below about strates. The diffraction peaks were matched with the stan-
10 nm film thickness, it drops slightly (by less than 7%). dard diffraction pattern of hexagonal wurtzite ZnO with a
This signifies the formation of high quality pinhole-free ZnO space group of P63mc (JCPDS PDF Card No. 01-079-2205),
films, with nearly complete surface coverage. illustrated in Fig. 2(b).
It should be noted that ZnO films grown on fused quartz The XRD pattern of our ZnO films shows a much stronger
(SiO2) substrates (ZnO/SiO2 samples) show similar film ZnO (002) peak compared to ZnO (101), whereas the stan-
thickness, electron density profile, and surface roughness, as dard powder XRD pattern of bulk ZnO (hexagonal wurtzite

JVST A - Vacuum, Surfaces, and Films

01B108-4 Pal et al.: Tunable optical properties in ALD 01B108-4

Mean grain
size from
XRD (Å)

30
133
218
212
214
RMS of surface
roughness from
AFM (Å)

11
14

19
roughness from
ZnO/SiO2

XRR (Å)
Surface

16
25
21
21
9
(Å/cycle)
Growth

1.45
1.56
1.63
1.73
1.67
rate
thickness from
ZnO film

XRR (Å)

188
375
520
685
87
Mean grain
size from
XRD (Å)

<50

123
208
194
212
56
RMS of Surface
roughness from
AFM (Å)
TABLE I. ALD grown ZnO films deposited at 200  C process temperature, on Si and SiO2 substrates.

11
15

18

FIG. 2. (Color online) (a) X-ray diffraction patterns of ZnO thin films with
from XRR (Å)

different thicknesses, on Si substrates. (b) Reference data. Standard diffrac-

roughness
Surface

tion pattern of hexagonal wurtzite ZnO with a space group of P63mc

15
20
19
17
7
9

(JCPDS PDF Card No. 01-079-2205). (c) Average or mean grain size,
derived from Scherrer’s formula, for different ZnO film thicknesses, on Si
substrates.
ZnO/Si

ZnO/Si interface
SiO2 thickness at

from XRR (Å)

bulk ZnO) shows the maximum intensity for the ZnO (101)
peak (JCPDS PDF Card No. 01-079-2205). This clearly indi-
11

10
0
0

cates that our ZnO films on Si exhibited a preferred orienta-

tion along the h0002i direction with the c axis
predominantly perpendicular to the substrate surface.
Average grain sizes (out-of-plane) were estimated using
(Å/cycle)

Scherrer’s formula,45 as shown in Fig. 2(c). The average

Growth

1.65
1.49
1.58
1.65
1.72
1.68
rate

grain sizes are about 20 nm for thicker ZnO films, but thin
ZnO films (at and below 20 nm) show lower grain sizes with
decreasing film thickness. It should be noted that our ZnO
thickness from

films grown on SiO2 show similar XRD pattern as ZnO/Si.

ZnO film

XRR (Å)

189
379
515
689

The summary of the extracted results for both the sample

50
89

types is shown in Table I.

The surface morphologies of ZnO films were examined by
FESEM and AFM. Two representative SEM micrographs are
No. of

cycles

shown in Figs. 3(a) and 3(c) for 69 and 9 nm ZnO films on Si,
ALD

120
230
300
410
30
60

respectively. Corresponding AFM images are displayed in

J. Vac. Sci. Technol. A, Vol. 35, No. 1, Jan/Feb 2017

01B108-5 Pal et al.: Tunable optical properties in ALD 01B108-5

Figures 4(a) and 4(b) show the ellipsometric angles, w

and D, for as-deposited 69 and 19 nm ZnO films on Si,
respectively. We found that the calculated w and D are in
good agreement with the experimental data. Excellent fits
with mean-squared-error below 5 were achieved for all our
samples. In this study, for ZnO film thickness of 5, 9, and
19 nm, a three layer model (i.e., air/ZnO layer/Si substrate)
and for ZnO film thickness of 38, 52, and 69 nm, a four layer
model (i.e., air/surface-roughness layer/ZnO layer/Si sub-
strate) have been used to extract the optical constants of the
films, while the optical constants of Si are well known.52
The Si substrate is about 1 mm thick and has been treated as
infinite. The surface roughness factor is omitted from the
model for the thinner films because the SE is not sensitive
enough to detect the surface roughness in very thin films.
ZnO is a direct band gap semiconductor with a fundamen-
tal absorption edge at about 3.37 eV, which corresponds to
FIG. 3. (Color online) (a) and (b) Top-view SEM and AFM images of 69 nm the direct transition.53 It is known that the excitonic interac-
ZnO/Si. (c) and (d) Top-view SEM and AFM images of 9 nm ZnO/Si. tion close to the fundamental band edge strongly influences
the optical properties of ZnO.53,54 For the parameterization
Figs. 3(b) and 3(d). The 69 nm ZnO films showed wedge- of the optical properties of ZnO, a Tauc-Lorentz (T-L)
shaped grains (in-plane size along major and minor axes are model has been employed in this work. The T-L oscillator
40 and 20 nm, respectively) in their surface morphology, was developed by Jellison and Modine.55,56 The complex
which is consistent with earlier reported findings on higher
temperature ALD-grown ZnO films.37 On the other hand,
SEM and AFM images show smooth and uniform surface
morphology for our 9 nm ZnO film. The root-mean-square
(RMS) roughness was estimated for characteristic ZnO film
thicknesses from AFM images, which were found to decrease
in thinner films (at and below 20 nm), as shown in Table I.
The results were consistent with the surface roughness
obtained from XRR measurements.
The surface roughness of ZnO films of thickness below
20 nm is found to be less than that of ZnO film of 69 nm
and also observed to decrease with film thickness. This is
further corroborated by the smaller grain sizes obtained from
XRD data for thinner ZnO films with thickness below
20 nm, as shown in Table I and Fig. 2(c).

C. Optical properties
The optical properties of as-grown ZnO thin films on Si,
namely, the complex dielectric function, absorption coeffi-
cient, and band gap, were determined using SE in the
0.8–6.5 eV photon energy range. The main advantages of the
SE technique are its precision and nondestructiveness46,47
and, particularly, the ability to measure simultaneously the
thicknesses and the optical constants of the system.47
Spectroscopic ellipsometry measures the Jones ratio, J, as a
function of photon energy (E) and angle of incidence (/),
described by the equation48–50

JðE; /Þ ¼ ðrp =rs Þ ¼ ðtan wÞeiD ; (7)

where rp and rs are the complex Fresnel reflectance ratios for

p and s polarized light, respectively. w and D are the ellipso- FIG. 4. (Color online) Ellipsometric angles w and D as a function of photon
energy for ZnO films of (a) 69 nm, and (b) 19 nm film thickness, grown on
metric angles corresponding to the amplitude ratio and the Si substrates, acquired with incidence angles ranging from 60 to 70 ;
relative phase change, respectively.49,51 circles and lines represent experimental data and theoretical fit, respectively.

JVST A - Vacuum, Surfaces, and Films

01B108-6 Pal et al.: Tunable optical properties in ALD 01B108-6

dielectric function (e ¼ e1 þ ie2) of the ZnO thin films as a films on Si. The magnitudes of both the real and imaginary
function of the photon energy can be written in the following parts of dielectric functions near the band edge significantly
functional form known as the T-L model:47,55,56 drop in thin ZnO films on Si (i.e., at and below 20 nm film
thickness). As compared to 69 nm film, the ZnO film on Si
AE0 CðE  Eg Þ2 1 with a thickness of 9 nm shows a reduction of 34% and
e2 ð E Þ ¼  2  ðE > Eg Þ ¼ 0 ðE  Eg Þ;
2 2
E  E0 þ C E 2 2 E 57% in the real and imaginary parts of the complex dielec-
(8) tric function at the photon energy of 3.3 eV, respectively,
þ while the ZnO film on Si with a thickness of 5 nm shows
2P ne2 ðnÞ a drastic reduction of 46% and 73%, respectively. The
e1 ð E Þ ¼ e1 þ dn : (9)
p n2  E2 peaks of e1 and e2 also show a blue shift with the decreasing
film thickness (at and below 20 nm).
The T-L oscillator model is based on the Tauc joint den- To explain the significant drop in the magnitudes of both
sity of states and the Lorentz oscillator; the fit parameters the real and imaginary parts of the complex dielectric func-
are A, E0, C, Eg, and e1.47,55 The parameter A stands for the tions, we compare the extracted electron density coverage,
transition matrix element, which is proportional to the mag- qcov (by fitting the XRR data using Parratt formalism39),
nitude of the real and imaginary part of complex dielectric with the relative (e1  1) (which is proportional to valence
constant.47 E0 corresponds to the peak transition energy, electron density, unless the transition matrix element
which is related to the Penn gap which represents an average changes57) of ZnO, versus ZnO film thickness in Fig. 6. The
separation between the valence band and conduction band.47 relative electron density (qrel) was estimated using the fol-
C is the broadening term, related to the degree of disorder in lowing equation:
the material.47 Eg stands for the optical band gap, e1 is the
high frequency dielectric constant, and P stands for the prin- electron density of a given ZnO film
qrel ¼  100:
cipal part of the integral.47,55 bulk ZnO electron density
The calculated e1 and e2 using the best-fit parameters for (10)
ZnO thin films on Si with various thicknesses are shown in
Fig. 5. As can be seen in Fig. 5, the film thickness has a sig- e1 was calculated at a photon energy of 0.8 eV. The relative
nificant effect on the complex dielectric functions of ZnO (e1  1) was estimated using the following equation:

ðe1  1Þ of a given ZnO film

ðe1  1Þrel ¼  100: (11)
ðe1  1Þ of 69 nm ZnO film

Figure 6 shows that for the same thickness range, the valence
electron density, proportional to (e1  1), starts decreasing
more sharply at and below 20 nm film thickness, and drops
by 45% in the thinnest film. On the other hand, XRR
results of ZnO films on Si indicate that the electron density
of ZnO films remains constant down to 20 nm thickness, and
then decreases only a little, by less than 7%. A slight
decrease of the electron density in our thinnest films,
obtained from XRR, is not sufficient to explain the following

FIG. 6. (Color online) Plot of the extracted relative electron density, qrel
FIG. 5. (Color online) Evolution of (a) real part (e1) and (b) imaginary part (by fitting the XRR data using the Parratt formalism), and relative (e1  1),
(e2) of the complex dielectric function with ZnO film thickness. These ZnO (e1  1)rel of ZnO, vs ZnO film thickness. Si was used as the substrate for
films were grown on Si. these films.

J. Vac. Sci. Technol. A, Vol. 35, No. 1, Jan/Feb 2017

01B108-7 Pal et al.: Tunable optical properties in ALD 01B108-7

phenomena: (1) the significant drop in (e1  1) and (2) the

significant reduction in near-band gap absorption.
The reductions in the complex dielectric functions could
be explained by using the concept of the Tanguy–Elliot
amplitude prefactor. According to Tanguy’s theory for
excitonic absorption, the complex dielectric function,
(e ¼ e1 þ ie2), can be written34,35 as
pffiffiffi
A R
ð Þ
e E ¼ fga ðnðE þ iCÞÞ
ðE þ iCÞ2
þ ga ðnðE  iCÞÞ  2ga ðnð0ÞÞg; (12)

where the amplitude prefactor

 32
2 q2
h 2l
A¼ je  Mcv ð0Þj2 ; (13)
2pe0 m20 
h2

where je  Mcv ð0Þj is the dipole matrix element which corre-

sponds to the overlap of electron and hole.34 R is the energy
of the fundamental exciton bound state, Eg is the band gap
energy, l is the reduced mass of the exciton, and C is the
broadening of the energy levels.34

ga ðnÞ ¼ 2 ln n  2p cotðpnÞ  2wðnÞ  1=n; (14)

sffiffiffiffiffiffiffiffiffiffiffiffiffi FIG. 7. (Color online) (a) Absorption coefficients a (determined from
R Ellipsometry) of ZnO films of different thicknesses grown on Si at 200  C.
nðzÞ ¼ ; (15) The inset of (a) shows wider-band gap ZnO deposited on narrower-band gap
Eg  z
Si, with staggered type-II alignment and (b) absorption coefficients a (deter-
mined from UV-VIS) of ZnO films of equivalent thickness grown on fused
d ln CðzÞ
w ðzÞ ¼ : (16) Quartz (SiO2) at 200  C. The inset of (b) shows ZnO deposited on wider
dz band gap SiO2 corresponding to type-I quantum well.

In our study, in thinner ZnO films on Si (at or below 20 nm below 20 nm. Whereas in the case of ZnO deposited on
film thickness), the exciton is deconfined because of the stag- wider band gap SiO2 corresponding to type-I quantum well,
gered band alignment. The electron remains mostly confined the thinner ZnO films show higher absorption coefficient at
in the ZnO conduction band quantum well (at least at low and above the band edge, shown in Fig. 7(b).
temperatures, where thermal excitation of the electron across In the case of ZnO deposited on Si, which is a staggered
the barrier into the Si substrate can be ignored), while the type-II quantum well, shown in inset of Fig. 7(a), the photo-
photoexcited ZnO hole will quickly relax across the interface generated holes at ZnO are deconfined to the Si substrate at
into the Si substrate. This reduces the overlap of the electron the interface, whereas electrons are confined in ZnO thin
and hole wave functions and thus the amplitude prefactor, film, causing a lowering of electron–hole overlap factor and
A, in the Tanguy dielectric function [Eq. (12)]. For thinner thus exhibits low excitonic absorption in thinner films, con-
films, where the thickness is near or below the excitonic sequently bringing about a decrease in real and imaginary
Bohr radius, the delocalization of excitons near the interface parts of the dielectric function.
plays an important role. These excitons are effectively The inset of Fig. 7(b) illustrates the ZnO/SiO2 system,
probed by optical techniques such as ellipsometry, where the which is a thin type-I quantum well, consisting of a
excitonic absorption strength modulates the magnitude of narrower-bandgap semiconductor grown on a wider-bandgap
the real and imaginary parts of the dielectric function. substrate. In this case, both the electron and the hole are con-
However, for thicker ZnO films, with film thickness fined in the ZnO film, which leads to an increase in the
above 20 nm, the delocalization phenomenon will still electron–hole overlap matrix element in thin ZnO films,
occur at the ZnO/Si interface, but the contribution of the resulting in higher absorption coefficient at the band edge. In
probed interface is much less, resulting in negligible effect our study, the absorption coefficients for ZnO/Si samples
in dielectric function. were calculated from ellipsometry data, while the absorption
To understand the phenomenon clearly, the absorption coefficients for ZnO/SiO2 samples were estimated from UV-
coefficients of ZnO/Si systems, shown in Fig. 7(a), were VIS absorption spectra, measured in the transmission mode.
compared with those of the ZnO/SiO2 shown in Fig. 7(b). The absorption coefficients of thicker ZnO films (69 nm)
Figure 7(a) shows that wider-band gap ZnO deposited on for both the systems, ZnO/Si and ZnO/SiO2, show similar
narrower-band gap Si, with staggered type alignment, values (1.5  105 cm1), indicating the negligible effect
absorbs less light with decreasing film thickness, at and of the interface (ZnO/substrate). With decreasing film

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6
thickness, the absorption coefficient of thinner ZnO films (at E. Guziewicz et al., J. Appl. Phys. 103, 033515 (2008).
7
P. F. Carcia, R. S. McLean, and M. H. Reilly, Appl. Phys. Lett. 88,
and below 20 nm) was found to decrease for ZnO/Si sam-
123509 (2006).
ples whereas that increases for ZnO/SiO2 samples. These 8
A. M. Peiro, P. Ravirajan, K. Govender, D. S. Boyle, P. O’Brien, D. D.
observations show that the thickness dependent variations of C. Bradley, J. Nelson, and J. R. Durrant, J. Mater. Chem. 16, 2088
the optical properties of ZnO thin films are also influenced (2006).
9
P. Banerjee, W.-J. Lee, K.-R. Bae, S. B. Lee, and G. W. Rubloff, J. Appl.
by the choice of the substrates. Phys. 108, 043504 (2010).
10
M. Suchea, S. Christoulakis, K. Moschovis, N. Katsarakis, and G.
IV. SUMMARY AND CONCLUSIONS Kiriakidis, Thin Solid Films 515, 551 (2006).
11
B. N. Illy et al., J. Mater. Chem. 21, 12949 (2011).
ZnO thin films of different film thicknesses, ranging from 12
J. Huang, Z. Yin, and Q. Zheng, Energy Environ. Sci. 4, 3861 (2011).
70 to 5 nm, were grown by ALD at 200  C with DEZn 13
M.-J. Jin, J. Jo, G. P. Neupane, J. Kim, K.-S. An, and J.-W. Yoo, AIP Adv.
and water precursors. The films were grown on two different 3, 102114 (2013).
14
N. O. V. Plank, M. E. Welland, J. L. MacManus-Driscoll, and L. Schmidt-
substrates, namely, Si (100) and fused quartz (SiO2). The Mende, Thin Solid Films 516, 7218 (2008).
thickness dependent optical properties of the ALD grown 15
T.-B. Hur, Y.-H. Hwang, and H.-K. Kim, Appl. Phys. Lett. 86, 193113
thin films and the effect of the substrates were studied in (2005).
16
depth. Their thickness, structure, and morphology were A. L. Schoenhalz, J. T. Arantes, A. Fazzio, and G. M. Dalpian, J. Phys.
Chem. C 114, 18293 (2010).
characterized by XRR, XRD, SEM, and AFM. We have 17
B. P. Zhang, N. T. Binh, K. Wakatsuki, C. Y. Liu, Y. Segawa, and N.
demonstrated from SE and UV-VIS absorption spectroscopy Usami, Appl. Phys. Lett. 86, 032105 (2005).
18
studies that for thinner ZnO films (at and below 20 nm) on Y. Gu, I. L. Kuskovsky, M. Yin, S. O’Brien, and G. F. Neumark, Appl.
Phys. Lett. 85, 3833 (2004).
Si, the absorption coefficient drops, while it increases for 19
K. Kitamura, T. Yatsui, and M. Ohtsu, Appl. Phys. B 97, 825 (2009).
similar ZnO films on SiO2. These phenomena have been 20
H. T. Ng, B. Chen, J. Li, J. Han, M. Meyyappan, J. Wu, S. X. Li, and E. E.
explained consistently in terms of Tanguy–Elliott amplitude Haller, Appl. Phys. Lett. 82, 2023 (2003).
21
prefactor. For ZnO on Si with its type-II band alignment, the J. G. Lu, Z. Z. Ye, Y. Z. Zhang, Q. L. Liang, S. Fujita, and Z. L. Wang,
Appl. Phys. Lett. 89, 023122 (2006).
exciton disintegrates near the interface, and therefore, the 22
K.-F. Lin, H.-M. Cheng, H.-C. Hsu, L.-J. Lin, and W.-F. Hsieh, Chem.
Tanguy–Elliott overlap factor drops, leading to a drop in the Phys. Lett. 409, 208 (2005).
23
absorption coefficient. For ZnO on SiO2, on the other hand, J. C. Nie, J. Y. Yang, Y. Piao, H. Li, Y. Sun, Q. M. Xue, C. M. Xiong, R.
the type-I band alignment strongly confines the excitons in F. Dou, and Q. Y. Tu, Appl. Phys. Lett. 93, 173104 (2008).
24
A. A. Mosquera, D. Horwat, A. Rashkovskiy, A. Kovalev, P. Miska,
thin ZnO films, increases the overlap factor, and therefore D. Wainstein, J. M. Albella, and J. L. Endrino, Sci. Rep. 3, 1714
the absorption coefficient increases. (2013).
25
Our study establishes that for ZnO thin films, where the X. D. Li, T. P. Chen, P. Liu, Y. Liu, Z. Liu, and K. C. Leong, J. Appl.
Phys. 115, 103512 (2014).
thickness is near or below the excitonic Bohr radius, the 26
T. Tommi and K. Maarit, Semicond. Sci. Technol. 29, 043001 (2014).
delocalization and localization of excitons near the interface 27
M. Godlewski et al., Thin Solid Films 518, 1145 (2009).
28
(ZnO/substrate) based on the selection of the substrate play E. Guziewicz et al., J. Appl. Phys. 105, 122413 (2009).
29
an important role in systematically tuning its optical Z. Shi and A. V. Walker, J. Phys. Chem. C 119, 1091 (2015).
30
R. W. Johnson, A. Hultqvist, and S. F. Bent, Mater. Today 17, 236
properties. (2014).
31
S. M. George, Chem. Rev. 110, 111 (2010).
32
S. M. George, A. W. Ott, and J. W. Klaus, J. Phys. Chem. 100, 13121
ACKNOWLEDGMENTS (1996).
33
The authors would like to acknowledge IIT Indore for all N. El-Atab, S. Alqatari, F. B. Oruc, T. Souier, M. Chiesa, A. K. Okyay,
and A. Nayfeh, AIP Adv. 3, 102119 (2013).
kinds of support to this work. The authors would also like to 34
C. Tanguy, Phys. Rev. Lett. 75, 4090 (1995).
thank the Department of Science and Technology (DST), 35
C. Tanguy, Phys. Rev. Lett. 76, 716 (1996).
36
Government of India, and Sophisticated Analytical Z. Baji, Z. Labadi, Z. E. Horvath, M. Fried, B. Szentpali, and I. Barsony,
J. Therm. Anal. Calorim. 105, 93 (2011).
Instrument Facility (SAIF), IIT Bombay, for the SEM 37
S. Jeon, S. Bang, S. Lee, S. Kwon, W. Jeong, H. Jeon, H. J. Chang, and
measurements, and the Nanoscale Research Facility (NRF) H.-H. Park, J. Electrochem. Soc. 155, H738 (2008).
38
at IIT Delhi for the AFM measurements. The work at NMSU S. Chattopadhyay and A. Datta, Macromolecules 40, 3313 (2007).
39
was supported by the National Science Foundation (DMR- L. G. Parratt, Phys. Rev. 95, 359 (1954).
40
S. Chattopadhyay and A. Datta, Phys. Rev. B 72, 155418 (2005).
1505172). This work was partially supported by the 41
S. Chattopadhyay, A. Uysal, B. Stripe, G. Evmenenko, S. Ehrlich, E. A.
Department of Science and Technology (DST), India, Karapetrova, and P. Dutta, Phys. Rev. Lett. 103, 175701 (2009).
42
Project No. SB/S2/CMP-077/2013 and Council of Scientific S. Chattopadhyay, A. Uysal, B. Stripe, Y.-G. Ha, T. J. Marks, E. A.
and Industrial Research (CSIR), India, Project No. 03 Karapetrova, and P. Dutta, Phys. Rev. Lett. 105, 037803 (2010).
43
C. V. Weiss, J. Zhang, M. Spies, L. S. Abdallah, S. Zollner, M. W. Cole,
(1310)/14/EMR-II. and S. P. Alpay, J. Appl. Phys. 111, 054108 (2012).
44
N. Ghobadi, Int. Nano Lett. 3, 2 (2013).
1 45
J. Anderson and C. Van de Walle, Rep. Prog. Phys. 72, 126501 (2009). B. M. Han, S. Chang, and S. Y. Kim, Thin Solid Films 338, 265
2
A. B. Djurisić, A. M. C. Ng, and X. Y. Chen, Prog. Quantum Electron. 34, (1999).
46
191 (2010). Q. H. Li, D. Zhu, W. Liu, Y. Liu, and X. C. Ma, Appl. Surf. Sci. 254,
3
Z. L. Wang, Appl. Phys. A 88, 7 (2007). 2922 (2008).
4 47
D. Bagnall, Y. Chen, Z. Zhu, T. Yao, S. Koyama, M. Y. Shen, and T. J. P. Zhang, G. He, L. Q. Zhu, M. Liu, S. S. Pan, and L. D. Zhang, Appl.
Goto, Appl. Phys. Lett. 70, 2230 (1997). Surf. Sci. 253, 9414 (2007).
5 48
S. T. Tan, B. J. Chen, X. W. Sun, W. J. Fan, H. S. Kwok, X. H. Zhang, H. Fujiwara, Spectroscopic Ellipsometry: Principles and Applications
and S. J. Chua, J. Appl. Phys. 98, 013505 (2005). (Wiley, West Sussex, England, 2007).

J. Vac. Sci. Technol. A, Vol. 35, No. 1, Jan/Feb 2017

01B108-9 Pal et al.: Tunable optical properties in ALD 01B108-9

49 53
R. M. Azzam and N. M. Bashara, Ellipsometry and Polarized Light S. Logothetidis, A. Laskarakis, S. Kassavetis, S. Lousinian, C. Gravalidis,
(North-Holland/Elsevier Science, Amsterdam, Netherlands, 1987). and G. Kiriakidis, Thin Solid Films 516, 1345 (2008).
50 54
H. G. Tompkins and W. A. McGahan, Spectroscopic Ellipsometry and G. E. Jellison and L. A. Boatner, Phys. Rev. B 58, 3586 (1998).
55
Reflectometry: A User’s Guide (Wiley, New York, 1999). G. E. Jellison and F. A. Modine, Appl. Phys. Lett. 69, 371 (1996).
51 56
H. Tompkins and E. A. Irene, Handbook of Ellipsometry (William G. E. Jellison and F. A. Modine, Appl. Phys. Lett. 69, 2137
Andrew, New York, 2005). (1996).
52 57
C. M. Herzinger, B. Johs, W. A. McGahan, J. A. Woollam, and W. A. M. Fox, Optical Properties of Solids (Oxford University, New York,
Paulson, J. Appl. Phys. 83, 3323 (1998). 2001), Vol. 3.

JVST A - Vacuum, Surfaces, and Films