Nanomaterials deposition

techniques

Deposition

of thin films from solution

 Learning Outcomes
 LO1: To have a scientific understanding of processing/deposition techniques,
such as: electroplating, evaporation, sputtering, chemical vapor deposition.
 LO2: Ability to apply the knowledge and practical skills in the analysis and
solution of mechanical engineering problems.
 LO3: An in-depth understanding of the ranges of properties and
characteristics exhibited by the materials.
 LO4: To equip the students with skills necessary to carry out research in
advanced and emerging materials
 LO5: Have an in-depth understanding of the principles and a knowledge of
the capabilities of the different types of analysis covered in the module.
Nanomaterials - deposition methods
Outline - Solution process

1. Spin coating

2. Dip coating

3. Electrochemical deposition

4. Ink-jet printing

Langmuir Blodgett; Spray coating ; Screen printing

Sci. Technol. Adv. Mater. 14 (2013) 023001 (23pp)
 Solution process
Source Material is in the solution/liquid form

Steps:
1. Materials is applied to the substrate
2. The solvent evaporates
3. Solid state thin films remain on the substrate

Objectives:
1. Uniform
2. Defect-free film over the entered substrate
3. Adherent
Spin coating process A process of making thin films
from solution facilitated by a fast rotation of the substrate.

Four main processing steps: http://www.intechopen.com/books/solar-cells-new-approaches-and-reviews/inorganic-organic-perovskite-

solar-cells

https://nanoequipment.wordpress.com/2011/03/08/spin-
Step 1: Applying solution - Solution is disperse onto substrate . coater/

Step 2: Spin-up - Accelerate wafer to final speed.

Step 3: Spinning at constant speed – stable fluid out - flow dominated. The film forming process is driven by the viscosity of
the fluid and spin speed at which the wafer is spinning and time of spinning
Step 4: Evaporation dominated/drying - Solvent is evaporated from the film – thin film formation . 
 
Process theory behind spin coating

Physical system: Viscous fluid on a rotating disk

1. Spread of liquid across the substrate –

 rotational velocity (Spin speed) affects the force (circular motion) responsible
for the spread of liquid across the substrate
2. Drying/ change in viscosity / evaporation of the solvent
Viscous force determined by solution viscosity (molecular weight/concentration)
There is a balance between the force applied to shear the solution towards
the edge of the substrate and the drying rate which affects the viscosity of the
fluid.
As the fluid dries via solvent evaporation, the viscosity increases until the radial
force of the spin process can no longer appreciably move the solution over the
surface.
http://www.cise.columbia.edu/clean/process/spintheory.pdf
Thin Film thickness
Film Thickness is proportional to
1. the inverse of the spin speed
In which:
h: thickness
ω:angular speed
2. Polymer concentration n constant (n=1/2)

C is the polymer concentration

3. Molecular weight (intrinsic viscosity) The thickness vs. spin speed of spin coated film

η viscosity Thickness of a film depends by

1. Spin speed
𝐾 𝐶𝛼 𝜂 𝛽 2. Viscosity via polymer
h 𝑛 concentration/molecular weight
𝜔
3. Solvent volatility
Dip coating process
Dip coating techniques can be described as a process where the substrate is immersed in a solution and then
withdrawn from it at a controlled speed.

1. Immersion /dipping of substrate vertically in the coating solution.

2. Wet film formation
Start-up & Deposition/drainage Depending on the speed the substrate is
raised, film thickness can be controlled based on the relationship between the
withdrawn speed, solution viscosity and gravity causing adhered liquid to fall.
3. Solvent Evaporation A uniformly thin film is formed after eliminating excess
solution from the substrate by drying it. http://www.dip-coater.com/english/about_dip_coating.html
Thin Film thickness
Thin thickness is mainly defined by:
1. the withdrawal speed
2. solution viscosity
3. solution concentration/density
4. Liquid – vapour surface tension

If the withdrawal speed is chosen such that the shear rates keep the system
in the Newtonian regime, the coating thickness can be calculated by
the Landau-Levich equation.

Using: h = coating thickness, η = viscosity, v = dragging speed,

γLV = liquid-vapour surface tension, ρ = density and g = gravity.
 Electrochemical deposition

Electrodeposition (electroplating) is a process in which a

source material is removed from a chemical solution and
deposited onto a charged substrate.

Zn plating
Electrochemical process – what you need ?
Electrolyte or bath – a conductive solution
(aqueous solution of metal salt MA) containing
the metal you want to coat.

Cathode must be the substrate/object that you

want to cover (connected to the negative
terminal of the power supply)

Anode must the source material you are using to

deposit (connected to the positive terminal of
the power supply)

Power supply/battery
http://www.dynamicscience.com.au/tester/solutions1/chemistry/redox/Electrolysis1.htm
 Electrochemical process – how it works?
Cathode (-ve electrode)
Anode (+ve electrode)
Battery Ag+(aq) + e− ⟶ Ag(s)
Ag(s) ⟶ Ag (aq) + e
+ −

Ag atoms LOSING Ag+ ions GAINING

electrons to become ions electrons to become
Ag+ is called atoms is called
OXIDATION ‘REDUCTION’

https://courses.lumenlearning.com/chemistryformajorsxmaster/chapter/
electrolysis/
https://www.youtube.com/watch?v=BZGDxL9pBC4

Oxidation Is Loss of electrons, Reduction Is Gain (OILRIG)

Thin Film thickness

M .I .t
x
 .A.z .F

The thickness of thin film depends on:

- the current (I)
- the time for which it passes (t)
- the exposed area of the cathode (A)
- a constant (M/ρzF) which depends on the metal and the electrolyte
 Ink jet printing

Inkjet is method of printing, by propelling tiny drops

of liquid ink onto substrate

 Creates an object through adding material(s)

 No further steps of material removal are needed

http://www.educatorstechnology.com/2013/03/importance-of-3d-printing-in-education.html
 Why Inkjet printing ?

Patterning capability – “digital” method

Mask less
 Efficient use of material - Reduction of waste material (spin
coating  Reduce waste materials & energy&
losses 95%)
High speed manufacturing
and low cost cost
fabrication
 An environmentally
Room temperature deposition friendly approach
& no vacuum required
The printing process is highly scalable and suitable from
small to large-area
Flexible substrate
Compatible with wide variety of materials from polymers to
metal particles
Why 3D printing/ Additive manufacturing ?

Esa Kunnari*, Jani Valkama, Marika Keskinen, Pauliina Mansikkama¨ ki, Journal of Cleaner Production 17 (2009) 791–799
Inkjet printing

Fused Deposition Modelling

http://openwetware.org/wiki/3D_Bioprinting
 Inkjet Printing
Novel Method for functional materials deposition

Steps in the printing process: Role /Control

IJP involves 1. Drop formation Printhead/formulation / ink

3 basic elements: Inkjet printer types:
 Thermal (bubble jet) (HP;
Canon)
 Piezoelectric (Epson; Xerox)

2. Drop ejection Printhead/formulation

3.Drops on substrate & wetting  Formulation/substrate
 Interfacial interactions
4. Film formation Competition between solvent
evaporation and spreading of the
ink
 Brookfield DV2T

Ink

From printing viewpoint the ink should ensure:

Liquid  Viscosity range (2-20)cP;
Functional
Carrier  Surface tension (30-40) mN/m;
material
solvent
 pH (4-9)
Ink
 Stability/aging
Humectant
Ethylene Surfactant  Visual examination:
glycol  Sedimentation
 Dispersion
Other  Homogeneity
additives
 Konica Minolta
KM512

Inkjet print-heads
Formation of droplets

Difficult to use with non-water

Thermal (bubble jet) based ink and heat sensitive
materials

Advantage: Compatible with most

Piezoelectric solvents
Disadvantage: more complex to
fabricate

http://supplies-outlet-blog.com/different-types-ink-printing-inkjet-printing/
 Optical tensiometer
Liquid-Solid Interfaces:
Wetting

Young's equation define the relationship between:

 contact angle θ, the 
 surface tension of the liquid σl,
  interfacial tension σsl between liquid and solid
 surface free energy σs of the solid

𝜎 𝑠 =𝜎 𝑠𝑙 +𝜎 𝑙 𝑐𝑜𝑠 𝜃

Figure1 Wetting behaviour of a drop

according to the contact angle
Michael L.Chabinyc; Injket printing in microelectronics
 Inks
Properties
The nanoparticles silver (AgNPs) ink PEDOT: PSS ink (Sigma
Small
(Drycure Ag-j) amount of Aldrich),
Particle Size 15~20nm alcohol 2wt% PEDOT: PSS
10wt% - Silver Particles reduces
98 wt% water & Ethylene
90wt% - Water & glycerol & the surface
tension glycol & alcohol
small amount of alcohol
Parameters / Ink NP Silver PEDOT:PSS
Dispersion Solution
Viscosity (cP)  6  14
Surface tension (mN/m)  35   30
pH  9  3
Functionalisation  sintering 120°C & 5 mins  drying 70°C & 3hrs
 Inks
Properties
Graphene oxide ink (Sigma Aldrich), Graphene ink
stabilized with (Cambridge graphene Ltd),
poly(sodium 4-styrenesulfonate) 0.2-0.5 g/L graphene
10 mg/ml GO ~0.1 wt.% solid content
Dispersion in water Dispersion in water
Torsion Balance Brookfield DV2T

3520-pH meter
 Inkjet print-heads
Formation of droplets

A commercial desktop inkjet A inkjet printer, ThallosJet

printer, Epson Stylus P5O, was Flatbed A3, was employed to
employed to deposit Ag and deposit Graphene and
PEDOT: PSS patterns. Graphene oxide patterns.
The Epson Stylus P5O is a
piezoelectric printer with the
printhead having:
 90 nozzles, 65 μm nozzle
diameter,
 1.5 pL drop size and 360 dpi
resolution.
 Nanoparticles silver ink
Liquid-Solid Interfaces:
Method: Sessile Drop shape analysis
Wetting

Figure_1: Contact angles

measured four Figure_2:
potential substrates. Contact angle versus time

Figure_3: Image of a ink droplet on ceramic coated paper

 Liquid-Solid Interfaces:
PEDOT:PSS ink Wetting

Figure_1: Contact angles Figure_2:

measured four Contact angle versus time
potential substrates.

Figure_3: Image of a ink droplet on ceramic coated paper

 Electronic Grade Paper Substrate

The inorganic coated paper NanoP60 substrate:

 ceramic coated (non-organic/plastic )
 has a pore size of 60nm that absorbs solvents and
preferentially leaves the nano-particles behind 1000μm
 can be heated to 1500 C (low temperature sintering)
with minimal discolouration.
 Promotes chemical interactions that enhance sintering
 Surface energy of 45 mN/m

Surface wetting occurs when the surface energy is able to

suitably overcome the surface tension of the liquid
Surface tension of Ag ink = 35mN/m
Surface tension of PEDOT:PSS = 30mN/m

Both Ag and PEDOT:PSS inks were compatible with the ceramic coated paper.
 Inkjet printing of silver ink– quality of the printed patterns
(a) (b) (c)
Figure_1: Optical
micrograph of inkjet
printed Ag pattern
100 μm 100 μm 100 μm
(a) 1 pass
(b) 2 passes
(d) (e) (f)
(c) 3 passes
(d)(e) 5 passes
(g)(h) SEM image of 5
passes (i) SEM cross
100 μm 100 μm 1000 μm
section image of Ag
printed pattern of 5
(g) Printed pattern (h) Printed pattern
(i) passes

Substrate Ag printed pattern Thickness @ 5 passes

Substrate
d = 1.1 and 1.8 μm
10 µm
(a) (b) (c)

Figure_1: Optical
micrograph of
inkjet printed
PEDOT:PSS
1000μm 100 μm 100 μm pattern
(a) paper only
(d) (e) (f) (b) One pass
(c ) 2 passes
(d) 3 passes
(e) 4 passes
(f) 5 passes

100 μm 100 μm 100 μm

Inkjet printing of Graphene & Graphene oxide inks– quality of
printed patterns

(a) & (b) graphene

ink
(c ) & (d) graphene
oxide ink
Inkjet printed silver (Ag) – mechanical properties
adhesion behaviour

1. adhesive force between ink

droplets/printed patterns and the substrate

2. cohesive force between printed patterns

Figure_1: Schematic diagram showing the types of the

forces involved in the substrate/printed patterns
 Inkjet printed silver (Ag) – adhesion behaviour
Adhesion tape test

Figure_1: Optical microscopic images of printed Ag patterns. – 5 layers (a) before (b) after
removing of adhesion tape (c) photograph of the Ag surface where the adhesive part of the tape has
been attached.
 Inkjet printed PEDOT:PSS patterns – adhesion behaviour

Figure_1: Optical microscopic images of PEDOT:PSS patterns. (a) 1 layer before (b) 1 layer after
removing of adhesion tape (c) 5 layers before (d) 5 layers after removing adhesive tape.
Multilayers Inkjet printing - Reaction between Ag/Ag & PEDOT/PEDOT
layers and Ag/PEDOT:PSS & PEDOT:PSS/Ag

Figure_2: Model for successive printing of layers

 Printing Multilayers

Multilayer printing – more

complicated fluid flow pattern
Control of non-uniformity in
thickness

Thickness ~ 0.3 µm

Surface and thickness

profiles of the printed
“Warwick” logo using PVOH
based inks
Multilayer printing – more complicated fluid flow pattern

liquid evaporating from the edge is replenished by liquid from the interior.
 Summary

Material is deposited on the

substrate in the solution/liquid form

1. Spin coating

2. Dip coating

3. Electrochemical deposition

4. Ink jet printing

Nanomaterials deposition methods