Deposition of solar energy material

by magnetron sputtering

ESL740 Non-conventional Sources of Energy

Bibhuti Bhusan Sahu

Department of Energy Science and Engineering, IIT Delhi

August 2023
 Outline
▪ Overview of transparent conductive oxide films

▪ Typical magnetron sources for thin film deposition

▪ New TCO film for flexible device

▪ Design of high conductivity TCO film by magnetron sputtering

▪ Results for ITO films by 3D source

▪ Summary

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 Overview of transparent conductive
oxide films

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 Transparent conductive oxide (TCO) applications
Flexible Device Touch panel
Solar cells

Smart window

Flat panel display TRANSPARENT CONDUCTIVE

OXIDE

Smart coatings
Transparent E-paper

Other display device

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 Overview of various conductive oxides (with film thickness 200 nm)
Hall mobility Bandgap Temperature
Materials Structure Resistivity (ohm-cm) Carrier concentration (cm-3)
(cm2/V-s) (eV) (°C)
In2O3 amorphous 51 3.75 3×10-4 4.1×1020 RT
Post
In2O3 polycrystalline 150 4×10-4 1×1020 annealing
200 C
SnO2 polycrystalline 20.77 3.9~4.6 4.5×10-3 8.9×1019 >150 C
4.5 ~ 8×10-4,
ITO amorphous 27−41 4.4 5×1020, 2.23×1021 RT
2.56×10-4
5.46×10-4,
ITO polycrystalline 16−53 4.3 7.13×1020, 5.03×1020 RT, 250 C
2.92×10-4
AZO polycrystalline ~10-30 3.5~3.8 5×10-4 1×1020 −1×1021 > 100 C
Single
GaZnO 15~66 3.28 1.69×10-3 4×1019 900 C
crystalline
InZnO amorphous 10~50 3.88~3.76 1×10-3~ 1×10-4 1×1021 RT
Post annealed
InZnO polycrystalline 15~40 1×10-3~ 3×10-4 4~6×1020
500 C
ZnO polycrystalline 20 3.07~3.17 15.6 2×1016 RT

TCO (ITO/AZO) films shows the application prospects for the industry due to their
comparable properties with respect to other conductive oxides
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 Overview of Ultra-thin TCO film properties in different techniques
Film a.Resistivity ( cm) 1. Grain size (nm)
Film deposition Transm.
Thick. b.Carr. Conc. (cm-3) 2. Process Temp (C) Device Reference
methods (%)
(nm) c. Mobility (cm2/Vs) 3. Substrate
a. 9 x 10-4 1. Grain Size ~ 20-30 nm Jpn. J. Appl.
Dual pulse ITO film
b. 6 x 1020 ~ 85−88 2. Dep. Temp. > 120C OLED Phys. 54
Magnetron source 50 nm 090301 (2015)
c. 13 3. Substrate: PET
Solar Energy
Facing target a. 3−8 x 10-4 1. Grain Size ~ 14-30 nm
ITO film 80−90 Si-Solar Mater. Solar
Magnetron b. 3 −7 x 1020 2. Dep. Temp. = 300C
< 40 nm cell Cells, 149,
sputtering c. 15−20 3. Substrate: Si, Glass 250 (2016)
Magnetron a. 7−4 x 10-4 1. Grain Size ~ 10-20 nm Ceram. Inter.
ITO film
sputtering + b. 3 x 1020−2 x 1021 80−90 2. Anne. Temp. = 300C ─ 40 1116,
< 30 nm
E-beam eradiation c. 25−35 3. Substrate: Glass (2014)

a. 7.2 x 10-4 1. ─
ITO film ~ Langmuir, 29,
Solution Processing b. ─ 85−90 2. Anne. Temp. = 350C ─
100 nm 13836 (2013).
c. ─ 3. Substrate: Glass
ITO film a. 6−1.8 x 10-4 1. Grain Size ~ 5-20 nm Jpn. J. Appl.
65−80 ─
PLD 90~ 150 b. 7 x 1020−1x 1021 2. Sub. Temp. = 350C Phys. 38, 2710
nm c. 10−35 3. Substrate: Si, SiO2 (1999)

• Mostly high deposition temperature is required.

Remark However, we need low-temperature process.

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 Typical magnetron sources for thin
film deposition

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 Typical magnetron sputtering systems
planar magnetron Facing magnetrons
▪ Poor magnetic
confinement
▪ Better magnetic
confinement
▪ Low plasma density
▪ Moderate plasma
▪ Low target efficiency
density
▪ High-process
▪ Higher target
temperature
efficiency

▪ Moderately High-
process temperature

Dual magnetrons Cylindrical magnetron

▪ Moderate magnetic
▪ Better magnetic confinement
confinement
▪ Low-plasma density
▪ Moderate plasma
density ▪ High target efficiency

▪ Low-Moderate ▪ Moderate-process
target efficiency temperature

▪ High-process
temperature

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 Some Difficulties/Disadvantages of Magnetron sputtering

High energy particle bombardment sometimes

degrade the substrate

 Materials or thin films are degraded by high energy atom and ion bombardments
 It is also challenging for the crystallization of the film at low-temperature < 100C
 Complexity of plasma based process and process control is not straightforward

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 Our key demands /requirements
Our demand on process and material Necessity
Process requirement ➢ New-type and high density plasma
source
• High rate deposition ➢ Control of plasma parameters
• High target efficiency and large area (electron temperature, plasma
density, etc.)
deposition ➢ Energy control of sputtered particles
and ions
• Low-temperature deposition process ➢ Process understanding, optimization,
and control by diagnostics
Material aspect ➢ To reduce amorphization or to
Good crystallinity enhance crystallinity by reducing ion
High transmittance flux on the substrate (need good
High conductivity in ultra thin film charge trapping).
➢ To find the way to sputter a bunch of
Film adhesion and flexibility
atoms or to form clusters to add up
crystallinity at low-temperature.

There is the need of advance plasma process with new-type of sources.

There is the need of integrated study of film properties and plasma chemistry.
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 Plasma parameters (in TCO thin film processes)
Measurements are at the substrate position
Plasma Electron Plasma Sub.
Nature of
density (n0) temperature potential Temp. Reference
magnetron source
in cm-3 (Te) in eV (Vp) in V (℃)
109~1010 200 J. Appl. Phys. 117, 023301
Planar Magnetron source 1.3 ~ 3 1~5
Low High (2015)
1x1010~7x1011 <8 < 120 Jpn. J. Appl. Phys. 54 090301
Dual Magnetron source Moderate 2~4
Moderate (2015)

1x1010~8x1011 Thin Solid Films, 587, 88

Facing target and Moderate, < 120 (2015)
magnetic better 3~5 8~10 Moderate Sci. Adv. Mater. 7, 107 (2015)
field source (FTMS) confinement

1x1011~3x1011  120 Plasma Process. Polym. 13,

High, better 4~5 10~30 Moderate
ICP hybrid with FTMS 134 (2016)
confinement
~1011 5 ~ 20 J. Instrument, 2012,
PLD High ─ > 200
doi:10.1088/1748-
High High
0221/7/05/C05017

ICP assisted facing magnetron sputtering has shown similar performance of high electron
density to that of the PLD process
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 New TCO film for flexible device

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 There is increase demand of TCO films on flexible substrates

Example: Flexible light emitting

devices require:
→ Ultra thin plastic / glass ITO films (Thickness
< 40 nm)
→ High transparency (> 85%)
Ultra thin
→ Low resistivity ~ 10-4 ohm cm ITO film
→ High flexibility (20-40 nm)

Flexible OLED lighting device

We need advanced magnetron process for the
deposition of ultra-thin ITO films on flexible substrate
at low-temperature

Ok et al. Scientific Reports, 5 , 9464 (2015)

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 Design of high conductivity TCO film
by magnetron sputtering

1. Materials’ design
2. Consideration of plasma chemistry
3. Consideration of source design
4. Development of source
5. Magnetic field profile

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 Realizing the cluster evaporation/deposition by PLD process

In PLD method target materials are knocked by laser irradiation.

Evaporated atoms and clusters are deposited onto the substrate.

One has to consider the way to generate cluster in magnetron sputtering.

http://www.emrl.de

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 Approach for making ultra thin ITO film
Conventional approach: Two steps Present Design: Simultaneous process
Step 1: During deposition of the thin film an We consider a very high density magnetron
ultra thin amorphous layer is deposited plasmas. For this,
initially.
1. A very strong magnetic field
Amorphous ITO layer 10-50 nm confinement is designed to generate a
high temperature sustaining high electron density (or plasma
Flexible/glass substrate density)
plastic substrate

2. Incorporate electron-neutral collision to

Step 2: Post annealing  150 C for 1-3 assist neutral-neutral coagulation for
Hours to transform into crystalline the cluster formation.
microstructure.
3. Enhancement of crystallinity by
Crystalline ITO film 10-50 nm nanoclusters deposition at low
high temperature sustaining temperature.
Flexible substrate
plastic substrate
4. Without post annealing.
Film prepared by sputtering followed by post
annealing
Appl. Phys. Lett. 99, 043503 (2011)

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 Design of ultra-thin ITO films by magnetron plasma process
Advanced magnetron plasma process
Design of plasma source, process and plasma control
(enhance plasma density & reduce ion bombardment)

Control of Plasma
density & Energy
Cluster formation in flux
high density plasma

Crystalline ITO film by

10-50 nm
cluster deposition

PET substrate

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 Plasma chemistry and source design consideration
Approach
Very well confined magnetic field
to traps electron and high energy ions near the target

Generation of high plasma density

High ion density assists High electron density

higher sputtering yield and enables higher electron
high growth rate neutral collisions and assist
rapid thermalization

Cluster formation Higher collisions and thermalization Higher collisional environment

inside the rectangular enables energy control of the high will provides the opportunity to
magnetron energy neutrals that affects the neutral-neutral agglomeration to
film. form cluster.

Due to enhanced confinement ion flux on the substrate will be low Cluster and atoms
that will favors reduction of ion energy flux on the substrate.
diffuse into the growth site
to form bbsahu@dese.iitd.ac.in
ultra thin film
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 Collision model for enhancing probability to form cluster
We need a very high density plasma (or electron density) to enhance electron-neutral collisions
and thermalization so that neutral-neutral coagulation can occur inside the high density
magnetron trap.
Computations
▪ Electron temperature Te (eV ) ~ 2─3 eV
▪ Operating Pressure ~ 4-5 mTorr
▪ Plasma density n0 (cm-3 ) ~ 10 10 ─10 11 (cm-3 )
▪ Electron-neutral collision mean free path  ~ 20-25 cm[1]
▪ In atom Diffusion coefficient, Dn (cm2/s) ~ 396 cm2/s[2]
▪ Diffusion time t (s) ~ 2/Dn ~ 1.01 s ~ neutral/cluster
residence time[2]
▪ Magnetron source dimension (length x breadth) ~ 
▪ For typical lattice constant ~ 0.3 nm
= (neutral density x Cross section)-1
▪ No of atoms forming the cluster = 10
Dn = Do/no of atoms forming the cluster
D0 = 103 cm2/s x (Tg /200)3/2

[1] S. C. Brown , Basic Data of Plasma Physics 2nd edn (Cambridge, MA: MIT Press), 1967;
bbsahu@dese.iitd.ac.in
[2] N.B. Vargaftic, Tables of Thermophysical Properties of Liquids and Gases, Halsted Press, New York, 1975.
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 Magnetic field confinement of 3-D magnetron source
At target magnetic field is very high (~ 300─500 G) Contours of Magnetic field

central plane

• Central plane: Uniform distribution in large central area substrate plane

Very high B0 values: strong confinement of plasma in central plane. (Positive values: south polarity,
negative values: north polarity).

• Substrate plane: Small and quite uniform over large central area at the
substrate plane Uniform field in the substrate region assists a uniform
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plasma that adds up uniformity in the films
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 Results for ITO and AZO by 3D
source

Plasma chemistry investigation

Process optimization
Ultra-thin ITO film fabrication

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 Lagnmuire probe diagnostic in ITO film process
high density plasma
(cm )
-3

Pressure 4 mTorr
12
Abbreviation used
- 10

9 n0 = plasma density
n0 x 10

Te = electron temperature
6 Vp = plasma potential
3
4 Electron temperature control
Te (eV)

✓ Plasma density significantly increases even at

3
the substrate position with power ( > 1011 cm-3).
2 ✓ Electron temperature does not change much due

1 to slow decrease of plasma potential and weak

20 magnetic field that hold the electrons.
Vp (Volt)

15 ✓ At high power plasma density Te does not change

due to thermalization by increased collision. So,
10
the requirement of confinement by Vp decreases.
5 As a result, Vp falls at high power.
0.0 0.5 1.0 1.5 2.0 2.5 3.0 ✓ Power density  2 W/cm2 has generated a very
2
Operating Power density (W/cm )
high plasma density ~ 1011 cm-3
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 Plasma diagnostics: effect of power density on plasma and energy
flux on the substrate
Energy flux deposited on the substrate
Emission intensity of excited species measured by Calorimetric probe
Low-energy flux High-energy
High-energy flux
flux
Energy flux on substrate

Energy flux (mW/cm )

2
4
8
10 High-energy
flux
6
Intensity

Low-energy
10
3 4 flux Optimized
power density
Ar I - 419.8 nm condition
In I - 325 nm Ar I - 450.6 nm 2
In II - 409.2 nm Ar I - 811 nm
2
10 0
0.5 1.0 1.5 2.0 2.5 0.5 1.0 1.5 2.0 2.5
2 2
Power density (W/cm ) Power density (W/cm )

• Trace of In ion at high power density  2 W/cm2 - High energy influx at high power density is due
• Emission intensity increase with power density to the contribution of high density of excited
species.

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 Results: discharge curve and process temperature
Measurement of Discharge Voltage – current Low-temperature process

350 3mtorr
Discharge Voltage (V)

4mtorr
5mtorr
6mtorr
7mtorr
300 8mtorr

250

200
0.0 0.5 1.0 1.5 2.0 2.5
Discharge current (A)
Deposition time < 60 s for ultra
-Discharge voltage in 3D-source is much lower than thin films of thickness 10-50 nm
conventional MS
- A very high discharge current at low discharge voltage Working condition:
Power density 2 W/cm-2
suggests the generation of a very high plasma density. Pressure 4 mTorr

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 Results: Correlation between Optical and electrical
properties
Optical property Electrical property
-3
1.4x10 10 40
Resistivity Carrier concentration Mobility
100

Carrier concentration (X 10 /cm )

3
-3
1.2x10 35
8
80

20
Transmittance (%)

30

Resistivity (cm)
-4

Mobility (cm /Vs)

7x10
60 6
20nm

2
25
30nm 6x10
-4

40 40nm 4
50nm 20
-4
60nm 5x10
20 2
15

0 -4
0 10
200 400 600 800 1000 4x10
20 30 40 50 60
Wavelength (nm) Film thickness (nm)

Transmittance is changing with film

Carrier mobility is changing with the
thickness as expected
saturation in carrier concentration since we
fix the plasma chemistry due to fix
operation condition at 2 W/cm2.

Both the transmittance and electrical property are sensitively depends on the
carrier mobility
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 Results: Ultra-thin ITO films prepared at low-temperature:
Electrical property of the as deposited films Structural property
-3
1.4x10 10 40
Resistivity Carrier concentration Mobility In2O3 (222)

Carrier concentration (X 10 /cm )

3
-3
1.2x10 35 100 nm
8

Intensity (CPS)
20
60 nm
30
Resistivity (cm)

-4

Mobility (cm /Vs)

7x10 50 nm
6

2
-4 25 40 nm
6x10
4
20 30 nm
-4
5x10 20 nm
2
work by MS 15
by other study [1] 20 30 40 50 60 70 80
-4
4x10 0 10 2 theta (deg.)
20 30 40 50 60
Film thickness (nm)

Observations:
Plasma chemistry
▪ Ultra thin ITO films with resistivity ~ 5.8 x 10-4 cm at low-
• Ts  90 V (Low-temperature process) temperature is fabricated using high density plasma and
• Power density: 2 W/cm2 high energy flux at a high growth rate.
• High plasma density > 1011 cm-3
• High energy flux > 5 mW/cm2 ▪ Only one crystalline peak indicates that the films are c-axis
• Presence of In rich environment (by OES) oriented.
• High Deposition rate ~ 1.3 nm/s
▪ XRD peak are well observable from films with thickness 30
nm. Then, we do the HRTEM analysis.

[1] Jpn. J. Appl. Phys. 54 090301 (2015) bbsahu@dese.iitd.ac.in

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 Our achievement in conventional to 3-D confined magnetron
sources’ performances
FTS Advanced-3D confined MS
Conventional (better confinement) (The best confinement)
(poor confinement)

FTS + ICP

N0 Film
Processing Resistivity ( Mobility
Case Te (eV) ( x1010 Thickness Remark
Temp. (℃) cm) (cm2/Vs)
cm-3) (nm)
27−41 Moderate to
Conventional MS[1,2] > 100 1.3 ~ 3 1~2 10-3 −2 x 10-4 200
High Ts

ICP assisted FTS[3] > 120 3~5 ~6 7x 10-3 −6 x 10-4 12−14 200 High Ts

3D confined MS < 100 2.7 ~ 4 > 10 7−5.8 x 10-4 23−35 30 −60 Low Ts

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 Summary
▪ High conductivity flexible ITO films have been fabricated using a well confined 3-D
magnetron source.
▪ Due to a very high magnetic confinement the source can generate a very high
plasma density at a low electron temperature.
▪ High plasma density, low-electron temperature, high energy flux and with the
addition of O2 are found to be favorable conditions for the preparation of ultra-thin
ITO films with very high conductivity with the generation of nano cluster
microstructure.
▪ Plasma chemistry and energy control of plasma species in the process plasma is
crucial for the desired film properties.

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 Thank you !

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