Better Standards, Better Life 1
Gas Metrology Gas Metrology Gas Metrology Gas Metrology for Technology Innovation & for Technology Innovation & for Technology Innovation & for Technology Innovation & Sustainable DevelopmentSustainable DevelopmentSustainable DevelopmentSustainable Development
JinJinJinJin SeogSeogSeogSeog KimKimKimKim (KRISS)(KRISS)(KRISS)(KRISS)Chair of Gas Analysis WGChair of Gas Analysis WGChair of Gas Analysis WGChair of Gas Analysis WG
Better Standards, Better Life
Introduction of Gas Metrology
Example of Gas Metrology Application to High Technology for GHG Reduction
KRISS Capability on Gas Metrology
2
Better Standards, Better Life
National Metrology Institutes (NMI)
• Highest authority in metrology
• Maintain the national measurement standards
- Directly traceable to primary standards when NMI realize
the SI units of measurement standards
- Should insure that the measurements are traceable to a primary
standards when NMI does not realize the SI units.
• Responsible for disseminating the national measurement
standard
• Mission: Increase Competitiveness of National Economy
and Quality of Life through Metrology
(Technology Innovation & Sustainable Development)
Better Standards, Better Life
ROLE OF METROLOGY
Productivity
Product Quality
Product Defect Reduction
Impacts on Global Trade Issue
Increase Reliability on Legal Procedure
Over the last decade, there has been a significant increase in the recognition of
metrology and the important role it plays in improving
Better Standards, Better Life 5
SI
UNITS
Primary
Standard
Certified
Reference Material
Reference Gases
Working Standards, Samples
Measurement Hierarchy in Gas MetrologyMeasurement Hierarchy in Gas Metrology
mol/mol
National Metrology Institute (NMI)
Specialty Gas Company
Users
NMI/CRM producer
Gas Metrology
• Gas metrology for Industry and Quality of Life
- Produce Certified Reference Materials
- Improve Process Control, Quality Control
- Precise measurement of Emission,
Global warming, and Indoor air quality
• Gas Metrology for Science (as expert in measurement)
- Ar mole fraction in air: Air density
- Ne, Ar, He, C, N atomic weight (~ppm level accuracy)
- Triple point of gases, Boltzmann constant, Gas constant
Reference Material / National System
Primary Method
PRM
CRM
PTM
Key
Comp. Reg. CMC
Coding
Center
Testing Lab.
Regulation
Body
2nd RM
producers
(GLP, ISO/
IEC17025)RM, CRM
Roles of Gas Metrologist for Industry
CRM development
Environmental Effect : Global warming
Working Environmental Condition
Process Control for Quality
Testing services
Providing PT program
Education on Gas Analysis
Development of Analytical system :
simple & fast for quantification
Application Areas and Needs of CRMApplication Areas and Needs of CRMApplication Areas and Needs of CRMApplication Areas and Needs of CRM
Object Application FieldsNeeds of
CRM
Service to
industries
High Quality Products: Quality control
of manufacturing processΟ
Regulation for trade: RoHS, WEEE,
Safety RegulationΟ Ο Ο
New technology: R&D Ο
Regulations
Determine the limit for regulation:
Toxic chemical producers, Govnt Agency△△△△
Standards: Procedure, ISO/TC activity,
ValidationΟ
Testing report: QC, Traceability, Quantification Ο Ο Ο
Ability of Testing Lab: Participate in PT program Ο Ο
Better Standards, Better Life 10
Target Gas Chemicals for AnalysisTarget Gas Chemicals for AnalysisTarget Gas Chemicals for AnalysisTarget Gas Chemicals for Analysis
CFCs, PFCs : CF4, C2F6, SF6, NF3, Freon, Renewable refrigerants
Metal Hydrides : SiH4, PH3, AsH3, B2H6
Acids : F2, Cl2, HF, HCl, BF3, HBr, WF6
Odors : NH3, H2S etc.VOCs : BTX, Acetone, Alcohol, HCOHEnvironment: NO, CO, SO2, O3, Particles, GHGPure Gases : He, N2, H2, Ar, N2O, O2, AirGases in Liquid, Solid & BiomaterialsGases in Products (Lamps, Package, Vacuum,
Detectors, Display Pane ……)
Better Standards, Better Life 11
Procedure of Gas AnalysisProcedure of Gas AnalysisProcedure of Gas AnalysisProcedure of Gas Analysis
• Validated procedure• Calibration of Instrument & Apparatus• Confirm of Environmental Condition• Get Gas CRMs• Comparison of Samples and Gas CRMs• Evaluation of results• Report Concentration & its Uncertainty
Better Standards, Better Life 12
GC-TCD : inorganic gas
GC-FID : organic gas
GC-SCD : S containing gas mixture
GC-FID-Methanator : CO, CO2
GC-MSD : unknown gas identification
GC-ECD : F, Cl chemicals
GC-DID : ppb – ppm
GC-AED : Metallic gas, similar PRM
FTIR, NDIR, CRDS: impurities, CO2, CO, CH4, N2O
Dedicated analyzer: NOx, SO2, O3, H2O etc.
Gas MS : isolated samples, limited amount
IRMS : isotopic ratio
Instruments for Gas Analysis
Better Standards, Better Life 13
Procedure of Comparison MeasurementProcedure of Comparison MeasurementProcedure of Comparison MeasurementProcedure of Comparison Measurement
Making calibration line: Making calibration line: Making calibration line: Making calibration line: One point calibration: linear line through originOne point calibration: linear line through originOne point calibration: linear line through originOne point calibration: linear line through origin Two points Calib.: linear lineTwo points Calib.: linear lineTwo points Calib.: linear lineTwo points Calib.: linear line Multi points Calib.: nonMulti points Calib.: nonMulti points Calib.: nonMulti points Calib.: non----linear lineslinear lineslinear lineslinear lines
Use CRMs with most similar concentrationUse CRMs with most similar concentrationUse CRMs with most similar concentrationUse CRMs with most similar concentration If matrix is different, correct that effectIf matrix is different, correct that effectIf matrix is different, correct that effectIf matrix is different, correct that effect Check repeatability & reproducibilityCheck repeatability & reproducibilityCheck repeatability & reproducibilityCheck repeatability & reproducibility Correct drift effectCorrect drift effectCorrect drift effectCorrect drift effect Keep good baseline (purity of carrier gas)Keep good baseline (purity of carrier gas)Keep good baseline (purity of carrier gas)Keep good baseline (purity of carrier gas)
Better Standards, Better Life 14
Main Export Products during 1960s and 1970s
13.0
12.6
6.7
5.8
5.5
4.5
4.2
3.3
3.3
3.0
19601960
Iron Ore
Tungsten
Raw Silk Thread
Coal
Squid
Live Fish
Graphite
Wood Board
Rice
Bristle (hair)
Products %
11
22
33
44
55
66
77
88
99
1010
[1960s: Raw Materials] [1970s: Light industry goods]
Textiles
Wood Board
Wig (false hair)
Iron Ore
Electronics
Vegitables
Shoes
Lead & Lead Products
Steel Products
Metal Goods
40.8
11.0
10.8
5.9
3.5
2.3
2.1
1.6
1.5
1.5
Products %
11
22
33
44
55
66
77
88
99
1010
19701970
Economy of Republic of Korea : 50 year Ago
Better Standards, Better Life 15
[2000s: High Tech & Heavy Chemicals]
20002000
Semiconductor
Computer
Car
Petroleum Chemicals
Shipbuilding
Wireless Goods
Steel Plates
Clothes
Synthetic Textiles
Electronics
Products
11
22
33
44
55
66
77
88
99
1010
%
8.4
7.7
5.5
4.8
4.7
2.8
2.7
2.1
2.1
15.1
20062006
Semiconductor
Car
Wireless Goods
Shipbuilding
Petroleum Chemicals
Computer
Plat Panel Display
Synthetic Resins
Steel Plates
Automobile Parts
Products
11
22
33
44
55
66
77
88
99
1010
10.2
10.1
8.3
6.8
5.9
3.9
3.8
3.4
3.4
3.1
%
6.3
Main Export Products in Present
Economy of Republic of Korea : Recent
Better Standards, Better Life 16
Light Industries 1960-70
Heavy & Chemical Industries 1970-80
Electronics 1980-95
Information & Communication 1995-Present
Economic Growth of Korea
Better Standards, Better Life 17
○ DRAM: World market share 1st (45%)
○ Display Panel: World market share 1st (35%)
○ Shipbuilding: World market share 1st (40%)
○ Car: World market share 6th
○ Iron Plates: World market share 4 %
World Products from Korea
Better Standards, Better Life 18
▶ Monitor : From CRT to LCD/LED
▶ Large Screen TV : competition of LCD & PDP (> 50”)
▶ Mobile : LCD & OLED ( < 10” )
( VGA: 640 x 480, XGA: 1024 x 788, UXGA: 1600 x 1200, QXGA: 2048 x 1536)
10 15 20 30 40 50 100
VGA
XGA
Resolution
OLED
FED PDP
ProjectionCurrent LCD
Future LCD
Size(“)
Mobile
Display
Large TV
70
UXGA
(HDTV)
QXGA
Evolution of Display ScreenEvolution of Display ScreenEvolution of Display ScreenEvolution of Display Screen
Better Standards, Better Life 19
Development of OLED DisplayDevelopment of OLED DisplayDevelopment of OLED DisplayDevelopment of OLED Display
Large Screen OLED DisplayThin ~ 30 mm
amorphous-Si TFT– Large screen
poly-Si TFT– Long lifetime
Better Standards, Better Life 20
Oxidation
PR Coating
Coating
Etch
ImplantMetal Depo CMP
Photo Stepper
CVD
Ashing Wet
IngotSi Growth
Semiconductor Manufacturing ProcessSemiconductor Manufacturing ProcessSemiconductor Manufacturing ProcessSemiconductor Manufacturing Process
Sawing Wire Bond PKG IC Chip
Si Wafer
Better Standards, Better Life 21
Exhaust Gas Analysis for the Sustainable DevelopmentExhaust Gas Analysis for the Sustainable DevelopmentExhaust Gas Analysis for the Sustainable DevelopmentExhaust Gas Analysis for the Sustainable Development
VacuumPump
Process Tool POUScrubber
PFC TotalScrubber
Acid HouseScrubber
Abatement System Efficiency Analysis
Better Standards, Better Life 22
Efficiency of PFC Scrubber
ScrubberProcess
ChamberExhaust
In-let
Pin
Out-let
Pout
Qin Qout
)1()1()1( iiii dCFChFCofEmissio
FC
)1( iC )1( id
Ci = Qin ·Pin / FCin di = Qout ·Pout / Qin ·Pin
Qout = 1 / PHe
Emission Reduction Methodology for PFC & SF6
• Validated Procedures
Approved CDM Methodology by UNFCCC
Korean EPA modified UNFCCC methodology
• Reference Gas Mixtures (CRMs)
for calibration & validation
• UNFCCC: UN Framework Convention on Climate Change
Approved Methodology by UNFCCC
MethodologyApplying
CompanyReduction Mechanism
Monitoring
Instrument
AM0078
Display Process
in LG &
Samsung
SF6 Abatement by
fuel combustion
QMS, FTIR
Annubar
Water Analysis
AM0092
Semiconductor
in Chartered
Semi & Hynix
Substitution of C2F6
with c-C4F8
FTIR
QMS(Kr)
AM0096Semiconductor
in Samsung
CF4 Abatement by
electrical heaterQMS(He)
AM0092
Schematic:
Baseline &
project
emission
QMS
FTIR
MFC
Kr
Cal. System
Quantification by QMS with Reference Standard Gas:
N2, O2, CO2, Ar, SF6, He, Kr, Xe
Quantification by FTIR with Reference Standard Gas:
CO2, CO, SF6, NO, SO2
Quantification by FTIR with Library Information:
HF, SiF4, SOF2, SO2F2, …
Difficult components: F2, Cl2 (memory effect in QMS)
Strategy of Quantification
CCQM-K15 (2003)
Coordinating Lab: KRISS
Subatance: SF6 & CF4 hundred μmol/mol level
To support industry on PFC emission
28Better Standards, Better Life
Primary Reference MaterialPrimary Reference MaterialPrimary Reference MaterialPrimary Reference Material---- Purity assessment Purity assessment Purity assessment Purity assessment
¦ MolecularMolecularMolecularMolecular weightsweightsweightsweights ofofofof sourcesourcesourcesource gasesgasesgasesgases (isotopic(isotopic(isotopic(isotopic ratio)ratio)ratio)ratio)¦ ImpurityImpurityImpurityImpurity analysisanalysisanalysisanalysis basedbasedbasedbased onononon finalfinalfinalfinal concentrationconcentrationconcentrationconcentration
---- Accurate mixing (Gravimetry)Accurate mixing (Gravimetry)Accurate mixing (Gravimetry)Accurate mixing (Gravimetry)---- Internal consistency by comparisonInternal consistency by comparisonInternal consistency by comparisonInternal consistency by comparison (4 cyl. at a time)(4 cyl. at a time)(4 cyl. at a time)(4 cyl. at a time)---- Stability test (2 cyl. after 6 months)Stability test (2 cyl. after 6 months)Stability test (2 cyl. after 6 months)Stability test (2 cyl. after 6 months)---- Verification through KC (including uncertainty)Verification through KC (including uncertainty)Verification through KC (including uncertainty)Verification through KC (including uncertainty)---- Register to BIPM CMCRegister to BIPM CMCRegister to BIPM CMCRegister to BIPM CMC (as NMI)(as NMI)(as NMI)(as NMI)---- Validation of life time by periodical reproductionValidation of life time by periodical reproductionValidation of life time by periodical reproductionValidation of life time by periodical reproduction---- Economically not good (managing by national body)Economically not good (managing by national body)Economically not good (managing by national body)Economically not good (managing by national body)
29Better Standards, Better Life
“Maximum capacity 15 kg /
Readability 1 mg• Much easier, much faster, highly precise:
round type
• Pressure, temperature, relative humidity
recorded automatically
• Two or three cylinders measured
serially (e.g., A-B-A-B, A-B-C-A-B-C,
or A-C-A-C cylinders)
• Date, time, pressure, temperature,
relative humidity are all automatically
recorded by a customized program
developed at KRISS
A Recent Change in the Comparator Balance (2007)
Mettler Toledo AG (Model XP26003L)
Maximum capacity 26.1 kg / Readability 1 mg
※ Therefore, now we can measure the weights of cylinders having a
volumetric capacity of up to 10 L.
Fully Automated Weighing System (2006)Fully Automated Weighing System (2006)Fully Automated Weighing System (2006)Fully Automated Weighing System (2006)
NIST, NPL
NMISA,
ASTAR/NMC
NIM, LIPI
ITRI/NMC
30Better Standards, Better Life
• CFC & PFC Gases : For semiconductor companiesCFCl3, CF2Cl2, CF3Cl, C2F3Cl3 ---- 110-2 mol/mol, 1-100 μmol/mol
NF3, C3F6, SF6, CF4, CHF4, C3F8 ---- 110-2 mol/mol, 1-100 μmol/mol
• Green House Gases :CO2 ---- 110-2 mol/mol, 380 μmol/mol
CH4 ---- 110-2 mol/mol, 1.8 μmol/mol
CO2+CH4+N2O ---- mixture at ambient level
CFCs, PFC, NF3, SF6--- ambient level
• Air Pollution Monitoring Gases :CO, NO, SO2, VOCs, Aldehydes, ( O3 Primary calibration system)
Developed CRMs in KRISSDeveloped CRMs in KRISSDeveloped CRMs in KRISSDeveloped CRMs in KRISS
Primary Reference Gas Mixture for
Green House Gases
substance Range of Certified Values Uncertainty (k=2) ref
CO2 above 10 μmol/mol 0.06 at 380 μmol/mol CCQM-K52, K120
CH4 above 100 nmol/mol 0.002 at 1.9 μmol/mol CCQM-K82
N2O above 50 nmol/mol 0.24 at 320 nmol/mol CCQM-K68
SF6
NF3
above 6 pmol/mol for SF6
above 1 nmol/mol for NF3 (0.5 pmol/mol after
2011)
0.06 at 6 pmol/mol for SF6
0.01 at 1 nmol/mol for NF3
CCQM-K15
PFCs
above 10 pmol/mol for CF4
above 100 μmol/mol for C2F6
(50 pmol/mol after 2011)
0.1 at 10 pmol/mol for CF4 CCQM-K15
HFCs above 30 pmol/mol for HFC23 0.15 at 50 omol/mol CCQM-K84
CFCs μmol/mol~50 pmol/mol for CFC 11,12,113 0.5 at 50 pmol/mol CCQM-K84
32Better Standards, Better Life
Proficiency Test for Specialty Gas CompaniesProficiency Test for Specialty Gas CompaniesProficiency Test for Specialty Gas CompaniesProficiency Test for Specialty Gas Companies
---- PT provided by official bodyPT provided by official bodyPT provided by official bodyPT provided by official body---- Round Robin TestRound Robin TestRound Robin TestRound Robin Test---- 1:1 comparison (bilateral, trilateral)1:1 comparison (bilateral, trilateral)1:1 comparison (bilateral, trilateral)1:1 comparison (bilateral, trilateral)
A B C D E-5
-4
-3
-2
-1
0
1
2
3
4
5
CO2
Rela
tive D
evia
tio
n
Lab CodeLab CodeLab CodeLab Code
Better Standards, Better Life 33
Gas Analysis in IT industry by KRISSGas Analysis in IT industry by KRISSGas Analysis in IT industry by KRISSGas Analysis in IT industry by KRISS
Gas Analysis : Quality control of products, development of new Gas Analysis : Quality control of products, development of new Gas Analysis : Quality control of products, development of new Gas Analysis : Quality control of products, development of new product & problem solving in processproduct & problem solving in processproduct & problem solving in processproduct & problem solving in process
New Technology:
Backlight & PDP
Developing New product:
Organic Light Emitting Display
QC: Process Control
Reduction of GHGs:
Gas Scrubber
Better Standards, Better Life 34
융Abs. Isotope
Ratio, for ITS90
Industry
Support
ClimateChange/
Air Pollution
MetrologyKC
CRM
Social
Issue
(Fine Dust)
Researcher: 9
Engineer: 8
Technician: 3
Ph.D Std.: 4
Ms D Std: 9
Temp. member: 3
Human Resources of Center for Gas Analysis
Better Standards, Better Life 35
Technology Innovation & Sustainable Development
by Gas Analysis Center