Supporting Supplementary Information

A Hybrid Life Cycle Assessment of Atomic Layer Deposition ProcessEndong Wang, Chris Yuan*

Department of Mechanical EngineeringUniversity of Wisconsin, Milwaukee

Milwaukee, WI 53211*Corresponding author: Tel: 1 414 229 5639; Fax: 1 414 229 6958; email: cyuan@uwm.edu 1. Feedstock production inventoryThe inventory data for hydrogen chloride and wafer production are obtained from the Gabi 6.0 software professional database. The inventory data for methanol production is obtained from the DOE LCI database (DOE 2013) and the information for auxiliary production facility is obtained from Hellweg (2003). Chloromethane is synthesized by the reaction of methanol and hydrogen chloride. The reaction efficiency is assumed at 95% (Hischier et al. 2005). Due to the lack of accurate energy consumption data, an amount of energy at 22.29 kJ/mole estimated from NIST (2013) and verified by Accelrys Materials Studio simulation is used for this process. The generic Ecoinvent dataset of “chemical plant, organics” is adopted for calculation, with the annual production amount of 50,000 kg during 50 years’ service life (Zah and Hischier 2007; Hischier et al. 2005). TMA is generated from the chemical reaction between aluminum, chloromethane and sodium. An energy consumption of 42.90 kJ/mole is estimated from NIST (2013) and validated by Materials Studio simulation. The reaction efficiency is 95% (Hischier et al. 2005). Given the unavailability of environmental information about chloromethane, in order to get the best estimate, dichloromethane is used to represent chloromethane with 1/2 mol dichloromethane equivalent to 1 mol chloromethane. According to literature, such estimates are commonly used in LCA to deal with information scarcity (Griffiths et al. 2013).• Methanol production (For 1g Al2O3)

Inventory results for methanol production Source: DOE (2013) (For 1g Al2O3)Inputs OutputsDummy_Disposal, solid waste, unspecified, to sanitary landfill

2.07E-03g BOD5,Biological Oxygen Demand

2.40E-04g

Natural gas, processed, for olefins production, at plant

2.57g Carbon dioxide, fossil 2.19g

Water, process, unspecified natural origin/m3

2.23E-06 m3 Methanol, at plant 4.14g

Electricity, at grid, US, 2008 3.33E-05 kWh NMVOC,non-methane volatile organic compounds, unspecified

2.07E-02g

Natural gas, combusted in industrial boiler

5.38E-04 m3 Suspended solids, unspecified

3.64E-04g

Oxygen, in air 1.57gTransport, combination truck, diesel powered

4.13E-05 t*km

Transport, pipeline, natural gas 4.13E-03 t*kmTransport, train, diesel powered 4.13E-05 t*km

Methanol plant (Hellweg 2003) (For 1g Al2O3)Material Electricity, medium voltage, production UCTE, at grid, UCTE 8.72E-7 kWhinputs Diesel, burned in building machine, GLO 7.32E-6 MJ

Zinc for coating, at regional storage, RER 1.57E-7 kgNickel,99.5%,at plant, GLO 5.81E-9 kgSteel, electric, un-andLow-alloyed, at plant, RER

7.21E-7 kg

Steel, low-alloyed, at plant, RER 3.06E-7 kgChromium steel,18/8, at plant, RER 2.65E-7 kgCopper, at regional storage, RER 6.62E-8 kgConcrete, sole plate and foundation, at plant, CH 7.53E-

11m3

Disposal,concrete,5% water, to inert material landfill, CH 1.74E-7 kgTransport, lorry 32t,RER 1.14E-6 tkmTransport, transoceanic freight ship, OCE 8.33E-7 tkmTransport, freight, rail, RER 2.22E-7 tkm

Resource Occupation, construction site 6.62E-7 m2ause Occupation, industrial area, built up 1.49E-6 m2a

Occupation, industrial area, vegetation 4.94E-7 m2aTransformation, from unknown 6.62E-8 m2

Transformation, to industrial area, built up 4.97E-8 m2

Transformation, to industrial area, vegetation 1.65E-8 m2

Emission Heat, waste, air, low population density 2.37E-6 MJ

• Chloromethane production (For 1g Al2O3)Inventory results for CH3Cl production (Based on Zah and Hischier 2007; Hischier et al. 2005; NIST 2013)Input materials Quantity Output materials QuantityCH3OH 4.14g CH3Cl 6.21gHCl 4.73g H2O 2.21gEnergy 2.67kJ CH3OH 0.20gChemical plant, organics 2.48E-12 Unit HCl 0.24g

• Trimethylaluminium production (For 1g Al2O3)Inventory results for Al (CH3)3 production (Based on Zah and Hischier 2007; Hischier et al. 2005;NIST 2013)

Input Quantity Output QuantityAl 1.11g Al(CH3)3 2.80gCH3Cl 6.21g NaCl 6.83gNa 2.83g Al 0.06gEnergyChemical plant, organics

5.01kJ1.12E-12 Unit

CH3Cl 0.31g

Na 0.14g

• Wafer production (1g Al2O3) Materialinput

Electricity, medium voltage, production UCTE, at grid/UCTE U

9.20E-1 kWh

Natural gas, burned in industrial furnace low-NOx>100kW/RER U

7.30E-1 MJ

Tap water, at user/RER U 1.01 kgSilicon, production mix, photovoltaics, at plant/GLO U 1.00E-2 kgArgon, liquid, at plant/RER U 6.00E-2 kgNitric acid,50% in H2O, at plant/RER U 1.00E-3 kgAcetic acid, 98% in H2O,at plant/RER U 1.00E-3 kgAcetone, liquid, at plant/RER U 1.00E-3 kgSodium hydroxide,50% in H2O, production mix, at plant/RER U

4.00E-4 kg

Ceramic tiles, at regional storage/CH U 4.00E-3 kgLime, hydrated, packed, at plant/CH U 2.00E-3 kgTransport, lorry >16 t, fleet average/RER U 1.90E-2 tkmTransport, freight, rail/RER U 4.30E-2 tkm

Resourceuse

Water, cooling, unspecified nature origin/m3 2.50E-2 m3Water, river 2.20E-2 m3

Emission to air

Heat, waste 3.32 MJ

Emission to water

Hydrocarbons, unspecified 2.00E-4 kgAcetic acid 5.00E-4 kgBOD 5, Biological Oxygen Demand 1.00E-3 kgCOD, Chemical Oxygen Demand 1.00E-3 kgDOC, Dissolved Organic Carbon 4.00E-4 kgTOC, Total Organic Carbon 4.00E-4 kgNitrogen 1.00E-4 kg

2. ALD chemical reaction inventory (For 1g Al2O3)

ALD ( A 30 nm thick Al2O3 film; with 300-cycle ALD processes at 200℃)Input OutputTMA 2.80g CH4 0.94gH2O 26.03g Al2O3 1.00gN2 682.00g N2 682.00gALD system Cambridge NanoTech Savannah

20049.6%TMA emissions

1.39g

Reactor 4 inch standard wafer,150mm inner diameter and 5 mm inner depth

97.97%Waste water

25.48g

Total energy 1.71GJ

3. Infrastructure, equipment and tools (Economic inventory) (For 1g Al2O3)

The economic inventory with Cambridge NanoTech Company data and RS Means 2013Items Description quantities Total costALD system Savannah S100: Standard 4”

ALD- reactor; S100 Dome Lid w/ cassette: Dome lid with cassette for 10 wafers

0.0282 Piece $3,130(Price)

Roughing pump Alcatel 2005I – Fomblin prepped 0.0282 Piece $83(Price)

Precursor line Hot precursor lines 0.0282 Pieces $479(Price)

Laboratory Area is around 6m2 0.00376 Piece $48(Cost)

Computer Assume 3 years’ service life (Williams 2004)

0.094 Piece $94(Price)

4. Detailed process-based LCA modeling in Gabi 6.0

Full list of inventory data used in Gabi modeling Inventory data are listed as unit-process-based (i.e. individual module) with the top-down sequence in terms of module rows and the left-right sequence in terms of module columns in the above Gabi model.

Unit process Quantities

US: Natural gas mix PE 4.62E-4 kgUS: Electricity grid mix PE 3.33E-05 kWhGLO: methanol infrastructure [organics] 1.54E-13 piecesRER: Natural gas PlasticsEurope 2.57 E-03 kgBiomass (solid) for bioenergy [Biomass for energy use](included in methanol production from natural gas <u-so>)

2.07E-06 kg

Water [Water] (included in methanol production from natural gas <u-so>) 2.23 E-03 kgOxygen [Renewable resources](included in methanol production from natural gas <u-so>)

1.57 E-03 kg

CH: transport, tractor and trailer [work processes](included in methanol production from natural gas <u-so>)

4.13E-05 t*km

DE: transport, natural gas, pipeline, long distance [Appropriation](included in methanol production from natural gas <u-so>)

4.13E-03 t*km

CH: transport, freight, rail, diesel, with particle filter [Railway] (included in methanol production from natural gas <u-so>)

4.13E-05 t*km

US: Diesel mix at refinery PE 1.61E-5 kgDE: Hydrochloric acid mix (100%) PE 4.72 E-03 kgUS: Diesel mix at refinery PE 9.58E-6 kgGLO: Truck PE <u-so> 4.14 E-3kgUS: Electricity grid mix PE 1.20E-1 kWhGLO: Rail transport cargo - average PE <u-so> 4.14 E-3 kgGLO: Truck PE <u-so> 4.72 E-3 kgChemical plant, organics <u-so> 2.48E-12 kgUS: Electricity grid mix PE 1.13E-2 kWhUS: Electricity grid mix PE 6.12E-2 kWhUS: Diesel mix at refinery PE 1.44E-5 kgChemical plant, organics <u-so> 1.12E-12 kgUS: Diesel mix at refinery PE 1.58 E-3kgRER: Aluminum ingot mix (2005) EAA 1.11 E-3kgGLO: Truck PE <u-so> 6.21E-3 kgRER: Aluminum sheet (2005) EAA <p-agg> 1.11 E-3 kgEU-27: Nitrogen PE 6.80E-1 kgGLO: Rail transport cargo - average PE <u-so> 6.21E-3 kgUS: Diesel mix at refinery PE 2.56E-6 kgGLO: Truck PE <u-so> 6.80E-1 kgGLO: Truck PE <u-so> 1.11E-3 kgGLO: Rail transport cargo - average PE <u-so> 1.11E-3 kgUS: Diesel mix at refinery PE 6.48E-6 kgGLO: Truck PE <u-so> 2.80E-3 kgGLO: Rail transport cargo - average PE <u-so> 6.80E-1 kgRER: Process water PE 1.30E+3 kgUS: Electricity grid mix PE 6.48E-5 kWhGLO: Rail transport cargo - average PE <u-so> 2.80E-3 kg

US: Electricity grid mix PE 5.23E+2 kWhGLO: Rail transport cargo - average PE <u-so> 2.60E -2 kgGLO: Truck PE <u-so> 2.60E -2 kgGLO: Truck PE <u-so> 1.18E -2 kgDE: Lime (CaO; quicklime lumpy) PE 1.04 E-1 kgGLO: silicon, production mix, photovoltaics, at plant [refinement](Included in wafer production <u-so>)

5.21 E-1 kg

RER: acetic acid, 98% in H2O, at plant [organics](Included in wafer production <u-so>)

5.21 E -2 kg

RER: acetone, liquid, at plant [organics](Included in wafer production <u-so>)

3.12 kg

RER: natural gas, burned in industrial furnace low-NOx >100kW [heating systems] (Included in wafer production <u-so>)

1.06E+1 kWh

RER: nitric acid, 50% in H2O, at plant [inorganics](Included in wafer production <u-so>)

5.21 E -2 kg

RER: sodium hydroxide, 50% in H2O, production mix, at plant [inorganics] (Included in wafer production <u-so>)

2.08 E -2 kg

RER: tap water, at user [Appropriation](Included in wafer production <u-so>)

5.26 E+1 kg

RER: transport, freight, rail [Railway](Included in wafer production <u-so>)

2.24 t*km

RER: transport, lorry >16t, fleet average [Street](Included in wafer production <u-so>)

0.99 t*km

Water (river water) [Water] (Included in wafer production <u-so>) 1.15E+3 kgEU-27: Landfill of municipal solid waste PE <p-agg> 1.18E-2

5. Results• Life cycle impact assessment results

LCIA results with TRACI FP FT CR WD IETAA (kg SO2 eq) 5.96E-04 8.47E-05 1.35E+00 3.01E-07 1.11E+01AW(kg SO2 eq) 7.74E-07 3.19E-08 1.28E-03 1.57E-10 1.90E+00ET (CTUe) 2.52E-02 3.71E-06 2.51E-02 3.10E-08 1.98E+02EA (kg N eq) 2.56E-05 3.80E-06 1.32E-01 2.60E-08 3.10E-01EW (kg N eq) 2.43E-04 5.02E-07 1.06E-02 3.32E-07 1.40E-03GWP (kg CO2 eq) 1.69E-01 1.33E-02 3.28E+02 1.17E-03 2.14E+03HH (kg PM 2.5 eq) 5.11E-05 4.05E-06 9.31E-02 2.97E-07 6.47E-05HTC (CTUh) 1.80E-11 2.49E-13 9.69E-09 7.12E-15 1.55E-07HTN (CTUh) 1.26E-10 2.28E-14 7.28E-10 6.92E-15 5.98E-06ODA (kg CFC-11 eq) 1.49E-09 3.66E-12 1.44E-07 2.61E-14 1.21E-03RFF (MJ energy) 2.02E-01 1.66E-02 2.02E+02 9.61E-05 3.05E+02SA (kg O3 eq) 7.58E-03 1.60E-03 1.13E+01 7.73E-06 1.69E+02

6. Normalized results• Normalization factors table (Based on Bare et al. 2006; Lautier et al. 2010)

AA (kg SO2 eq)6.66E+13

AW(kg SO2 eq)3.01E+10

ET (CTUe)1.77E+13

EA (kg N eq)1.44E+09

EW (kg N eq)3.58E+09

GWP (kg CO2 eq)6.85E+12

HH (kg PM 2.5 eq)2.13E+10

HTC (CTUh)2.14E+01

HTN (CTUh)7.32E+03

ODA (kg CFC-11 eq)8.69E+07

RFF (MJ energy)1.14E+07

SA (kg O3 eq)8.38E+11

• Normalized impact results

FP FT CR WD IETAA 8.95E-18 1.27E-18 2.02E-14 4.52E-21 1.66E-13AW 2.57E-17 1.06E-18 4.25E-14 5.22E-21 6.31E-11ET 1.43E-15 2.10E-19 1.42E-15 1.75E-21 1.12E-11EA 1.78E-14 2.64E-15 9.14E-11 1.81E-17 2.15E-10EW 6.80E-14 1.40E-16 2.96E-12 9.28E-17 3.92E-13GWP 2.46E-14 1.94E-15 4.79E-11 1.71E-16 3.13E-10HH 2.40E-15 1.90E-16 4.37E-12 1.39E-17 3.04E-15HTC 8.42E-13 1.16E-14 4.53E-10 3.33E-16 7.24E-09

HTN 1.72E-14 3.12E-18 9.94E-14 9.46E-19 8.17E-10ODA 1.72E-17 4.21E-20 1.65E-15 3.01E-22 1.40E-11RFF 1.77E-08 1.46E-09 1.77E-05 8.43E-12 2.68E-05SA 9.04E-15 1.90E-15 1.35E-11 9.22E-18 2.02E-10

ReferencesBare, J., Gloria, T., Norris, G., 2006.Development of the method and U.S. normalization

database for life cycle impact assessment and sustainability metrics. Environmental Science & Technology 40(16), 5108-5115.

DOE,2013.U.S. Life Cycle Inventory Database. National Renewable Energy Laboratory. Accessed July19, 2013: https://www.lcacommons.gov/nrel/search.

Griffiths, O. G., O’Byrne, J. P., Torrente-Murciano, L., Jones, M. D., Mattia, D., McManus, M. C., 2013. Identifying the largest environmental life cycle impacts during carbon nanotube synthesis via chemical vapour deposition. Journal of Cleaner Production 42, 180-189.

Hellweg, S., 2003. Chemicals Part I. Special LCA forum. ETH Lausanne.Hischier, R., Hellweg, S., Capello, C., Primas, A., 2005. Establishing life cycle inventories of

chemicals based on differing data availability. The International Journal of Life Cycle Assessment 10 (1), 59-67.

Lautier, A., Rosenbaum, R. K., Margni, M., Bare, J., Roy, P., Deschênes, L., 2010. Development of normalization factors for Canada and the United States and comparison with European factors. Science of the Total Environment 409,33–42.

NIST,2013.NIST Chemical Kinetics Database. Accessed December 2, 2013: http://kinetics.nist.gov/kinetics/index.jsp

Zah R and Hischier R (2004). Life cycle inventories of detergents. Ecoinvent Report No. 12, Swiss Centre for Life Cycle Inventories: Du¨bendorf, Switzerland, 2004.