Synthesis and characterization of

nano-dimensional GeO2
By
Mrinal seal
Registration No. Phd/R/2011/0099

Under the Guidance of

Dr. Sampad Mukherjee

Department of Physics, IIEST, Shibpur, Howrah-711103
 Germanium oxide has various applications like electro optical
modulators, piezoelectric glass materials, optical fiber materials.
In nano-structured form Germanium oxide can exhibit typical
properties
The material specially in rod shaped structure has a huge
application in opto-electronic devices due to its wide band gap and
high refractive index
 Analytical grade GeO2 powder (Alfa Aesar, 99.99%) is used to
prepare a stock solution with moderately hot double distilled water.
Twenty milliliter of this solution is taken in an in-house designed
autoclave attached with a pressure gauge.
After sealing properly, the autoclave is heated in a furnace at
different required temperatures corresponding to various pressures
measured with pressure gauge attached with the autoclave as
mentioned in table I for twenty-four hours.
After that, the autoclave is cooled naturally to ambient temperature
and the samples are collected from the product solution by
evaporating water.
 Prepared samples are characterized with XRD
Table I

Name Synthe Synthes

of the sis is
sample Pressu Temper
re ature
(bar) (0C)
Ge1 1.0133 100
Ge2 4.7600 150
Ge3 15.500 200
Ge4 21.060 215
Ge5 69.186 285
Ge6 105.00 315
FIG. 1. XRD Pattern of the samples Ge1-Ge6

These XRD patterns shows the samples are crystalline in nature having -quartz
type hexagonal structure and of phase P3221 (as mentioned in JCPDS data, PDF-
85-1519).
We have applied the theoretical Model as followed by B. Bridge
et.al. in GeO2 system [10].
Germanium Oxide system is considered as a three dimensional
network of A-O-A (A- Cations , O Anions) considered, where A-
O-A angle is not necessarily 1800.

Here, A and O represents Oxygen and Germanium ions

respectively.

a first order approximation of mutual potential energy of two

atoms of diatomic molecule takes the form

U= -(a/r)+(b/rm) (1)
GeO2 is a three atomic system, where a single anion is conjugated
with two cations. Therefore, the system can be considered as a
combination of two diatomic systems where, each system consists
of a single cation and an anion respectively. Such consideration
makes the form of the mutual potential as

U= -(a/r)+(b/rm)- {a/(R-r)}+{b/(R-r)m} (2)

According to the consideration B.Bridge et al. [10] R is the actual

separation between two extreme cations (A-A bond length) which
is smaller than the equilibrium bond length (2r0). Therefore the
strain exist inside the molecule is the ratio of the actual length
and the equilibrium length, which B. Bridge et al. [10] described
as elongation factor (e) and modified the equation 2 as below.

U= -a{(1/r) + 1/(2er0-r)}+b{(1/rm) + 1/(2er0-r)m} (3)

In the crystalline GeO2system, Ge-O bond length (r0) is
considered 1.73 [13], which results that a single GeO2
molecule contains energy -14.78 eV. This potential energy for a
single GeO2 molecule within a crystalline system is considered
as the minimum potential energy (U0) [10]. The constants as
mentioned in equation 3 are calculated respective to U0 [10].
The variation of atomic potential with the variation of
interatomic distance (r) is calculated and plotted against
elongation factors (e) according to equation 3.
 According to the potential suggested by B.Bridge et. al. figure 2
shows the variation of potential energy with atomic distance at
0% e, which has a single minimum.

FIG.2. Variations of
potential energy (U)
respect to atomic
distance at 0% e.
Figure 3(a) shows the potential energy curves for small values
of elongation factor. However, in figure 3(b) it is observed that
double well shows prominent at 30 % of e value (well above
the value of previous e) . It is observed that the depth of well
is 0.01 eV for 30 % e. We calculate the same for higher values
of e and found that the depth of such two level system (TLS)
remains same. A plot of double well depth respect to
elongation factor is shown in figure 3(c).
 FiG. 3(b) Variations of potential
energy (U) respect to atomic
distance at the value of
elongation factor 8%, 30%

FIG.3(a) Variations of potential

energy (U) respect to atomic distance
at the value of elongation factor 4%,
6%
 0.012

0.010

double well depth (eV)

0.008

0.006

0.004

0.002

0.000

0 5 10 15 20 25 30 35 40 45 50

elongation factor (%)

Fig. 3(c) Double well depth respect vs. elongation factor plot
 The peak as marked with hkl values, in figure 1 analyzed respect to the broadening

The amount of broadening of each XRD- peak is obtained by fitting each X-ray peak as
Gaussian function and measuring the full width at half maxima (X) value [11]. Such X-ray
peak broadening analysis is one of a conventional way to determine particle size (D) and
lattice distortion (d/d) [15], as according to the following relation.

XCos () = (K/D) + 4(d/d) Sin (4)

0.40
Ge4

0.35

0.30
FIG.4. Xcos vs.
Sin

Ge6
Sin plot for samples
0.25

Ge5
Ge3
0.20 Ge2

Ge1
0.15

0.20 0.25 0.30 0.35 0.40 0.45 0.50

X Cos
The respective values of grain size, lattice distortions are used in equation 3
replacing the elongation factors (e) and we observed variations in potential energy
curves as occurred previously with elongation factor values. Figure 5 shows the
variation of potential energy with the atomic distance at different lattice distortion
values. It has been observed that the potential energy curves also become flat as
lattice distortion increase.

FIG.5. Variations of
potential energy (U)
respect to atomic distance
at various lattice
distortion (d/d)
Therefore, elongation factor
(e) and the lattice distortion
(d/d) are dimensionally
equivalent
Ge1
Ge4

Ge2

Ge 5

Ge3
It is observed that the particles developed within each samples are uniform
and identical. This arouses us to calculate average particle size from each
TEM image with the help of Image-J software. The obtained particle sizes
respects to the samples are presented in table II

Name of the Particle size

sample as obtained
from TEM
images
(nm)
Ge1 175.52
Ge2 98.15
Ge3 61.63
Ge4 43.25
Ge5 34.27
Ge6 22.44
 Taking into account the particles of all the samples as observed in the TEM images are
spherical in nature and the particle size as diameter the volume (V) of particles for each
samples have been calculated.
Considering the particle size of sample Ge1as initial form of the material, the
differences in volume (V) is calculated for the respective samples (Ge2-Ge5).
This allows to get the volume strain by taking the ratios of V and V (volume of the
sample Ge1) for the samples Ge2-Ge5.
The volume strains are plotted against the synthesis pressures as shown in following
figure
This plot is recognized as similar to well establish stress-strain plot.
After finding this plot, we deliberately go
for a synthesis at such pressure that is
well above the synthesis pressure of
sample Ge5
 It is observed that a single grain of the material bursts into several small fragments
The average grain size of the smaller grains are calculated with the previous-mentioned process
as used for the grain size calculations of sample Ge1-Ge5
One more Germanium oxide nano particle synthesis made at more higher synthesis pressure
( nearly 150 bar)

A huge change in grain size occurred and GeO2 grains of the order of 10 nm is obtained.
 PL spectra of Ge7

FTIR Spectrum of Ge7

 From PL Spectra

Peak at 427nm remains unchanged with the increase of excitation energy. This
indicates blue light emission due to the oxygen-vacancies and oxygen-germanium
vacancy centre [35-38]
Another peak is observed at 371 nm for the excitation wavelength 325nm, which
shifts towards smaller value of wavelength regions as the excitation wavelength
decreases. This phenomenon is being observed probably due to the Raman scattering
[33]

From FTIR Spectrum

A broad peak is observed at 556 cm-1 instead of three separate peaks in this
region as reported due to hexagonal structure of GeO2 [39-42]
This phenomenon is due to the very small particle sizes of the particles.
There is no peak observed at 880 cm-1. Therefore, the sample does not maintain
any layered structure as reported before [32]
 Current reaches at a peak value of 18.75mA at 0.03 volt
and decreases with the voltage and then shows the bulk
behaviour.
This phenomenon repeats as the polarity of the voltage
changes.
Presence of oxygen vacancy in the sample is responsible
for such incident.
An evidence of similar type of phenomenon in Cerium
Oxide (CeO2) has been observed [27].

In GeO2 molecule, Ge atom shares two electrons from 4p

band to oxygen 2p band. Due to oxygen vacancy, if an
oxygen atom leaves its lattice position an electron at 4p
band of Ge atom becomes unpaired, which increase the
possibility of electron hopping. Besides this, as proposed by
A.V. Shaposhnikov et.al. [31] oxygen vacancies remaining in
GeO2 is a type of defect and defects generate a disturbance
in the lattice periodicity through the crystal. Such irregularity
is responsible for the conducting path between the
electrodes [31]. Therefore, the carriers produced due to the
formation of oxygen vacancy conduct as the voltage is
applied. The number of carrier increases with the increasing
voltage and reaches at the peak value and subsequently the
number of carriers available for conduction drops.
Therefore, current is found negligible as comparable to the
bulk behaviour
Oxygen vacancy concentration calculation in sample
Ge7
Table -III

Mod of Consequent Energy Energy related to No of Oxygen

Peak voltage related to the peak of PL vacancy present
value of peak spectrum occurs in the sample
(Volt)
current due to oxygen
(Joule) (cm-3)
(Amp) vacancy (Joule)
0.01875 0.03 5.625 10-4 0.0465510-17 3.021016
 There are so many preoperational technique of GeO2 rod
like laser ablation, thermal oxidation, carbothermal reduction
etc.
Those methods needs high temperature to create sufficient
vapor pressure of either Ge or GeO2
It is also an established method that the shape of the nano
particles can be controlled in solvothermal technique by
changing the solvent [9].
The presence of organic solvent in the solvothermal process
creates mainly a mixture of sphere and rod like structure [10]
Procedure of Preparation

The preoperational technique is exactly same as the synthesis

process of nano particle as mentioned previously, except mixing of
4ml Acetone in 40 ml of water as used in hydrothermal process
The synthesis temperature is kept around 3600C
The sample characterized with

X-ray diffraction (Mini Flex2 X-ray powder diffractometer with Cuk

radiation, wave length-1.54)

High-resolution Transmission Electron Microscope (TECNEI20)

Scanning Electron Microscope with Energy Dispersive X-ray (Hitachi -

S3400N microscope)

Photo luminescence spectroscopy (Perkin Elmer Model: Lambda45)

SQUID magnetometer
 XRD pattern
as compared
with JCPDF
data confirms
that the
material is
GeO2 and
crystalline in
nature

XRD Pattern of GeO2 rods

 SEM image
infers that
the sample as
prepared is a
mixture of rod
like structure
and particle
form

SEM image of GeO2 rods

 Confirms that
sample is in
rod shape
length of the
rod is nearly
550 600 nm
Diameter of
the rod is
nearly 100 nm

HRTEM image of GeO2 rods

 EDX pattern of GeO2 rods

EDX spectrum as shown in figure confirms existence of germanium and

oxygen only inside the sample
 The PL spectrum obtained
for GeO2 rods at an excitation
wavelength 300 nm.
It shows an emission peak
around 420 nm (Position-a)
and at 450 nm (Position-b)
The 1st one is responsible
for presence of defects
including oxygen vacancy .
The second one is due to rod
shape particularly as observed
PL Spectrum of GeO2 rods by Z. Jiang et al.[8]
excitation energy 300nm
The most unusual property of the sample,
contradictory to the bulk or crystalline GeO2, is
the magnetization effect. Although the amount
of magnetization is not considerable at room
temperature but still a hysteresis curve is
obtained for the sample as placed within high
magnetic field.
Hysteresis curves of the sample at 295K and 2K respectively
 The figure shows that the area covered by the hysteresis loop is
greater at lower temperature for the sample, which is obvious.
Ferromagnetism due to oxygen vacancy in some oxides (viz.
SnO2, CeO2 especially in nano-order phase) is already reported
[14, 15].
Chang et al [14] illustrated that the sample (nano sized SnO2)
loses its ferromagnetic nature due to absence of Oxygen vacancy
as the material is annealed at 7000C in oxygen atmosphere.
From the study concerning the magnetic behaviour of such
samples, it is clear that oxygen vacancy plays an important role
for exhibiting the property of magnetization.
 Therefore briefly :
GeO2 rod is prepared by hydrothermal technique using a mixture of
water and acetone as solution.
XRD pattern shows the characteristic peaks of GeO2
The SEM and HRTEM images establish that the samples are rod
shaped
Length of produced GeO2 rods are of the order of a few micrometers
and the diameter is nearly 100 nm respectively
The PL spectroscopy reveals the existence of defects inside the
sample
A characteristic blue peak near 450 nm is also observed for such rod
shaped sample. Such peak produced at low energy region indicates the
increment of surface area due to formation of GeO2 rod (a part of the
internal energy is used for the increment of surface area).
The magnetic hysteresis curve as observed for the sample, both at
room temperature (295K) and at 2k are the first ever reported for GeO2
and this property is certainly due to the presence of oxygen-vacancy for
the rod shaped sample.
Work done till now
Synthesis of Germanium oxide nano particle by Hydrothermal technique
Different structural and optical characterization of the samples
Optimization of Hydrothermal synthesis temperature to produce extremely
small grain ( of the order of 10 nm) of GeO2 nanoparticle
Establishing the equivalency of elongation factor (e) and lattice distortion
(d/d) of the samples.
Novel synthesis of rod shaped GeO2 using a mixture of water and an
organic solvent (Acetone) as solution in Hydrothermal process
Characterizations of prepared GeO2 rod
 Publications:
1) Seal M., Mukherjee S., 2015, Approach for selection of a
synthesis procedure of GeO2 ultra-small nanoparticles and its
characterization, International Journal of Phys., 3, (3), pp 133-
138.
2) Seal M., Mukherjee S. Simplified Synthesis Procedure of GeO2
NANO-ROD and its Characterization , Advances in Engineering
Applications, 4(2015) 1-4
3) Accepted in Nanomaterials Today
Fwd: Your Manuscript ID: ICFNM 2016 SC45 has been accepted
Inbox
x
Sampad Mukherjee
Dec 9
to me
---------- Forwarded message ----------
From: Arijit Sinha <sinharijit@gmail.com>
Date: Tue, Dec 6, 2016 at 9:07 PM
Subject: Your Manuscript ID: ICFNM 2016 SC45 has been accepted
To: Sampad Mukherjee <smukherjee.besu@gmail.com>
Cc: Amitava Basu Mallick <icfnm2016@gmail.com>, Mallar Ray <mallar.r@gmail.com>

Ref: Manuscript ID: ICFNM 2016 SC45

Title: Determination of hydrothermal synthesis pressure of crystalline GeO2 nano particle of the order of 10 nm through a Central Force Potential model

Publication: Materials Today: PROCEEDINGS, Elsevier

Dear Dr. Mukherjee,

I am pleased to inform you that your paper has been accepted for publication. The reviewer(s) comments are appended as below.
Reviewer: The revised manuscript with above mentioned number now may be accepted for publication.
Thank you for submitting your work in Materials Today:PROCEEDINGS.

Sincerely,
Arijit Sinha

--
Dr. Arijit Sinha
Assistant Professor
Dr.M.N.Dastur School of Materials Science and Engineering
Indian Institute of Engineering Science and Technology, Shibpur, Howrah-711103, India.
Work yet to be done
Preparation and characterization of Polymer composite
(PVDF) of GeO2 nano-rod and its different characterization
[ It should be mentioned that the synthesis part is almost done]
Study of photo catalytic behavior of GeO2 nanoparticle.
References:

[1] G.S Smith and P.B Isaacs: The crystal structure of quartz-like GeO2. Acta. Cryst. 17, 842(1964).
[2] W.H. Baur and A.A Khan: Rutile-type compounds. IV. SiO2, GeO2 and a comparison with other rutile-type structure.
Acta Crist.B.27, 2133 (1971).
[3] W.H. Zachariasen: XIII. Uber die Kristallstruktur der wasserl?chen Modifikation des Germaniumdioxyd. Zeitschrift
fur Kristallographie, 67, 226 (1928).
[4] B.E. Warren: The diffraction of X-rays in glass. Phys. Rev.45, 657 (1934).
[5] B.E Warren: X-ray determination of the structure of glass. J. Am. Ceram. Soc. 17, 249 (1934).
[6] J. Zarzycki: Study glass network by X-ray diffraction to high temperatures, Congres International du Verre (Paris)
p. 323330, 1956.
[7] J. Zarzycki: Sur langle de la liaison si-o-si de la silice vitreuse et celui de la liaison ge-o-ge de loxyde de
germanium vitreux ou liquide. Verres et Refractaires 11, 3 (1957).
[8] R.D. Oeffner and S.R. Elliott: Interatomic potential for germanium dioxide empirically fitted to an ab initio surface.
Phys. Rev. B, 58, 14791 (1998).
[9] T. Tsuchiya T. Yamanaka M. Matsui, Molecular dynamics study of pressure-induced transformation of quartz-
type GeO2, Phys Chem Minerals 27, 149 (2000).
[10] B. Bridge and N. D. Patel: Ultrasonic relaxation studies of the vitreous system Mo-P-O in the temperature range 4
to 300K, J. Mater. Sc. 21, 3783 (1986).
[11] T. Ekstrom, C. Chatfield, W. Wruss and M. Mally-Schreiber: The use of X-ray diffraction peak-broadening analysis
to characterize ground Al2O3 powders, J. Mater. Sc. 20 1266 (1985).
[12] M. Seal and S. Mukherjee: Approach for Selection of a Synthesis Procedure of GeO 2Ultra-small Nano Particles
and Its Characterization, Int. J. Phys. 3, 133 (2015).
[13] A. J. Leadbetter and A. C. Wright: Diffraction studies of glass structure. II. The structure of vitreous germania, J.
Non-Cryst. Solids 7, 37(1972).
[14] E. Ghobadi and J. A. Capobianco, Crystal properties of -quartz type GeO2, Phys. Chem. Chem. Phys. 2, 5761
(2000).
[15] J.P. Iti A. Polian, G. Calas, J. Petiau, A. Fontaine, and H. Tolentino, Phys. Rev. Lett. 63, 398 (1989).
[16] Yankov G, Dimowa L, Petrova N, Tarassov M , Dimitrova K, Petrova T, Shivachev B L, Synthesis, structural and
non linear properties of TeO2-GeO2-LiO2 Glasses, Opt. Mater., 35(2). 248-251. Dec 2012.
[17] Hermet P, Fraysse G, Lignie A, Armand P, Papet P, Density functional theory predictions of the nonlinear optical
properties in -quartz Germanium oxide, J. Phys. Chem. C , 116. 8692-8698. Mar 2012.
[18] Iti J P, Polian A, Calas G, Petiau J, Fontaine A, Tolentino H , Pressure induced coordination changes in crystalline
and vitreous GeO2, Phys. Rev. Lett. , 63. 398-401. July1989.
[19] Pei L Z, Zhao H S, Tan W, Yu H Y, Chen Y W , Fan C G, Zhang Q F , Smoot Germanium nanowires prepared by a
hydrothermal deposition process, Mater. Charact. , 60(11). 1400-1405. Nov 2009.
[20] Chang T C, Yan S T, Chsu C H, Tang M T, Lee J F, Tai Y H, Liu P T, Sze S M , A distributed charge storage with
GeO2 nanodots, Appl. Phys. Lett. , 84 (14) 2581-2583. April 2004.
[21] Yang J J, Pickett M D, Li X M, Ohlberg D A A, Stewart D R, Williams R S , Memristive switching mechanism for
metal/oxide/metal nanodevices, Nature Nanotech., 3 429-433. June 2008.
[22] Fors R, Khartsev S I, Grishin A M, Giant resistance switching in metal-insulator-manganite junctions: Evidence for
Mott transition, Phys. Rev. B , 71. 045305-045314. 2005.
[23] Sawa A, Fujii T, Kawasaki M, Tokura Y, Hysteretic current-voltage characteristics and resistance switching at a
rectifying Ti/Pr0.7Ca0.3MnO3 interface, Appl.Phys.Lett., 85. 4073-4075. Nov 2004.
[24] Fujii T, Kawasaki M, Sawa A, Akoh H, Kawazoe Y, Tokura Y, Hysteretic current-voltage characteristic and
resistance switching at an epitaxial oxide Schottky junction SrRuO3/SrTi0.99Nb0.01O3, Appl. Phys. Lett., 86. 012107-1 -3.
2005.
[25] Rozenberg M J, Inoue I H, Sanchez M J, Nonvolatile memory with multilevel switching: A Basic Model, Phys. Rev.
Lett., 92. 178302-14. 2004.
[26] Jooss C, Wu L B, Etz T, Klie R F, Beleggia M, Schofield M A, Schramm S, Hoffmann J, Zhu Y P , Polaron melting
and ordering as key mechanism for colossal resistance effects in manganites in Proceedings of the Natl. Acad. Sci.
U.S.A., 13597-13602.
[27] Baikalov A, Wang Y Q, Shen B, Tsui S, Sun Y Y, Xue Y Y, Chu C W, Field-driven hysteretic and reversible resistive
switch at the Ag-Pr0.7Ca0.3MnO3 interface , Appl. Phys. Lett., 83. 957-959. 2003.
[28] Nian Y B, Strozier J, Wu N J, Chen X, Ignatiev A , Evidence for an Oxygen diffusion model for the electric pulse
induced resistance change effect in transition-metal oxide, Phys. Rev. Lett., 98. 146403-1 - 4. 2007.
[29 ]Gao P, Wang Z, Fu W, Liao Z, Liu K, Wang W, Bai X , Wang E , In situ TEM studies of Oxygen vacancy migration
for electrically induced resistance change effect in Cerium Oxide, Micron , 41(4). 301-305. June 2010.
[30] Giberti A, Malagu C, Currentvoltage characteristics of nanostructured SnO2 films, Thin Solid Films, 548. 683-688.
Dec 2013.
[31] Peng Z , Chen Y, Chen Q, Li N, Zhao X, Kou C, Xiao D, Zhu J, Correlation between lattice distortion and electrical
properties on Bi4Ti3O12 ceramics with W/Ni modifications, J. Alloys Compd., 590. 210-214. March 2014.
[31] Shaposhnikov A V, Perevalov T V, Gritsenko V A, Cheng C H, Chin A, Mechanism of GeO2 resistive switching
based on the multi-phonon assisted tunneling between traps, Appl. Phys. Lett. , 100. 243506-1 4. 2012.
[32] Dey S N, Chatterjee P, Sengupta S P, Dislocation induced line-broadening in cold-worked Pb-Bi binary
alloy system in the -phase using X-ray powder profile analysis , Acta. Mater. , 51 (16). 4669-4677. Sept
2003.
[33] Bose N, Basu M & Mukherjee S, Study of optical properties of GeO2 nanaocrystals as synthesized by
hydrothermal technique, Mater. Res. Bull., 47 (6) 1368-1373. June 2012.
[34] Kim H W , Lee J W, Kebede M A, Kim H S, Lee C , Catalyst-free synthesis of GeO2 nanowires using the
thermal heating of Ge powders, Curr. Appl. Phys., 9 (6). 1300-1303. Nov 2009.
[35] Ramana C V, Franco G C, Vemuria R S, Troitskaiac I B, Gromilovd S A, Atuchin V V , Optical properties
and thermal stability of germanium oxide (GeO2) nanocrystals with -quartz structure Mater. Sci. Eng. B, 174
(1-3). 279-284. Oct 2010.
[36] Kim H W, Lee J W, GeO2 nanostructures fabricated by heating of Ge powders: Pt-catalyzed growth,
structure, and photoluminescence, Physica E, 40 (7). 2499-2503. May 2008.
[37] Wu X C, Song W H, Sun Y P, Du J J , Preparation and photoluminescence properties of crystalline
GeO2 nanowires, Chem. Phys. Lett., 349 (3-4). 210-214. Nov 2001.
[38] Vassileva M S, Tzenov N, Malinovs D D, Rosenbauer M, Stutzmann M, Josepovits K V, Structural and
luminescence studies of stain-etched and electrochemically etched germanium, Thin Solid Films, 255 (1-2).
282-285. Jan 1995.
[39] Lucovsky G, Chao S S, Yang J, Tyler J E, Czubatyj W , Differences between the bonding of oxygen in
glow discharge deposited a-Si:H and a-Ge:H, J.Non-Cryst. Solids, 66 (1-2). 99-104. July 1984.
[40] Gross T M, Tomozawa M , Fictive temperature of GeO2 glass: Its determination by IR method and its
effects on density and refractive index, J.Non-Cryst. Solids , 353 (52-54). 4762-4766. Dec 2007.
[41] Viswanathmurthi P, Bhattaraj N, Kim H Y, Khil M S, Lee D R , Suh E K , GeO2 fibers: Preparation,
morphology and photoluminescence property, J. Chem. Phys., 121. 441- 445. 2004.
[42] Clauws P, Oxygen related defects in germanium, Mat. Sc. Engg. B, 36 (1-3). 213-220. Jan 1996.
[43] Waser R, Dittmann R, Staikov G, Szot K, Redox-Based Resistive Switching Memories Nanoionic
Mechanisms, Prospects, and Challenges, Adv. Mater., 21 (25-26). 2632-2663. July 2009.
[44] Chen J, Yang D, Li H, Ma X, Tian D, Li L, Que D, Crystal-originated particles in germanium-doped
Czochralski silicon crystal, J. Cryst. Growth , 306 (2) 262-268. Aug 2007.
[45] Dang H. Y., Wang J., and Fan S. S., 2003, The synthesis of metal oxide nanowires by directly heating metal samples
in appropriate oxygen atmospheres, Nanotechnology,14, ( 7), pp 738-741.
[46] Zhang Y., Zhu J., Zhang Q., Yan Y., Wang N., Zhang X., 2000, Synthesis of GeO2 nanorods by carbon nanotubes
template, Chem. Phys. Lett., 317, (3-5), pp 504-509.
[47] Tang Y. H., Zhang Y. F., Wang N., Bello I., Lee C. S., Lee S. T., 1999, Germanium dioxide whiskers synthesized by
laser ablation, Appl. Phys. Lett., 74, pp 3824-3826.
[48] Wu C. I., Hogan T. P., 2006, Growth of GeO2 nanowires by thermal annealing, Mater. Res. Soc. Symp. Proc., 940.
[49] Wu X. C., Song W. H., Zhao B., Sun Y. P., Du J. J., 2001, Preparation and photoluminescence properties of crystalline
GeO2 nanowires, Chem. Phys. Lett., 349, (3-4), pp 210-214.
[50] Wagner R. S., Ellis W. C., 1964, Vapor-liquid-solid mechanism of single crystal growth, Appl. Phys. Lett., 4, pp 89.
[51] Khan M. A. , Farhan M. F., Hogan T. P., 2009, Low temperature synthesis of germanium oxide nanowires by thermal
evaporation of germanium in an oxidizing environment , IEEE NM DC.
[52] Jiang Z., Xie T., Wang G.Z., Yuan X.Y., Ye C.H., Cai W.P., Meng G.W., Li G.H., Zhang L.D., 2005, GeO2 nanotubes
and nanorods synthesized by vapor phase reactions, Mater. Lett., 59, (4), pp 416- 419.
[53] Khoza P.B., Moloto M. J., Sikhwivilu L. M ., 2012, The effect of solvents, acetone, water and ethanol on the
morphological and optical properties of ZnO nanoparticles prepared by microwave, Journal of Nanotechnology, 2012,
article Id. 195106.
[54] Xu L., Hu Y. L., Pelligra C., Chen C. H., Jin L., Huang H., Sithambaram S., Aindow M., Joesten R., Suib S.L., 2009,
ZnO with different morphologies synthesized by solvothermal methods for enhanced photo catalytic activity, Chem. Mater.,
21, (13), pp 28752885.
[55] Seal M., Mukherjee S., 2015, Approach for selection of a synthesis procedure of GeO 2 ultra-small nanoparticles and its
characterization, International Journal of Phys., 3, (3), pp 133-138.
[56] Kim H.W., Lee J.W., Kebede M.A., Kim H.S., Lee C., 2009, Catalyst-free synthesis of GeO2 nanowires using the
thermal heating of Ge powders, Curr. Appl. Phys., 9, (6), pp 1300-1303.
[57] Chang G. S., Forrest J., Z. Kurmaev E., Morozovska A. N., Glinchuk M. D., McLeod J. A., Moewes A., Surkova T. P.,
[58] Hong N. H., 2012, Oxygen -vacancy induced ferromagnetism in undoped SnO2 thin films, Phys. Rev. B., 85, pp
165319.
[59] Han X., Lee J., Yoo H. I., 2009, Oxygen-vacancy-induced ferromagnetism in CeO2 from first principles, Phys. Rev. B.,
79, pp 100403.
[60] Shah L. R., Ali B., Zhu H.,. Wang W. G, Song Y. Q., Zhang H. W., Shah S. I., Xiao J. Q., 2009, Detailed study on the
role of oxygen vacancies in structural, magnetic and transport behaviour of magnetic insulator: CoCeO2, J. Phys.
Condens. Matter, 21, (48), pp 486004.
[61]Pan X., Yang M. Q., Fu X., Zhang N., Xu Y. J., 2013, Defective TiO2 with oxygen vacancies: synthesis, properties
and photo catalytic applications, Nanoscale, 5, ( 9), pp 3601-3614.
Thank You