Accepted Manuscript

Title: Optical Properties of ZnO Semiconductor Nanolayers

Authors: Igor Khmelinskii, Vladimir I. Makarov

PII: S0025-5408(18)31835-X
DOI: https://doi.org/10.1016/j.materresbull.2018.09.030
Reference: MRB 10197

To appear in: MRB

Received date: 12-6-2018

Revised date: 29-8-2018
Accepted date: 17-9-2018

Please cite this article as: Khmelinskii I, Makarov VI, Optical Properties
of ZnO Semiconductor Nanolayers, Materials Research Bulletin (2018),
https://doi.org/10.1016/j.materresbull.2018.09.030

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Optical Properties of ZnO Semiconductor Nanolayers
Igor Khmelinskii (1) and Vladimir I. Makarov (2)

1
University of the Algarve, FCT, DQF and CEOT, 8005-139, Faro, Portugal
2
University of Puerto Rico, Rio Piedras Campus, PO Box 23343, San Juan, PR 00931-3343,
USA

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Corresponding Author: Dr. Vladimir Makarov
Department of Physics,
UPR, Rio Piedras Campus,

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PO Box 23343

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San Juan PR 00931
USA

GRAPHICAL ABSTRACT
U
N
0.7
0.6 (a) 4
A
0.5
OPtical Density

0.4
M

3
0.3
0.2 2
D

0.1
1
0.0
TE

0 1 2 3 4 5
4 -1
Energy (10 , cm )
EP

40
(b) 4
Emission Intensity (a.u.)

30
CC

3
20
2
10
A

0 1

-10
0 1 2 3 4 5
4 -1
Energy (10 , cm )

1
Graphical abstract: (a) absorption and (b) emission spectra of ZnO nanolayers with different
thickness

Highlights

1. We report a deposition technology of high-quality uniform ZnO thin films;

2. We report discrete bands in absorption and emission spectra of ZnO films deposited
on CaF2, interpreted in terms of one-dimensional quantum confinement;

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3. We report very long exciton lifetimes in ZnO films, as compared to other ZnO

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nanostructures.

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SC
Abstract

Presently we explore absorption and emission spectra of ZnO semiconductor nanolayers 4.1 –

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17.3 nm thick. We report that their absorption spectra have discrete structure, with the
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transition band density increasing with the nanolayer thickness. The emission spectra
recorded at 4.1 and 9.3 nm thickness have resolved band structure, with the bands partially
A
overlapping in the 9.3 nm sample. On the other hand, the emission spectra are strongly
M

overlapped in the 13.1 and 17.3 nm samples. We used our modeling approach that considers
electronic states in a one-dimensional infinite potential well, calculating the relative electron
D

mass of 0.205, and the starting quantum number for the absorption transitions of 7, 8, 9 and 9,
for the respective samples. We also discuss the present results using the traditional approach
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of solid-state physics, considering potential surfaces in the linear momentum space.

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Keywords: ZnO; absorption spectrum; emission spectrum; quantum confinement; thin film;
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exciton
A

I. Introduction

Presently physical properties of nanostructured systems attract a lot of attention, due to their
unique physical and chemical properties [1-3]. Nanostructured materials have promising
applications in optoelectronics [4-9], nanophotonics [10-14], and optical communications
2
[15-19]. Quantum confinement (QC) occurs when at least one of the system dimensions
becomes smaller than the de Broglie wavelength of the electrons [20-22]. QC may thus occur
in tree dimensions (3D), two dimensions (2D) or one dimension (1D) only. The 1D QC is
created in nanolayers, where both longitudinal (plasmon/polaron) and transverse (exciton)
oscillations may propagate. Quantum confinement results in significant changes in the
electronic structure of nanostructured materials, very interesting for both fundamental studies
and engineering applications, including development of novel optical devices. Earlier we
reported the analysis of spectral properties (generation of exitons) of metal and

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semiconductor nanolayers, determined by 1D QC [23-28]. We also reported superemission

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(SE) in metal nanolayers [9-12] that may be used to build lasers. Other authors reported SE

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within the QC – generated level system in homogeneous nanolayers and nanotubes [29-31].
One-dimensional QC in conductive nanolayers always operates along the direction normal to

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the layer surface. We found [23-25] that the absorption spectra of conductive nanolayers have
a discrete structure, with the energies of the absorption band maxima very well described by

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the simple model of electron in a rectangular potential box with infinite walls [32]. The
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absorption band maxima are given by the expression [32]
A
 n, n  m  3029.2
1

2
2mn  m2  (1)
M

fa

where f = meff/me is the relative electron mass, meff is the effective electron mass, which is an
D

empirical parameter depending on the material and less than me, the free electron mass, a is
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the nanolayer thickness expressed in nm, n is quantum number of the starting electronic state,
m is the quantum number difference in the transition, and the transition energy is expressed in
cm-1.
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The QC observed in metals is understood as quantization of the continuous electron energy

CC

spectrum upon a transition from bulk material to a nanostructure. However, the same effect in
semiconductor materials requires additional experimental and theoretical studies, as it was
explored in a limited number of semiconducting nanostructured systems. These include free-
A

standing nanolayers fabricated of InAs [29], and deposited nanolayers of Si and SnO2
[16,17]. In particular, optical absorption properties of free-standing InAs nanomembranes 3
to 19 nm thick were investigated by Fourier transform infrared spectroscopy [29], with the
room-temperature absorption growing stepwise towards higher energies. These spectra were

3
interpreted as arising from the interband transitions between the subbands of the two-
dimensional InAs nanomembranes. The absorbance change associated with each step was ca.
1.6%, independent on the membrane thickness. These experimental results are consistent with
the theoretically predicted absorbance quantum:

AQ = πα/nc

for each set of the interband transitions in a 2D semiconductor, where α is the fine structure
constant and nc is an optical local field correction factor [29]. The absorbance quantization

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appears to be universal in 2D systems including quantum wells and grapheme, with the

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experimental results and their theoretical interpretation reported in [29]. Comparing the

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experimental and modeling results obtained for deposited Si and SnO2 [24,25] and free-
standing InAs [21], we formulate several research tasks: (i) compare the absorption/emission

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spectra of free-standing and deposited semiconductor thin films; (ii) develop theoretical
approaches to the analysis of the absorption/emission spectra; (iii) explore superemission in

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such films, and (iv) further applications of the studied material using new properties coupled
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with QC phenomenon. The present paper uses ZnO as a model system in such a study, aiming
at a deeper understanding of the electronic structure and properties of semiconductors.
A
M

ZnO is a very interesting semiconductor material, with numerous studies devoted to its
optical properties [33-41]. Structural, thermal, morphological and optical properties of ZnO
D

nanoparticles were investigated by X-ray diffraction (XRD), differential scanning calorimetry

(DSC), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS),
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Ultraviolet (UV) –Visible (Vis) spectroscopy and Raman spectroscopy [33]. Thin films of
intrinsic and Al-doped ZnO were prepared by the sol-gel technique with spin coating onto
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glass substrates [34]. All of those films exhibited a transmittance above 80–90% along the
visible range up to 650 nm and a sharp absorption onset about 375 nm corresponding to the
CC

fundamental absorption edge at 3.3 eV. Intense UV photoluminescence was observed for
undoped and 1% Al-doped ZnO films [34]. Changes in structural, morphological, and optical
properties of sol-gel derived ZnO and ZnO:Fe nanoparticles occurred due to dense electronic
A

excitations produced by heavy ion irradiations using 200 MeV Ag+ ion beams [35,36]. UV-
Vis measurements found that the band gap increased on Fe doping [35], attributed to 4s–3d
and 2p–3d interactions and the Burstein-Moss band filling effect. Photoluminescence (PL)
intensity was enhanced and two new emission bands at ca. 480 nm (due to surface defects)

4
and at 525 nm (due to O vacancies) were observed in ion-irradiated nanoparticles [35]. A
review of current research on the optical properties of ZnO nanostructures was compiled
earlier [37]. The optical band gaps of the ZnO thin films deposited on Si substrate were
determined using UV spectra, varying from 3.24 to 3.29 eV in function of the oxygen ratio
[38]. Other authors explored graphene-ZnO sandwich assemblies and other nanostructured
devices containing ZnO [39-41]. However, there are no published absorption/emission
spectra of ZnO thin films demonstrating QC, although such data are important for
understanding whether QC is inherent to all semiconductors including ZnO, or it is dependent

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on the electronic structure of specific materials.

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Presently we investigate this latter issue, and research an adequate theoretical description for

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the recorded spectra. In particular, we report absorption and emission spectra of ZnO

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semiconductor nanolayers 4.1, 9.3, 13.1 and 17.3 nm thick, and discuss theoretical
approaches that may be used to analyze these spectra. The absorption spectra of these thin

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films have discrete structure, with the band density increasing with the nanolayer thickness.
The thinner films have a resolved discrete structure, although the emission bands in the 9.3
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nm film are already partially overlapped. On the other hand, the emission bands in the thicker
A
samples are overlapped quite strongly. We analyzed the absorption spectra in the frameworks
M

using our earlier modeling approach [23-25], calculating the relative electron mass of 0.2051
in ZnO films, independent on the film thickness, while the n value increased with the film
D

thickness, equal respectively to 7, 8, 9 and 9, for the four samples. We also interpret the same
results using the classic solid-state physics ideas [29]. Presently we also report an extension
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to our theoretical approach, with a detailed treatment of the interaction of the nanolayer with
the electromagnetic field, producing excitons, leaving any additional issues related to QC in
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semiconductors for future studies.

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II. Experimental

Fluorite (CaF2) substrates sized 2512.5 mm2 and 1 mm thick (Esco Optics) were used to
A

deposit the samples. We used commercial ZnO (Sigma/Aldrich) to deposit nanocrystalline

films using a commercial sputtering/thermo-evaporation Benchtop Turbo deposition system
(Denton Vacuum). The ZnO nanolayers were deposited using thermo-evaporation, with the
substrate at 375ºC in all experiments. The films were annealed for 2 hours at 900oC and

5
atmospheric pressure of pure nitrogen gas. Film thickness was controlled by XRD [42], on an
XPert MRD system (PANalytic), calibrated using standard nanofilms of the same material.
The estimated absolute uncertainty of the film thickness was 0.2%; the relative uncertainties
were much smaller, determined by the shutter opening times of the deposition system. The
method for measuring the thin film thickness is based on recording the scattering/interference
pattern of X-rays. The X-ray photons reflected from each of the atomic layers of the thin film
contribute to the total reflectivity. The observed reflections may be therefore used to calculate
the number of atomic/molecular layers in the film and thus its thickness.

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Absorption and emission spectra were recorded on a Hitachi U-3900H UV-Visible
Spectrophotometer and Edinburgh Instruments FS5 Spectrofluorometer, respectively. The

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absorption spectra in the middle- and near-IR were recorded on a PF2000 FTIR spectrometer

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(Perkin Elmer). Absorption spectra are presented as the difference of the transmission and the
reflection spectra. The spectral peak maxima were precisely located using PeakFit software

U
(Sigmaplot). The polynomials were fitted and the fitting uncertainties estimated using the
LINEST function in Excel (Microsoft). Photo-induced response measurements were
N
performed using a high-pressure Xe lamp (1000W, Ariel Corporation, Model 66023), a
A
monochromator (Thermo Jarrell Ash, Mono Spec/50), a DET10A Biased Si detector
M

(THORLABS, supplied with the spectral calibration curve), a model 2182A nanovoltmeter
(Keithley Instruments) connected to a computer by a GPIB interface, and home-made
D

software in the LabView programming environment (National Instruments). The light of the
Xe lamp was filtered by interference filters with the pass-band centered at 223 nm, and used
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to excite emission of the ZnO layers. Emission spectra recorded in IR and UV/VS spectral
regions were sewed and presented as common one.
EP

We recorded time-resolved emission using the fundamental harmonics of a dye laser for
excitation: LPD-2000 (-Physics) with Coumarin-4 dye (with frequency multiplication on a
CC

BBO crystal; -Physics). The Coumarin-4 dye fundamental could be tuned in the 370-580
nm spectral range (frequency-doubled to obtain 220-290 nm radiation), and pumped by the
A

fourth harmonics of a Nd-YAG laser (266 nm, Surelight-II, Continuum Inc.). The laser pulse
duration was 7-10 ns. The dye laser radiation was defocused onto the entire surface of the
respective sample. The emission was collected by a 30-cm spherical CaF2 lens and detected
by a photodiode (PD1; DET10A Biased Si Detector from THORLABS) or a photomultiplier
(PMT-H9305-03, Hamamatsu), after passing through a neutral density filter. The data
6
acquisition system contained a PC computer, a digital oscilloscope (WaveSurfer 400 series,
LeCroy), two digital delay generators (DG-535, Stanford Research), a photo-detector (PD:
DET10A Si Detector from THORLABS) or a photomultiplier (PMT-H9305-03,
Hamamatsu), two boxcar integrators (SR-250, Stanford Research), a fast amplifier (SR-240,
Stanford Research), and a computer interface board (SR-245 Stanford Research). For the
spectroscopy experiments, the LIF signal was monitored by the digital oscilloscope and
averaged, typically using 5 laser pulses per frequency step. The output energy was controlled
and the monochromator scan operated using a PD and PCI-6034E DAQ I/O board (National

T
Instruments), with the control code in the LABVIEW environment running on a second Dell

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PC. The presently used experimental methods produced 2.5 ns time resolution.

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All of the measurements were performed in an optical cryostat (Optistat DN-V2, Oxford

SC
Instruments) at 77K, unless expressly indicated otherwise.

III. Results U
N
A
a) Absorption and emission spectra of ZnO nanolayers
M

Absorption and emission spectra were recorded for the ZnO layers 4.1, 9.3, 13.1, and 17.3 nm
thick, with the results shown in Fig. 1.
D
TE

<Insert Figure 1>

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The absorption spectra of Fig. 1 were analyzed using commercial PeakFit software package,
CC

with the respective results listed in Tab. 1.

A

<Insert Table 1>

Table 1. Absorption band maxima and widths.

7
 4.1 nm film 9.3 nm film 13.1 nm film 17.3 nm film
Maximum, Width, Maximum, Width, Maximum, Width, Maximum, Width,
cm-1 cm-1 cm-1 cm-1 cm-1 cm-1 cm-1 cm-1
13179 1484 2902 934 1635 873 937 911
28115 1477 6147 897 3442 823 1973 894
44808 1481 13661 943 5422 817 3108 879
17930 952 12393 874 4342 923
22540 921 15061 913 5675 911
27493 917 17901 874 7106 932
32786 911 20913 892 13817 879
38421 931 24097 911 15742 823

T
44398 931 27454 874 17765 879

IP
50716 927 30982 816 19887 877
34683 853 22107 845
38556 875 24427 859

R
42601 907 26845 893

SC
46818 892 29362 872
51207 896 31977 813
34691 876
37504 811

U 40416
43426
894
003
N
46535 891
49742 859
A
M

Fig. 2 shows the band maxima in function of the quantum number increment of the respective
resulting absorption band.
D
TE

<Insert Figure 2>

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We fitted the plots of Fig. 2 using Eq. (1), with the fitting parameters n and f listed in Tab. 2.
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<Insert Table 2>

A

Table 2. Values of n (the starting quantum number for the transitions) and f (the relative
electron mass) fitting parameters for the band maxima of Table 1 in function of the quantum
number increment. Eq. (1) was used to fit the data.

Fitting Sample thickness, nm

parameters 4.1 9.3 13.1 17.3
8
 n 7 8 9 9
f 0.2050 0.2053 0.2049 0.2052

The emission spectra of the two thinner films were analyzed in the entire recorded range,
while the spectrum of the 13.1 nm was only simulated below 28500 cm-1. Note that resonance
emission at the excitation wavelength was cut off using an appropriate optical filter, which
passed longer wavelengths only. We did not analyze the emission of the 17.3 nm sample, as
the respective spectrum lacked discernible structure. Tab. 3 lists the emission bands that were

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identified.

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<Insert Table 3>

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Table 3. Emission bands of the three thinner ZnO films; the emission spectrum of the thickest

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film lacked a resolved structure.

4.1 nm
Maximum,
cm-1
Bandwidth,
cm-1
9.3 nm
Maximum,
cm-1 cm-1
U
Bandwidth,
13.1 nm
Maximum,
cm-1
Bandwidth,
cm-1
N
31629 3175 41496 1821 27540 1721
A
16693 3241 38251 1793 24700 1678
34665 1893 21688 1709
M

30737 1826 18504 1721

26468 1783 15147 1734
21858 1812 11619 1689
D

16905 1769 7918 1703

11612 1791 4045 1817
TE

5977 1804

Considering the data of Tab. 3, we conclude that the band maxima may be described by the
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expression
CC

 em   exc  n, n  m   exc  3029.2

1
fa

2
2mn  m 2 , (2)
A

where exс is the photon energy corresponding to the maximum of the absorption band used
for excitation. The following absorption bands were used for excitation: (1) n = 7  n = 10
(44808 cm-1); (2) n = 8  n = 18 (44398 cm-1); (3) n = 9  n = 25 (46818 cm-1); and (4) n =
9  n = 31 (43426 cm-1). Using Eq. (2) and the spectral band data, we fitted the emission

9
band maxima in function of the quantum number decrement for the two intermediate
samples. The data points and the respective fitting curves are shown in Fig. 3.

<Insert Figure 3>

Note that the fitting parameters n (8 and 9, respectively) and f = 0.20480.0003 agree quite

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well with the same parameters obtained for the absorption spectra and listed in Tab. 2.

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Below we shall discuss the bandwidth formation mechanism in thin films.

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b) Time-resolved experiments

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Time-resolved experiments were carried out for all samples of interest using the same

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excitation wavelengths provided by a pulsed laser. The data recording was started with 20 ns
delay after the maximum of the excitation laser pulse, to reduce scattered laser light and fast
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resonance emission. The emission waveforms are shown in Fig. 4a.
A
M

<Insert Figure 4>

D
TE

The recorded waveforms were fitted with good accuracy by an exponential function

t

EP

I em t   Aeme  em
(3)

where A0 is the signal amplitude and em is the emission lifetime, with the values of the latter
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listed in Tab. 4.
A

<Insert Tab. 4>

Table 4. Measured emission lifetimes in ZnO thin films.

Sample 4.1 nm 9.3 nm 13.1 nm 17.3 nm

em, ns 38.22.1 43.62.3 51.13.3 31.52.1

10
 las, ns 7.30.2 7.50.4 7.10.3 7.70.4
prop,1, ns 12.20.9 11.10.8 13.10.8 9.70.7
prop,2, ns 37.22.2 41.72.1 48,92.7 29.82.2

These emission lifetimes are longer in comparison with the data reported earlier [43-46] in
other nanostructured systems, which fell into the 1 – 20 ns time range. Time-resolved
experiments on nanostructured ZnO systems also reported much shorter lifetimes in the 1 –

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10 ps time range [47-52]. However, we found no reported emission lifetimes in ZnO

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nanofilms. Note also that earlier reported emission lifetimes in Co metal nanofilms are even
longer than the currently reported lifetimes in ZnO [47]. We shall discuss these results in

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more detail below.

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We also studied the dynamics of exciton propagation along the ZnO film. In these
experiments, the film was excited at 22 mm2 area in its center, while the emission was
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collected from a rectangle at the edge of the film, sized 12.52 mm2. To take into account the
N
eventual propagation of the excitation light along the CaF2 substrate, we used an clean CaF2
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substrate for reference, subtracting reference signal from the sample signal. The recorded
M

emission signal dynamics from the films is shown in Fig. 4b. We fitted the plots by a tri-
exponential function:
D

2
 t t 
 0    t 
t

I prop,em t   A1e

 las

 
 A2 e e
 prop, 2 
TE

prop,1
(4)
 
 

With the values of the fitting parameters las, prop,1 and prop,2 are also listed in Tab. 4. We
EP

conclude that prop,2  em, las value coincides with the laser pulse duration, while prop,1 may
CC

be interpreted as the exciton wave package propagation along the 10.5 mm of ZnO film,
corresponding to the propagation velocity of ca. 108 cm/s, about 300 times slower than the
speed of light in vacuum. Presently we only report this experimental result, without its
A

analysis, which we shall provide in a follow-up publication.

IV. Discussion

11
We shall discuss quantization in the absorption and emission spectra and the mechanisms of
optical transitions, the mechanisms of spectral bandwidth formation, and the mechanism
describing the emission lifetimes in ZnO nanofilms, starting from the first issue.

i. Quantization in the absorption and emission spectra and the mechanism of optical
transitions

The analysis we presented for the absorption and emission spectra is based on a simple
physical model, with quantum confinement (QC) operating in the direction perpendicular to

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the film surface, with the system states quantized in this direction. We described the ZnO

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film as a rectangular potential box with infinite walls. This remains an acceptable

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approximation while the energy of excited states considered remains significantly below the
ionization energy of the material. In practice, Eqs. (1-2) describe the respective absorption

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and emission band positions with the errors below 1 cm-1 for the states that are several eV
below the ionization energy, with only one fitted parameter (the effective electron mass). We

U
analyzed the results reported earlier by Fang, et al. (2013) [29] using the same model to
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simulate their reported absorption spectra, for example, the spectrum of the 19 nm thick InAs
thin film (see Fig. 5a).
A
M

<Insert Figure 5>

D
TE

We took the band position maxima in the 19 nm InAs film from the earlier reported data [7].
The spectrum was simulated as a superposition of the discrete component defined by QC and
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of the continuous spectrum defined by the dielectric constant of the semiconductor material.

The continuum contribution is proportional to h exc [53], where exc is the frequency of the
CC

electromagnetic field interacting with the semiconductor. Our simulated spectrum reproduces
the earlier reported spectrum [7] with good accuracy, if we disregard the details of the
A

spectral structure attributed to different types of holes. Fig. 5b shows the band maxima in
function of the quantum number increment, that may be fitted to a second-order polynomial,
Eq. (1), with the fitting parameters of n = 1 and f = 0.125. In other words, a simple QC model
may be used to successfully describe the experimental spectra. This model, however, imposes
certain selection rules that define the allowed transitions. Indeed, only transitions with an odd
12
quantum number increment are allowed in the electric dipole approximation, represented as n
+ 2m-1  n, for integer m values. We may obtain this result analyzing the interaction of our
system with the electromagnetic field. The respective matrix elements may be written as [53]:

e   e 2   
Vij    i p  Ak '  j    i p  sk 'eik 'r  j (5)
mc m k

where Ak’ is the k’-th component of the vector potential

T
  
A   Ak 'eik 'r ,

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k'

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p is the electron linear momentum, sk’ is the unit vector directed along the vector potential
component Ak’, k’ is the wave vector of the respective component, r is the radius-vector of

SC
the electromagnetic wave distribution in space, k’ is the frequency of the k’-th component of
the vector potential. The wavefunctions in the k-space are given by:

1 U 
2 Sin  n  kl 
N

n 2 
 n  p   n  x e ikx dx 
1 l

2   n  kl n  kl
A

 2kn2
En  ; n  i or j  integer values.
M

2m (6)
D

pn
and integration is performed over the ki-space. Here, the kn  values are defined by the

TE

zeroes of the function (5). Taking into account the perturbations due to the finite amplitude of
the potential walls (the amplitude of 12 eV seems to produce the best model for the
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experimental spectra, see Appendix) and using the definition of the optical transition
efficiency:
CC

2
Pij  Vij , (7)
A

we calculated the relative band intensities for the 9.3 nm ZnO thin film using the assignment
presented above, with the results shown in Fig. 6.

<Insert Figure 6>

13
The results of Fig. 6 qualitatively reproduce the intensity distribution in the experimental
absorption spectrum of Fig. 1a(2). The results obtained for the emission spectrum using the
band assignment based on Eq. (2) are also shown in Fig. 6b, being qualitatively similar to the
experimental emission spectrum of Fig. 1b(2).

ii. Emission lifetimes

We already noted that the presently measured emission lifetimes in ZnO thin films (31 – 51
ns) are anomalously long compared to earlier reports on other ZnO nanostructures, all in the

T
picosend time range [32-37]. This discrepancy may be explained by significant differences

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between the respective systems. The emission dynamics of nanostructures is typically

R
described in the simple case by a biexponential function [39]:

SC
t t
 
I em t   Af e
f s
 As e (8)

U
where Af and As are the amplitudes of the fast- and slow-decaying components of the
emission signal, and f and s are the respective lifetimes. Presently we assume that the
N
relationships Af >> As and f << s are satisfied, proposing two different mechanisms for the
A
emission: (1) the short component describes fast dephasing of the initially prepared wave
M

package, while the long component describes independent emission dynamics of the
quasistationary states forming the initial wave package. In an ideal case, with no radiationless
D

relaxation operating, we obtain

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Af f = Ass.

(2) the initially prepared excited state is transformed into an exciton (a bound electron-hole
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pair), which recombines on a longer time scale, emitting a photon. We presume that the first
mechanism is not operating, as the excited state quickly transforms into an exciton. The
CC

second mechanism may be presented as follows:


1. NL + hexc  NL*; Wexc t   W0 t  1  e D 
A

2. NL*  NL + hem; 1/em

3. NL*  (h+…e-); k1

4. (h+…e-)  NL + hrec; krec,em

14
 5. (h+…e-)  NL; krec,nr

where NL is the ZnO nanolayer, NL* is the excited state in the ZnO nanolayer, (h+…e-) is the
exciton, W0(t) is a Gaussian function describing the laser pulse shape:

2
 t t0 
  
W0 t   W0e  0 
, (9)

with its parameters defined in section II, and t0 is an instant of time corresponding to the peak

T
of the laser pulse, D is the optical density, determined by the absorption spectra of Fig. 1a,

IP
em is the excited state lifetime, k1 is the rate constant of exciton formation, krec,em is the
radiative exciton recombination rate constant defining the recombination emission rate of the

R
slow component, krec,nr is the nonradiative exciton recombination rate constant. This scheme

SC
produces

1/f = 1/em + k1 and  s1  krec, em  krec, nr  .

U
N
The time resolution of our measurement system is about 10 ns, therefore we are can’t observe
the fast decay component and the rising part of the slow emission component. In order to
A
explain the slow emission component that we observe, we have to assume that
M

1/em << k1 and krec, nr  krec,em  k1 ,

D

or the excited states generate excitons with unitary yield, and the radiationless recombination
TE

is negligible. In the following subsection, we shall analyze the excited state transformation
into the exciton, and the exciton recombination, using the ab initio approach.
EP

iii. Ab initio analysis of the electronic structure of ZnO monoatomic layer

The monoatomic-layer ZnO electronic structure was investigated using DFT using the plane
CC

wave pseudopotential method implemented in the generalized gradient approximation (GGA)

[49] as parameterized by Perdew, Burke and Ernzerhof [40] and as implemented in the
A

SIESTA package [41,42]. The calculations were performed using Heyd-Scuseria-Ernzerhof

hybrid density functional, which mixes the exact non-local exchange of Hartree-Fork
potential with the exchange and correlation potential from GGA [39,43-45]. The effects of
mixing ratio between GGA and HF exchanges were controlled by the calibration of the
structural parameters using the database on the compounds of interest. The norm-conserving
15
pseudopotentials including the Zn 3d state in its valence shell and the wavefunctions with the
energy cutoff at 80 Ry were chosen. In the current study, we analyzed hexagonal structure of
2D ZnO films [46-48].

We began with calculating the state structures and energies of 2D ZnO in the bonding and
conductive zones. The calculated state energy diagrams of the ground state – excited state
and ground state – exciton systems are shown in Fig. 7.

<Insert Figure 7>

T
IP
Here,  is the Brillouin zone center. The density function method can’t analyze the excited

R
states in ZnO directly, while neither MPT nor coupled-cluster methods could be used due to
insufficient computational resources. Therefore, we calculated the state structure for the

SC
originally prepared system configuration using the density function method (see Fig. 7a),
while the state configuration for the exciton (electron-hole pair) was calculated as average

U
between those of positively and negatively charged ZnO systems (see Fig. 7b). The
N
wavefunctions in the latter case were represented as combinations of the positively and
A
negatively charged systems. We tested this approximate approach against the results obtained
by MP2 for H2 molecules, with the resulting discrepancy of ca. 10%. The energy gap at the 
M

point is 3.87 eV in the ground-state – excited state system, and only 2.02 eV in the ground
sate – exciton system. Thus, the stabilization energy of the exciton with respect to the excited
D

state is 1.85 eV. The energy gap for the excited state system is in an acceptable agreement
TE

with the earlier reported data [46-49].

We next used the results of ab initio calculations as input data to calculate the rate constant of
the NL*  (h+…e–) process, using homemade FORTRAN software. We used the Golden
EP

Fermi rule to calculate the rate constant [50]:


2 2
CC

VExc ,h...e    EExc  Eh...e  dEh...e   VExc ,h...e  h...e  EExc 

2 2
k1  k f  (10)
 0

A

where

VExc, h...e   exc Vna   h...e (11)

16
  h...e  EExc 
Here is the exciton state density at the energy level of the excited state created

upon absorption of light, Vˆna is the nonadiabatic perturbation coupling the excited state and

the exciton states [51-57], exc and (h…e) are the wavefunctions of the excited state and the
exciton. We calculated the state density according to:

 2
h...e  EExc    ei  Ei  Eexc 
1
4 3 i 
dk (12)

T
Where ei is the eigenvector (normalized to unit length) corresponding to the energy

IP
eigenvalue Ei. We calculated k1 = 3.71011 s-1, corresponding to the exciton formation time

R
of 2.7 ps, in acceptable agreement with the emission lifetimes in nanostructured ZnO [32-37].

SC
We next calculated the radiative recombination rate constant of the exciton, once more using
the golden Fermi, see Eq.(5):

krec,em 
2
Vrad  rad Eh...e  
2
U
N
 (13)
  
Vrad   h...e  p  sk 'eik 'r  G
A
M

where G is the ground state wavefunction. Here we obtained the rate constant of 43 s-1,
corresponding to the natural emission lifetime of 23 ns.
D

Using the same approach as presented in Eqs.(9-11), we calculated the nonradiative

TE

recombination rate of the exciton. The resulting value is 79 s-1; combining this values with
the ratiative rate constant, we obtain ks = 122 s-1. Therefore, we have the slow component
EP

lifetime of 8.2 ns, and its emission yield of 0.35. Note that the calculated lifetime of the slow
emission is shorter than the measured value. This is attributable to the simple model we used,
CC

which only has a monoatomic layer of Zn and O atoms, while the real film that has dozens of
such layers.
A

Thus, taking into account the results presented in this subsection, we conclude that the
measured emission lifetimes are quite reasonable, and the observed emission is attributable to
exciton recombination.

V.Conclusion
17
We performed detailed measurements of optical properties of ZnO nanofilms. We found that
their absorption spectra (for all films, 4.1 to 17.3 nm thick) and emission spectra (for 4.1, 9.3
and 13.1 nm nanofilms the spectra are at least partially resolved) have discrete structure, with
the energies of the respective states proportional with very high precision to the quantum
number squared n2. We interpreted these spectra in terms of quantum confinement in the
direction perpendicular to the flat film. We also report the emission lifetimes in the
nanosecond range, much longer than the values reported earlier for bulk ZnO and ZnO
nanostructures. To explain these anomalously long emission lifetimes, we carried out a

T
detailed theoretical analysis, attributing such long lifetimes to the exciton recombination.

IP
However, additional studies are need to fully understand the underlying physics, preferably

R
with much higher time resolution, that would allow to monitor the faster initial processes,
including the exciton formation.

SC
U
Acknowledgements: the authors are grateful for the financial support of the Institute of
N
Functional Nanomaterials of PR and PR NASA EPSCoR grant (NASA Cooperative
Agreement NNX15AK43A) for V.M.
A
M

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EP

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A

21
Appendix

We consider the electron in a rectangular potential box schematically shown in Fig. A.1.

E
U2

T
U1

IP
a

R
SC
Figure A.1. Rectangular potential box with finite walls.

U
Three regions are should be taken into account for E < U1, U2.
N
The first region is
A
x0
M

 1  c1e k x1
(A.1)

2mU 1  E 
1
k1  
D

h
TE

The second region is

EP

0 xa
 2  c2 Sin  k 2 x    (A.2)
CC

i
k2   2mE
h
A

And the third

22
xa
 3  c3 e k x
3
(A.3)

2mU 3  E 
1
k3  
h

Taking into account boundary conditions

ln  1 x  x  0  ln  2 x  x  0
d d

T
dx dx (A.4)
ln  2 x  x  a  ln  3 x  x  a
d d

IP
dx dx

R
The first condition in Eq. (A.4) produces

SC
 '1 0  '2 0

 1 0  2 0

k2 Ctg    k1 
2m
U1  k 2 
2 1
2mU1  E  U (A.5)
N
2
h h
A
The second condition in Eq.(A.4) produces
M

 ' 2 a   '3 a 

 2 a   3 a 
D

(A.6)
k 2 Ctg a k 2     k3  2mU 2  E 
2m 1
U 2  k2  
2
TE

2
h h

Introducing k2  k , we obtain
EP

kCtg   2mU1  E 
1
CC

(A.7)
h

or
A

Sin   
kh
2mU1
(A.8)
 kh 
  Arc sin 

 2 mU1 

23
and

kCtg ak      2mU 2  E 

1
(A.9)
h

or

Sin ka     
kh
2mU 2

T
(A.10)
 kh 
ka     Arc sin 

IP
 2mU 
 2 

R
 kh   
  Arc sin kh   n

SC
ka   Arc sin (A.11)
 2mU   2mU 
 2   1 

U
where the n term describes the periodic properties of the Sin function. Therefore finally we
N
obtain the transcendent equation:
A
 kh   
ka  n  Arc sin   Arc sin kh 
M

 2mU   2mU 
 1   2 
(A.12)
 E   E 
2mE a  n  Arc sin   Arc sin 
D

U   U 
 1   2 
TE

Assuming U1 = U2 = U0, we obtain

EP

2mE a  n  E 
 Arc sin 

(A.13)
2  U0 
CC

The last equation may be rewritten as follows:

A

E
2mU 0 a  n
U0  E 
 Arc sin 

(A.14)
2  U0 

Defining the parameter

24
 E
z (A.15)
U0

We rewrite Eq. (A.14) as follows:

z  n
 Arc sinz  (A.16)
2

T
where

IP
  2mU0 a (A.18)

R
or

SC
z  n  (A.19)
Sin  z
 2 

U
N
This transcendent equation may be solved numerically or by graphical analysis; however, for
z << 1, Eq. (A.19) may be simplified:
A
M

z  n 
  z   z
1 2
Sin  
 2  4

   z  1
1 2
D

(A.20)
4
1
TE

 2ma2 EU 0  2
2
2ma
E  Vˆpert  
EP

U0

The latter relationship was used as a perturbation mixing different states represented by
CC

Eq.(5); this perturbation was transformed into the k-space as follows:

1 2ma Sin ka

 (A.21)
A

Vˆpert  p  
1
 Vˆperteikx dx  
2   2 U 0 k

The perturbed function is represented as follows:

25
  n  p Vˆ  p  m  p 
 n ' p   n  p   (A.22)
En  Em

Finally, the relative transition probabilities were calculated using the relationship

e  
V 'ij    'i p  Ak '  ' j . (A.23)
mc

T
R IP
SC
U
N
A
M
D
TE
EP
CC
A

26
Figure captions

T
R IP
SC
U
N
A
M
D
TE
EP

Figure 1. Absorption (a) and emission (b) spectra of ZnO layers: (1) 4.1 nm thick (excitation
at 223 nm); (2) 9.3 nm thick (excitation at 225 nm); (3) 13.1 nm thick (excitation at 235 nm);
CC

and (4) 17.3 nm thick (excitation at 230 nm).

A

27
 T
R IP
SC
U
N
A
M
D
TE

Figure 2. Band maxima in function of the quantum number increment for the four ZnO film
samples: (1) 4.1 nm thick, (2) 9.3 nm thick, (3) 13.1 nm thick, and (4) 17.3 nm thick.
EP
CC
A

28
 T
R IP
SC
U
N
A
M
D
TE

Figure 3. The emission band maxima in function of the quantum number decrement for the
ZnO thin films: (2) 9.3 nm film, and (3) 13.1 nm film.
EP
CC
A

29
 T
R IP
SC
U
N
Figure 4. Emission kinetics for the ZnO thin films (1) 4.1 nm think (excited at 223 nm); (2)
A
9.3 nm thick (excited at 225 nm); (3) 13.1 nm thick (excited at 235 nm); and (4) 17.3 nm
thick (excited at 230 nm) (a) and propagated emission (1) 4.1 nm think (excited at 223 nm);
M

(2) 9.3 nm thick (excited at 225 nm); (3) 13.1 nm thick (excited at 235 nm); and (4) 17.3 nm
thick (excited at 230 nm) (b).
D
TE
EP
CC
A

30
 T
R IP
SC
Figure 5. (a) The simulated absorption spectrum and (b) dependence of the band position

U
maxima on the quantum number increment in the 19 nm thick InAs thin film [7].
N
A
M
D
TE
EP
CC
A

31
Figure 6. The relative transition probabilities in the 9.3 nm ZnO thin film: (a) absorption and
(b) emission.

T
R IP
SC
U
N
A
M
D
TE
EP
CC

Figure 7. Calculated state diagrams of three bonded and two unbounded states: (a) ground
state –excited state system; (b) ground state – exciton system for a hexagonal ZnO film.
A

32