Department of Physics & Astrophysics

University of Delhi

Semester - III
M.Sc.Physics (F) (2022-2024)
Nanomaterials-I Lab (PH-EL512)

Experiment – I: To synthesize different samples of ZnO nanoparticle

by sol gel method and to study its XRD pattern.

Submitted by:
Gunjan, Samarth, Anchal and Jeptha
Aim: To synthesize different samples of ZnO nanoparticles by sol gel
method and to study its XRD pattern.

Apparatus Required:
Beakers, Spatula, Magnetic Stirrer, Ceramic Plates, Magnetic bead, Centrifuge
and Centrifuge tubes, mortar pestle, tubler furnace, weighing machine, oven and
tubes.

Chemicals Required:
Zinc acetate dihydrate (powdered), Sodium hydroxide pellets, Ethanol, Acetone,
distilled water.

Equations used:

Theory:
Bottom-up and top-down approaches are two fundamental strategies in
nanotechnology for creating and manipulating nanoscale structures and
materials:
1. Bottom-Up Approach:
 In the bottom-up approach, nanoscale structures and materials are built
from the ground up, starting with individual atoms or molecules.
 This approach relies on self-assembly and chemical synthesis techniques
to construct nanoscale structures. Examples include molecular self-
assembly and chemical vapor deposition.
 Bottom-up methods are often used to create nanomaterials with unique
properties and structures, such as nanoparticles, nanowires, and quantum
dots.
 They are particularly suitable for designing materials with precise control
over their properties at the nanoscale.
2. Top-Down Approach:
 In the top-down approach, larger structures or materials are reduced in
size to the nanoscale through various techniques and processes.
 This approach involves cutting, carving, or etching larger materials to
achieve nanoscale features. Examples include photolithography and
mechanical milling.
 Top-down methods are often used in semiconductor manufacturing and
other industries to create nanoscale features on surfaces.
 They are useful for scaling down existing technologies and devices
to the nanoscale.
The sol-gel method is considered a bottom-up approach in nanotechnology and
materials science. In this method, materials are built from small building blocks
(such as molecules or nanoparticles) and are assembled into a larger, more
complex structure. It starts with a solution or sol and allows the formation of a
three-dimensional network or gel.
Sol: In the sol-gel method for nanoparticle synthesis, a "sol" is a
colloidal dispersion, where solid nanoparticles are uniformly suspended within a
liquid medium. This dispersion is characterized by its homogeneity, stability,
and the precise control it offers over both the size and chemical composition of
the nanoparticles. This level of control is crucial in tailoring the properties of
the resulting nanoparticles for specific applications, making the sol-gel method
a versatile and valuable technique in materials science and nanotechnology. This
sol serves as the initial stage in the creation of advanced materials, and its
properties play a fundamental role in determining the characteristics of the final
nanoparticle product, ranging from electronics and catalysis to biomedical
research. In this experiment, we prepared the sol of Zinc Oxide using zinc
acetate dihydrate as the precursor.

Gel: A "gel" is a three-dimensional, continuous network structure that

forms when a sol, the colloidal dispersion of solid nanoparticles in a liquid,
undergoes a controlled gelation process. This gelation transforms the liquid sol
into a semi-solid or gel state. The gel structure is characterized by a porous and
interconnected framework of solid particles, which can entrap the nanoparticles,
effectively locking them into position. The resulting gel provides a stable and
moldable matrix for further processing and can be used as a precursor for the
synthesis of advanced materials, including nanoparticles, thin films, and gels,
with tailored properties. The gelation process is a critical step in the sol-gel
method, as it determines the final structure and properties of the materials being
produced.

Sol-gel method: The sol-gel method is a versatile and widely used

technique in materials science for creating various advanced materials,
including nanoparticles, thin films, and gels. It involves the transformation of a
sol, a colloidal dispersion of solid particles in a liquid, into a gel, a three-
dimensional network structure. Here are the basic steps involved in the sol-gel
process:
1. Sol Preparation: The process begins with the careful preparation of the
sol. Solid nanoparticles are uniformly dispersed in a liquid medium. The
choice of solvent and precursor materials determines the chemical
composition and properties of the nanoparticles to be synthesized. As
discussed above, our precursor is zinc acetate dihydrate and the solvent is
NaOH.

2. Gelation: Controlled gelation is the crucial next step. This involves

inducing a transition from the liquid sol to a semi-solid or gel state.
Various methods can be used to initiate gelation, such as adjusting
temperature, pH, or adding a gelling agent. We mixed the solutions of the
precursor and the solvent on a magnetic stirrer drop wise, which resulted
in the formation of a white precipitate.

3. Aging: The gel is allowed to age or mature for a period of time. During
this stage, the gel structure continues to develop and solidify, leading to
changes in its properties.

4. Drying: The gel is carefully dried to remove the liquid component,

leaving behind a porous, three-dimensional network of solid particles.
The drying process can be performed through techniques like air drying,
supercritical fluid extraction, or freeze drying. We put the solution in an
oven for 2 hours at 90 degree Celsius.

5. Thermal Treatment: Depending on the desired properties, the resulting

dried material may undergo thermal treatment or annealing. This step
 helps to further solidify the structure and may induce changes in
crystallinity or other material characteristics. Here, our samples were put
through calcinations at different temperatures in a tubler furnace.

6. Final Processing: The material in its final form is often obtained after
additional processing steps. For nanoparticle synthesis, this may involve
grinding, milling, or other techniques to achieve the desired particle size
and morphology. We grinded our samples to get them in their powdered
form.

XRD:
XRD Diffraction: To study and characterize the crystalline structure of a
material, a powerful non-destructive technique of X-Ray diffraction is used.
XRD peaks are produced by constructive interference of a monochromatic beam
of X-ray scattered at specific angles from each set of lattice plane in a sample.
The peak intensities are determined by the atomic positions within the lattice
planes. Consequently, the XRD pattern is the fingerprint of periodic atomic
arrangements in each material. The XRD analysis is done with an X-ray source
of Cu kα radiation (λ=1.5405Å). The standard database (JCPDS database) for
XRD pattern is used for hkl in identification for a large variety of
crystalline structures.

X-Ray Diffractometer: A diffractometer is a measuring instrument for

analysing the structure of a material from the scattering pattern produced when
a beam of radiation of particles (such as X-rays or neutrons) interacts with it. X-
ray diffractometers consist of a source of radiation, a monochromator to choose
the wavelength, slits to adjust the shape of the beam, a sample and a detector.
 Source- X-rays are generated both by deceleration of electrons in target
material and inelastic excitation of core electrons in the atoms of the
material. The first process gives a broad spectrum and the second one
gives a sharp line. When electrons hit the copper target the radiations
show a strong line (the kα1 line) at 1.541Å; a molybdenum target has its
kα1 line at 0.709Å.
Procedure:
1. Take 7g of zinc acetate dihydrate in a beaker filled with 100ml of distilled
water. Stir on the magnetic stirrer for 30 mins at room temperature
(40°C).
2. In another beaker take 2g of NaOH pellets and fill it with 100 ml of
distilled water. Stir on the magnetic stirrer for 30 mins at room
temperature (40°C).
3. Add the NaOH solution to the zinc acetate solution drop by drop at 760
rpm and stir it rigorously on the magnetic stirrer at room temperature for
30 mins. A white precipitate is formed after 30 mins
4. Put the solution in an oven for 2 hours at 90°C for drying.
5. Divide the sample in four parts.
6. Centrifuge each part separately and wash it with 30ml distilled water in
20ml ethanol solution. Repeat it 4-5 times for 20mins per wash. The rate
of the centrifuge was set at 1500 rpm.
7. Sample 1 was calcined at 300°C for two hours. Sample 2, sample 3 and
sample 4 were calcined for 400°C, 500°C and 600°C respectively for
three hours.
8. All the calcined samples were separately grinded in mortar pestle to form
a powder.
9. The XRD data was obtained for all the samples.
Observations and Calculations
1)

X FWHM( ) (rad) (rad) ln(1/cos( )) ln( ) hkl D (nm)

31.79673 0.23004 0.004015 0.277479 0.039002 -5.51773 100 35.8939
34.44762 0.22231 0.00388 0.300612 0.045881 -5.55191 002 37.39838
36.28248 0.23444 0.004092 0.316624 0.050986 -5.49878 101 35.64488
47.5753 0.25546 0.004459 0.415173 0.08878 -5.41292 102 33.97189
56.63436 0.28305 0.00494 0.494228 0.127453 -5.31036 110 31.86946
62.89604 0.31139 0.005435 0.548871 0.158862 -5.21494 103 29.89332
66.4197 0.32127 0.005607 0.579621 0.178325 -5.1837 200 29.54346
67.99046 0.32564 0.005683 0.593329 0.187434 -5.17019 112 29.41369
69.12391 0.33193 0.005793 0.60322 0.194176 -5.15106 201 29.05151
72.60037 0.27729 0.00484 0.633558 0.215763 -5.33092 004 35.535
76.99721 0.32544 0.00568 0.671927 0.245104 -5.1708 202 31.179

y = 2.532x - 5.6359
400oC R² = 0.9907
-5.1
0 0.05 0.1 0.15 0.2 0.25
-5.15
-5.2
-5.25
-5.3
LN(FWHM)

-5.35
-5.4
-5.45
-5.5
-5.55
-5.6
LN(1/COS(THETA))
Determination of D using modified Debye Scherrer Formula:

Thus from the data

Lattice parameters a and c :

 For plane (1 0 0)
We know that the Bragg’s law is

Calculating from this

We use the formula

And we get
  For plane (0 0 2)

We use the formula

And we get

2)

FWHM
X value (rad) (rad) ln(1/cos( )) ln( ) D (nm) hkl
( )
31.97106 0.2259 0.0039427 0.27900013 0.0394362 -5.53588982 36.56760855 100
34.61816 0.23296 0.00406592 0.30210044 0.0463438 -5.50511548 35.70519163 002
36.45069 0.2437 0.00425337 0.31809228 0.0514683 -5.46004428 34.30699785 101
47.74173 0.26874 0.0046904 0.41662519 0.0894217 -5.36223788 32.31386502 102
56.79662 0.3162 0.00551873 0.49564401 0.1282169 -5.19960732 28.55011544 110
63.05665 0.33737 0.00588822 0.55027308 0.1597208 -5.13480199 27.61501326 103
66.5734 0.33117 0.00578001 0.58096251 0.1792047 -5.15335041 28.68550357 200
68.14519 0.35545 0.00620377 0.59467897 0.1883456 -5.08259765 26.97148096 112
69.27799 0.36047 0.00629139 0.60456451 0.1951032 -5.06857351 26.77620344 201
72.74951 0.24386 0.00425616 0.63485924 0.2167202 -5.45938795 40.44508006 004
77.13746 0.31579 0.00551158 0.67315133 0.2460785 -5.20090481 32.16310908 202

y = 2.8887x - 5.6238
500°C R² = 0.9748

-5
0 0.05 0.1 0.15 0.2 0.25
-5.1

-5.2
LN (FWHM)

-5.3

-5.4

-5.5

-5.6
LN(1/COS(THETA))
Determination of D using modified Debye Scherrer Formula :

Thus from the data

Lattice parameters a and c :

 For plane (1 0 0)
We know that the Bragg’s law is

Calculating from this

We use the formula

And we get
  For plane (0 0 2)

We use the formula

And we get

3)

X FWHM( ) (rad) (rad) ln(1/cos( )) ln( ) hkl D (nm)

34.46153 0.34099 0.0059514 0.30073358 0.045918874 -5.12413 100 24.38297
31.80616 0.33518 0.00584999 0.27756111 0.039025088 -5.14131 002 24.6352
36.2922 0.37018 0.00646086 0.31670919 0.051013907 -5.04199 101 22.57501
47.5923 0.41145 0.00718116 0.41532117 0.08884566 -4.93629 102 21.09376
56.65266 0.43447 0.00758293 0.49438772 0.127538647 -4.88186 110 20.76421
62.92252 0.50879 0.00888006 0.54910257 0.159003643 -4.72395 103 18.29792
66.44681 0.4703 0.00820828 0.57985781 0.178480263 -4.80261 200 20.18477
68.01738 0.54338 0.00948377 0.59356361 0.187592121 -4.65817 112 17.63001
69.12771 0.58171 0.01015275 0.60325307 0.194198495 -4.59001 201 16.57749
72.64941 0.31248 0.0054538 0.6339857 0.216077399 -5.21144 004 31.54314
77.02685 0.38701 0.0067546 0.67218607 0.24530957 -4.99753 202 26.22408

600°C y = 3.0239x - 5.2379

R² = 0.9357
-4.5
0 0.05 0.1 0.15 0.2 0.25
-4.6

-4.7
LN(FWHM)

-4.8

-4.9

-5

-5.1

-5.2
LN(1/COS (THETA))
Determination of D using modified Debye Scherrer Formula :

Thus from the data

Lattice parameters a and c :

 For plane (1 0 0)
We know that the Bragg’s law is

Calculating from this

We use the formula

 And we get

 For plane (0 0 2)

We use the formula

And we get

Result:
a c c/a Relative error
JCPDS value 3.205 5.122 1.598 -
Sample 2 3.246 5.202 1.602 ±0.004
Sample 3 3.229 5.177 1.603 ±0.005
Sample 4 3.002 5.622 1.873 ±0.275

1. Sample 1 was not calcined properly and turned into gel while grinding.
2. ZnO nano particles of crystalline size, D= 38.86 nm were obtained from
sample 2.
3. ZnO nano particles of crystalline size, D= 38.39 nm were obtained from
sample 3.
4. ZnO nano-particles of crystalline size, D= 26.10 nm were obtained from
sample 4.

Discussion:
During the grinding of sample 1, it turned back to its previous gel form. Low
temperature and less time for calcination could be the possible reasons for this.
So, the calcination time and temperature for the other three samples were taken
care of. We increased both these parameters and thus obtained better results as
evident from the XRD analysis. We also made sure that every beaker, tube etc.
was cleaned properly with soap and acetone before and after usage. We used
Origin software to analyse the data obtained from the X-ray diffractometer. The
graphs were then compared with the standard peaks.
References:
1. J.N. Hasnidawani, H.N. Azlina, H. Norita, N.N. Bonnia, S. Ratim, E.S.
Ali.
Synthesis of ZnO Nanostructures Using Sol-Gel Method.
Procedia Chemistry, Volume 19, 2016, Pages 211-216
https://iopscience.iop.org/article/10.1088/1757-899X/1219/1/012019/pdf
2. Vignesh K, Anju S Nair, C. Udhayakeerthana & T..Kalaivani
Synthesis and characterization of ZnO nanoparticles using sol-gel method
and their antibacterial study.
K Vignesh et al 2022 IOP Conf. Ser.: Mater. Sci. Eng. 1219 012019
https://www.sciencedirect.com/science/article/pii/S1876619616001418