Introduction of our core competence "Pure ozone" and related process by Meiden Nanoprocess Innovations,Inc

1. Pure Ozone Generator &
Process with POG
MEIDEN NANOPROCESS INNOVATIONS, INC.
1/19/2022
Document.No NPA-210182-0

2. 2/22
1. Features of Pure Ozone Generator (POG)
2. Working principle
3. Comparison with competing techniques
4. System Structure
5. Customer A (O source for Molecular Beam Epitaxy)
6. Customer B (In-situ mask/ reticle optics cleaning)
7. Customer C (Surface hydrophilization)
8. Pure Ozone deposited ALD (SiO2, TiO2, Al2O3)
9. Specifications (Batch Type)
Contents

3. 3/22
1. Features of POG
1. Extremely high ozone concentration (>90%)
2. Extremely high purity (elimination of NOx, metal & organic
particle)
3. No damage (electrically neutral & thermal energy O* source)
4. High efficiency (minimize pre-decomposition of ozone)
5. Real-time fine control of flow rate and pressure of supplied ozone
6. High compatibility with low pressure processes (e.g. ALD, CVD,
MBE PVD, PLD)
7. Intuitive operation (easily interface with the process chamber)
8. Diverse lineup of products from R&D to mass production
9. Continuous safe handling of high volume liquid ozone (NPI original
hardware and software)
**AIST=The National Institute of Advanced
Industrial Science and Technology

4. 4/22
2. Working Principle (Accumulation)
Evacuation
Cryocooler
Ozonator
Open Open
Cu block
(set around 90K)
Liquid O3
Ｏ２
Ｏ3/O2 mixture gas
Close
Open
Stainless-steel vessel
Liquefaction
O2
O3
Evacuation
Use of high purity O2 (semiconductor
grade) with 0.1wt % Ar is recommended
for ultra high purity demand

5. 5/22
2. Working Principle (Supply)
Ozonator
Ｏ２
Close
Phase 2 (Supply)
Close
Close
Pure O3 gas
Impurity (e.g., NOx) free
80 100 120 140 160 180
温度 [K]
蒸気圧
[Pa]
O2
NO
O3
N2O
NO2
105
103
101
10-1
10-3
Temperature [K]
Cryocooler
Cu block
(set around 120K)
Stainless-steel vessel
Vapor
Pressure
[Pa]
Open
･Basically control O3 pressure at supply
･Keep liquid O3 at stand-by of supply
Supply
Accumulation

6. 6/22
3. Comparison with competing techniques (O3)
Pure Ozone generator Competing Technology
(Conventional ozonizer)
Customer’s benefits
Ozone
Concentration
2,000g/Nm3
(more than 90wt.%)
210g/Nm3
(14wt.%）
- Lower temp process
- Compatible with low pressure
process such as MBE, sputter
and pulse laser deposition
Ozone gas flow rate Up to 0.5L/min
(5L/min when 10% duty (e.g.,
ALD process, standby as O3
vapor)
1 - 24L/min Flexible (e.g., step-by-step
time-variant) ozone supply
possible
Impurity Lower than 1 ppm
(distilled out)
0.1% level of NOx, H2O
included
No damage caused by impurity
and NOx-induced defects and
disorders
Controllability
(Repeatability)
Extremely high
(Mass flow + O3 vapor pressure)
High
(Mass flow)
Precise metal oxide
composition (stoichiometry)
control achieved
Safety Extremely high even in case of
mixing with other process gases
thanks to high purity of ozone
Mixing with other process
gases in high pressure may
cause explosive reaction
Applicable to various processes

7. 7/22
4. System Structure
O2, Ar（N2）
O3/O2, Ar
N2
Pure O3
Ceramic Filter
Cryocooler
Dry
Pump
Vacuum for
thermal
insulation
Stainless-steel
enclosure
Copper Block
Liquid Ozone
Enclosure（negative pressure inside）
Vessel
Ozonator
Pump
O3 decomposer Check
Valve
N2
O3 sensor
・Automatic operation by sequencer
・Continuous display of machine status
・Quick detection of failure and
necessity of maintenance
・Sensors, interlocks & emergency
operation at blackout
Flow
Meter
O3 pressure, flow rate
O3 concentration,
Time profile
Machine Status
Remaining supply time
NPI Patented

8. Copyright © MEIDEN NANOPROCESS INNOVATION, INC. All Rights Reserved.
４.Safe Operation Area of Ozone gas
Throughout the operation time, ozone gas concentration and pressure are monitored
and controlled so as to keep them inside the red area above.（No need to care for users)
1atm
(100,000Pa)
0.1atm
(10,000Pa)
0.01atm
(1000Pa)
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Our Experiment
(Explosive decomposition of ozone)
0.44atm
Guaranteed by a manufacturer of Ozonators
SOA (Safe Operation Area) of O3/O2/N2 mixture gas
(in case without initiators such as UV light, electric
energy and co-existing organic particles)
Ozone Concentration [vol.%]
Total Pressure
SOA controlled by our Pure Ozone Generator
3atm, 20%
8/22

9. 9/22
5. Customer A (O source for Molecular Beam Epitaxy)
ZnO Sub
1. High Concentration (highly oxidation), 2. High Purity (NOx free), 3. Damage free
(replacement of plasma oxidation), 4. High Efficiency (minimize pre-decomposition of ozone),
5. Real-time fine control of flow rate and pressure of supplied ozone, 6. High compatibility
with low pressure processes, 7. Intuitive operation & easily interface with the process
chamber, 8. Affordable price for R&D (future mass production)
Customer’s Satisfactions
Sample Structure
Ti
2DE Gas Ni/Au Electrode

10. 10/22
5. Data 1 of Customer A
O2 Plasma Pure Ozone
Depo Temp. = 880C Depo Temp. = 790C Depo Temp. = 750C
2m
MgZnO
ZnO buffer layer
ZnO substrate
・ POG can achieve a smooth
surface by MBE deposition at low
temperature and prevent
crystallization.
・ No metal (Mg) diffusion
ZnO Sub ZnOSub

11. 11/22
Achieved the highest level of mobility in the world because of smooth surface and
elimination of impurities = 1.3x106 cm2 /Vs @n=8.3 x 1010 cm-2
T<100mK
T=500mK
Insufficient screening of
impurities within the
crystal structure
Increased interface
roughness or alloy
scattering induced by
random potential of Mg
content
In comparison to historic data,
the maximum  of films has
occurred at decreasing
densities with the employment
of Pure Ozone Gas .
Sci. Rep. 6, 26598; doi: 10.1038/srep26598 (2016)
5. Data 2 of Customer A

12. 12/22
6. Customer B (In-situ mask/reticle optics cleaning)
Electron beam mask writer
O source
(Pure Ozone Gas)
Customer’s Satisfactions
6. Highly compatible with low pressure processes, 1. High Concentration (highly oxidation),
3. Damage free (no reflectivity change of mirror surface ), 2. High Purity (NOx free, no
corrosion), 4. High Efficiency (minimize pre-decomposition of ozone after 20 meter transfer),
8. Capability of 24/7/365 mass production
In-situ cleaning
exhaust of carbon contamination
and
gas

13. 13/22
6. Customer B (Ozone Ethylene Radical “OER“Process)
Developed OER (Ozone Ethylene Radical) process to generate OH,O,H radicals
effectively at lower than 100ºC and applies OER to actual processes.

14. 14/22
Mirror
* Material from EUVL symposium 2009 with Selete (Semiconductor Leading Edge Technologies, Inc.)
Substrate
[Mo/Si] layered
Mo
Si
Si (or Ru or TiO2/Nb2O5)
capping layer
Pure Ozone Gas
Graphite contamination
6. Customer B (low temperature & damage free process)
Carbon contamination can be removed without oxidation of mirror
substrate (metal cap & Si layers) and degradation of reflectivity of mirror.

15. 15/22
More than
one month
duration of
hydrophilicity
No thermal
and physical
damage
Increased
permittivity of
the fiber
OER process
(40 min)
Results
7. Customer C (surface hydrophilization)
Hydrophilization on carbon fiber: Persistence of hydrophilicity (high surface energy)

16. 16/22
Carrier
gas
(Ar)
Al2O3 film (25nm) on Si
deposited at Room temp.
Substrate (200mm)
Vacuum
C2H4
(option)
Precursor
Time
Flow rate
Pure O3
Pure O3
C2H4
Precursor
O+ OH radical
0
0
0
ALD mode CVD mode
Al２O３ (ALD)
SiO2 (CVD)
Substrate
Depth-profile-
optimized coating film
1-5 sec
0
Carrier gas
8. ALD process (Plasma-defect free oxides grown at <130C)
Developed low temperature
deposition process utilizing a
big advantage of Pure
Ozone gas.
・Low temp, low impurity, defect free
・High efficiency of gas usage
・On demand supply of ozone
・Multilayer (universal oxidation source)
TMA (Orthrus,
TDMAT, TDMAS)

17. 17/22
10
-10
10
-8
10
-6
10
-4
10
-2
10
0
Leakage
current
density
(A/cm
-2
)
10
8
6
4
2
0
Applied electric field strength (MV/cm)
 7%O3 100%O3
30
o
C
100
o
C
150
o
C
(a)
Ar
Time
Pure O3
C2H4
TMA
（Al(CH3)3）
0
0
0
0
0.1sec
1cycle (12sec)
4sec
40nm
8. Superior dielectric Property
Flow rate
Better dielectric property

18. Copyright © MEIDEN NANOPROCESS INNOVATIONS, INC. All Rights Reserved.
Sharp interface
200nm
8. Sharp interface (<1nm) and small carbon impurity
SiO2
TiO2
SiO2
TiO2
SiO2
C impurity
free
Glass (SiO2) substrate
18/22

19. Copyright © MEIDEN NANOPROCESS INNOVATIONS, INC. All Rights Reserved.
8. Superior Coverage (Underlying morphology independent process)
～5 um
～200
um
Process conditions
Process temperature 120C
Substrate Si wafer (200mm)
G.P.C. 0.24 nm/cycle
ALD one cycle 120 sec
Top Surface Trench Bottom
Conformal deposition to 40:1 high-aspect ratio trench structure
SiO2
Si
SiO2
Si
19/22

20. 20/22
8. High gas usage efficiency (environment friendly process)
Required
Ozone
Volume
for
1nm
Al
2
O
3
film
deposition
(cc)
NPI proprietary process (on demand supply: no ozone gas is disposed during the whole ALD process)
achieves higher efficiency of ozone usage than conventional low concentration O3 ALD process where
ozone gas flow needs to be kept besides the ozone pulses to outside the ALD chamber for repeatability.
*1 Chem. Mater., Vol. 18, No. 16, 2006 3765
*2 J. Phys. Chem. C 2008, 112, 19530–19539
Wafer size: 8inch (200mm)
Deposition temp. :120C
Our data
Efficient, Low process running cost
C
Competitor A Competitor B
*1 *2

21. 21/22
Item Specification
Size, Weight 900(W)900(D)1700(H) 470kg
Input Power 3-phase AC 200-230V, 30A 50/60Hz
Utility components Compressed dry air for ventilation, Nitrogen gas,
oxygen gas, cooling water
Max ozone storage
volume
8,000 cm3
(at 0deg.C 1atm gas phase)
O3 gas flow rate stability ±5%（Option ±1%） 20~200sccm
O3 concentration 90% or higher (at the outlet of our system)
O3 pressure 1,000Pa - 10,000Pa at the exit of the liquid O3 vessel
(Piping) Transfer distance
of O3 gas
<20m
Utility ratio 120min charging – 800min operation (@10sccm)
9. Specifications (Batch Type)
Refer to product brochures for specifications of continuous type

22. 22/22
Conclusions: Pure Ozone as Oxidation Source for ALD
Pure Ozone
• Ozone ~100%, theoretically no impurity of metal and organic materials
• Generated high volume pure ozone safely (SEMI S2 compliant) only by Pure
Ozone Generator (POG)
 Widely used at semiconductor foundries in the world!
Expected effect from ALD with POG
A. Rapid reaction with precursor because no other interference gas for oxidation
like over 80% oxygen exists.
B. Possible to reduce pure ozone pressure to at least 1/5 compared to a
conventional ozone gas if ozone molecular numbers are identical.  This
prevents inactivity of ozone by thermal decomposition at high temperature
because it can reduce thermal conductivity of gas.
C. Possible to reduce impurity of metal and organic materials that causes defect
for ALD high-k films.
Suitable to oxidation source for high
temperature ALD process