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Solar Energy Material by MS - Unlocked
Solar Energy Material by MS - Unlocked
by magnetron sputtering
August 2023
Outline
▪ Overview of transparent conductive oxide films
▪ 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
Smart coatings
Transparent E-paper
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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. > 120C 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. = 300C
< 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. = 300C ─ 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. = 350C ─
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. = 350C Phys. 38, 2710
nm c. 10−35 3. Substrate: Si, SiO2 (1999)
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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
▪ Low-Moderate ▪ Moderate-process
target efficiency temperature
▪ High-process
temperature
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Some Difficulties/Disadvantages of Magnetron sputtering
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 < 100C
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.
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
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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
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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
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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
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
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;
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[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
• 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
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Lagnmuire probe diagnostic in ITO film process
high density plasma
(cm )
-3
Pressure 4 mTorr
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Abbreviation used
- 10
9 n0 = plasma density
n0 x 10
Te = electron temperature
6 Vp = plasma potential
3
4 Electron temperature control
Te (eV)
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
20
Transmittance (%)
30
Resistivity (cm)
-4
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)
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)
Intensity (CPS)
20
60 nm
30
Resistivity (cm)
-4
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.
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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