Understanding Fluorine

(F2) Gas Emissions and

Control
Rod J. Gravley
Aketon Technologies

Rod J. Gravley, Aketon Technologies - Slide 1

 Presentation Topics

• NF3 • Fluorine Gas

– Advantages – Formation
– Liabilities – Impacts
– Future – Measurement
– Abatement

Is there room for improvement?

Rod J. Gravley, Aketon Technologies - Slide 2

 Advantages of NF3 Cleans
Steady State Metric
Global Warming Potential
Tons Carbon • 4 to 12 Times Faster
50,000

40,000
• Greater Conversion
30,000
– 70 to 90% Insitu
20,000 – >99% Remote
10,000
• Reduced Global
0
NF3 Warming Impact
CF4

C2F6

C3F8

Source: Solid State Technology, July 1996

Rod J. Gravley, Aketon Technologies - Slide 3

 Liabilities of NF3 Cleans
• Fluorine Gas Emissions
• Geometry Size Drives Usage
10

F2 Mass Emissions
6
Clean Frequency
4

0
0.50 0.35 0.25 0.18 0.13 0.10
Geometry

Rod J. Gravley, Aketon Technologies - Slide 4

Increasing Global NF3 Demand
8
7

6
5
Demand
(106 pounds) 4

1
0

1995 2000 2001 2002 2003 2004

Year

Source: SEMI - Industry Research & Statistics,

November 2000

Rod J. Gravley, Aketon Technologies - Slide 5

 F2 Formation & Fate
• Remote Plasma Chamber
-
2NF3 (g) + plasma → N2 (g) + 6F (g)
• Between Chamber and Pump
-
6F (g) → 3F2 (g) 99%
-
4F (g) + Si (s) → SiF4 (g) <1%
• Abatement Conversion
H2 (g) + F2 (g) → 2HF (g) + Heat
• Liquid Scrub
HF (g) + excess H2O (aq) → 2HF (aq)

Rod J. Gravley, Aketon Technologies - Slide 6

 OF2 Formation Mechanisms
• Adding Electrical Energy
2HF (aq) + 6H2O (l) → OF2 (g) + O3 (g) + H2O (g)
• Passing Fluorine Through >1 Molar Aqueous Alkaline
- -
2F2 (g) + 2H (aq) → OF2 (g) + 2F (aq) + 7H2O(l)
• Passing F2 over Cooled Ice
F2 (g) + H2O (s) → HF (g) + OF2 (g)
Sources:
Encyclopedia of Inorganic Chemistry, vol 3, p 1236, 1994
Journal of the American Chemical Society, 57(1):246-248, 1935
Journal of the American Chemical Society, 106(15):1754-1757, 1987

Rod J. Gravley, Aketon Technologies - Slide 7

 Impacts to Operations

• Degradation of FRP Ducts

• Odor Complaints - Threshold is 0.02 to 0.08
ppmv
• Exposure Symptoms - Low TLV of 1.0 ppmv
• Yield Impacts - F2 is Strongest Known
Oxidizer
• Corrosion of Abatement Equipment

Rod J. Gravley, Aketon Technologies - Slide 8

 Desired Characteristics of a
Chemical Sensor

• Responsive to Fluorine
• Components Compatible with Fluorine
• Not Cross Sensitive to other Common
Species (HF, SiF4, Silane, Hydrogen, etc.)
• High Sensitivity
• Continuous

Rod J. Gravley, Aketon Technologies - Slide 9

 Measurement Methods
• Mass Spectrometer
+ Continuous and able to see other species
- Equip degradation and stability
• Electrochemical Cells
+ Continuous and Low Cost
- Poisoning, cross sensitivity, and stability
• Colorimetric Tubes
+ Simple and Low Cost
- Not Continuous, cross sensitivity, and poor
quantitaion

Rod J. Gravley, Aketon Technologies - Slide 10

 Measurement Methods
(continued)

• URS Technology
+?
- ?
• Impinger Trains
+ Simple and Low Cost
- Not Continuous, cross sensitivity, and long sample
duration

Rod J. Gravley, Aketon Technologies - Slide 11

 Fluorine Gas - DRE
Demonstration
TransChem™ 150 - Laboratory Evaluation
Performance Data - Shot 21
8,000 100

Reactor Exhaust Emissions 90

7,000
Reactor "Off"
Fluorine Concentration (ppmv)

F2 Gas Off
Reactor "On" 80
6,000 Tube 8, Exhaust Temp
70

5,000
60

4,000 50

40
3,000

30
2,000
20
F2 Gas On
1,000
10

0 0
15:36 15:50 16:04 16:19 16:33 16:48 17:02

Time

Rod J. Gravley, Aketon Technologies - Slide 12

 Desired Characteristics of an
Abatement System

• Treats Both Fluorine and Process Gases

• Components Compatible with Fluorine
• Minimal Footprint
• Minimal Maintenance
• Minimal Utility Usage
• Minimal Installation Costs

Rod J. Gravley, Aketon Technologies - Slide 13

 F2 & Acid Scrub Performance

F2 DRE for Liquid Scrub

• Poor Performance for
100
Standard Configurations
80
• Elevated pH has Minimum
DRE (%) 60 Impact on DRE
40
• Secondary Chemical
20 Addition is Problematic
0
• Potential for Evolution of
pH 11
pH 7.4

pH 10

KI
Na2O3S2

F2 back to the Gas Phase

Rod J. Gravley, Aketon Technologies - Slide 14

 Bond Strength
Bond Strength (KJ/mol)
1000

800

600

400

200

F6
Am e

r
e

en
Ph ne
ine

n
ia

ate

en
ine
an
sin

ge
W
on

yg
a

og
or

Sil

W
ph
th
Ar

tro
m

Ox
Flu

dr
Me

os

Ni
Hy
Source: Handbook of Chemistry & Physics,
63rd Edition

Rod J. Gravley, Aketon Technologies - Slide 15

 Ineffective Solutions

• Short Contact Time Combustion

• Water Ring Pumps
• Ambient Temperature Resins
• Heated Salts
• Nitrogen Dilution

Rod J. Gravley, Aketon Technologies - Slide 16

 How is F2 currently abated?
Conventional Approach:
• Thermal Oxidation with Water
Contact Cooling

Rod J. Gravley, Aketon Technologies - Slide 17

 Conclusions
• NF3 Usage will Increase Dramatically
• Fluorine Gas Emissions Across the
Industry are Increasing
• An Ideal Measurement System is in
Development
• Current Abatement Strategies are
Adaptions of PFC Designed
Equipment

Rod J. Gravley, Aketon Technologies - Slide 18

 Questions
Contact
Rod Gravley
Aketon Technologies
(541) 758-1510
rod.gravley@aketontechnologies.com

Rod J. Gravley, Aketon Technologies - Slide 19