## Developing a Reliable Fluorinated Greenhouse Gas (F-GHG)

Destruction or Removal Efficiency (DRE) Measurement Method for

Electronics Manufacturing: A Cooperative Evaluation with IBM

June 2009

Office of Air and Radiation

Office of Atmospheric Programs, Climate Change Division

EPA 430-R-10-004

## Acknowledgements

The analytical measurements, data interpretation, and report preparations were funded by the U.S.

Environmental Protection Agency under contract EP

‐ W

‐ 07

‐ 068 to ICF International and Air Products and

Chemicals, Inc. The authors wish to express their appreciation and thanks to IBM for their gracious

support to this study by not only providing their facilities but also their valuable assistance and advice.

The U.S. EPA looks forward to continued collaborations with IBM and other Partners in the PFC

Reduction/Climate Change Partnership for Semiconductors.

1

### Table of Contents

Acknowledgements

.............................................................................................................. .............................. 1

1. Introduction

............................................................................................................................... ................... 4

2. Experimental Procedures

....................................................................................................... .................... 5

3. Results and Discussion

........................................................................................................ ...................... 8

3.1 Process Dilution

.......................................................................................................... ........................ 8

3.2 Scrubber Dilution

......................................................................................................... ....................... 9

3.2.1 Scrubber DRE While Measuring Process Diluti on Determination—No Wafer Processing

.......... 12

3.2.2 Etch Process Emissions and Scrubber DRE Measurements during Wafer Processing

.............. 14

3.3 Multiple Inlet Experiment—Simultaneous Multi-chamber Monitoring During Wafer Processing

....... 22

3.4 NDIR-FTIR Comparison

...................................................................................................... .............. 27

3.4.1 NDIR Data Collected on FK15

.............................................................................................. ........ 27

3.4.2 NDIR Data Collected on FE05

.............................................................................................. ........ 29

4. Summary and Conclusions

....................................................................................................... ............... 30

2

### Abbreviations

BE Back End

DRE Destruction or Removal Efficiency

CF4 Carbon Tetrafluoride

FE Front End

FTIR Fourier Transform Infrared

Kr Krypton

MFC Mass Flow Controller

NDIR Non

‐ Dispersive Infrared

NF3 Nitrogen Trifluoride

PFC Perfluorocarbon

PPMV Parts per million

POU Point of Use

QMS Quandrupole Mass Spectrometer

SCCM cm3/min

SF6 Sulfur Hexafluoride

SL Standard Liter

SLM Standard Liters per Minute

TPU Thermal Processing Unit

3

## 1. Introduction

In 2007, U.S Environmental Protection Agency (EPA) initiated measurements of the Destruction or

Removal Efficiency (DRE) of perfluorocarbons (PFC), sulfur hexafluoride (SF

6 ) and nitrogen trifluoride

(NF

3 ) by Point of Use (POU) abatement systems or scrubbers during semiconductor processing. EPA

funded this work in support of the PFC Reduction/Climate Partnership for the Semiconductor Industry

and to inform the development of a protocol for measuring DREs of PFCs, SF 6 , and NF 3

. The work

presented in this report builds on DRE protocol

‐ development work conducted at two other North

American integrated device manufacturing sites in 2007 as well as comments EPA received during

review of an initial draft of the DRE measurement protocol.

For the work reported here, testing was conducted at IBM’s East Fishkill, New York 300

‐ mm wafer

facility on 1

– 5 December, 2008. The tests were performed on two multi

‐ chamber etch process tools.

The etch chemistries employed carbon tetrafluoride (CF

4 ) and sulfur hexafluoride (SF

6 ), which represent

two of the more problematic etchants to abate. One process tool, FE05, enabled a front end (FE)

polysilicon etch process with a nitride break through step. The second process tool, FK15, enabled a

back end (BE) dielectric etch for dual damascene Cu patterning. Testing was performed during normal

multi

‐ chamber wafer processing.

The output of each tool was fed into a POU scrubber. Each etch tool had four chambers feeding the

single scrubber. Different experimental configurations, data collection and data reduction methods were

tested to identify differences, if any, on the scrubber DRE measurement. In addition, CF 4 scrubber

effluents were monitored with a Non

‐ Dispersive Infrared (NDIR) device.

The scrubbers were thermal/wet systems, each containing a natural

‐ gas

‐ fired combustion chamber

followed by a post combustion water scrubber. No adjustments were made to the scrubbers and they

were tested under normal operating conditions. One scrubber had recently completed its scheduled

preventative maintenance.

An essential feature of the protocol under development is the use of a chemical tracer or spiking

approach to measure the total scrubber flow, which accounts for the total dilution across the scrubber.

Previous tests have demonstrated the efficacy of krypton (Kr) as a spiking agent. Using other spiking

agents, such as CF 4 , may require disabling the combustion chamber, which undesirably releases CF 4

directly to the atmosphere.

The analytical equipment deployed to determine DRE values included a Quadrupole Mass Spectrometer

(QMS), which was used to monitor Kr emitted by the scrubber after its addition as a tracer at the inlet to

the scrubber. Two Fourier Transform Infrared (FTIR) spectrometers were used to monitor process and

scrubber emissions. In addition, an (NDIR) detector was deployed to monitor CF 4 emissions from the

scrubber.

The report describes two methods for measuring etchant scrubber DRE for the tool/recipe

combinations. The first (Method 1) measures scrubber DRE with process plasma off (no wafer

4processing), but with etchant gas flowing through the tool. The second method, which may be

approached in two ways, measures etchant DRE during actual, multi

‐ wafer processing, typically greater

than five wafers. The first of these two approaches (Method 2a), sequentially measures etchant PFC

volumes for each chamber while simultaneously measuring the corresponding etchant volumes exiting

the scrubber from all chambers. The second approach (Method 2b) measures scrubber effluent etchant

volumes while simultaneously extracting a slip

‐ stream of process gases from each chamber, which are

then combined and the total etchant volume flow is measured prior to entering the scrubber. 1 The

results of all three methods are presented and compared.

This report begins by describing the experimental procedures used during the testing, which is followed

by a description of key data necessary for calculating the DREs including the process dilution, scrubber

dilution, and process and scrubber emissions during wafer processing. This report then presents and

compares results and discussion regarding Method 1, Method 2a, and Method 2b, as well as results

from a multiple inlet experiment. This report also presents a comparison of emission profiles for data

collected by FTIR and NDIR. This report ends with a summary of methods and results and conclusions

based on the testing and results.



## 2. Experimental Procedures

Sampling was conducted by monitoring process and scrubber emissions simultaneously. Scrubber

dilution was determined through the use of chemical spiking. Process and scrubber emissions data were

collected in parallel using Fourier Transform Infrared Spectroscopy (FTIR). Data used to determine

scrubber dilution were collected using Quadrupole Mass Spectrometry (QMS). The experimental

configuration for Methods 1 and 2a is shown in Figure 1 and the two methods are described here. The

configuration for Method 2b (the multiple

‐ chamber method) is described in section 3.3 (cf. Figure 11).

Two FTIRs were used to determine process and scrubber emissions. Both systems were MKS 2010 Multi

Gas Analyzers equipped with liquid nitrogen cooled mercury cadmium telluride detectors. The FTIR that

measured pre

‐ scrubbed gas concentrations was equipped with a 10 cm path length single pass gas cell.

The FTIR used to measure scrubber effluent concentrations was equipped with a 5.6 m path length multi

pass gas cell. Both FTIRs were operated at 0.5cm ‐ 1 resolution. Four scans were co

‐ added for each data

point yielding a sampling frequency of 2.2 seconds. Calibration curves for CF 4 , SF 6 and other

perfluorinated compounds were developed at Air Products laboratories located in Allentown PA.

A UTI 2221 QMS system was used to sample scrubber effluent during dilution determination. The QMS

was operated in Selective Ion Monitoring (SIM) mode and a secondary electron multiplier was used to

enhance sensitivity. A two second sampling frequency was used for each data point. To account for

1 This sampling approach was implemented following the suggestion of a reviewer of the first draft of the DRE

Protocol and an assessment that mixing the gas streams from the different etch chambers during the planned

testing posed no safety risks.

5potential changes in QMS sensitivity, ion signals were normalized to the signal obtained for the nitrogen

fragment (N+), which is formed during electron impact ionization of N 2

.

Sampling of effluent streams was done using metal bellows sampling pumps that were located after the

instruments. The sample flow rate was controlled using adjustable flow rate valves. The sample line

pressure for both FTIRs and the QMS were monitored using capacitance manometers. A sample filter

was installed in the sample line used for monitoring scrubber emissions to ensure that particulate

emissions from the scrubber would not coat the FTIR internal optics or the pressure reducing orifice

used for the QMS. Since the scrubber DRE determination and the scrubber dilution determination were

independent events, it was possible to use the same sample line for both operations. This was

accomplished by switching the instrument inlet sample fitting from the FTIR to the QMS.

A CS Clean Systems NDIR model CIP1281 was used to monitor CF 4 emissions from the scrubbers. The

system used an external sample pump to extract gas through the gas cell. Data were collected and

recorded at 1 Hz. CF 4 concentrations were reported as whole number values. The sample configuration

of the NDIR sampling is also shown in Figure 1. Sample gas was extracted through 0.25” o.d. PFT tubing.

A pre

‐ filter supplied by the vendor was deployed to remove any HF emitted by the scrubber.

The QMS was calibrated to determine its response to Kr on site using a dynamic dilution blending

system. Test atmospheres containing Kr were created by blending a calibration standard containing 1%

Kr with N 2 diluent. These calibration standards are specified with an accuracy of ± 5% or better. 

### Figure

2 shows the QMS response to 84 Kr during calibration and the calibration curve resulting from a

regression analysis of these data. The calibration curve, which showed a small non

‐ zero, positive

intercept, was used for the tests on both tools. These data were used to quantify Kr emissions from the

scrubber.

6Figure 1 : Sampling scheme used to monitor process and scrubber emissions on FK15 and FE05.

0.00E+00 5.00E

‐ 04 1.00E

‐ 03 1.50E

‐ 03 2.00E

‐ 03 2.50E

‐ 03 3.00E

‐ 03

0 50 100 150 200 250 300 350 400 450IonIntesityRatio(m/e84:m/e14)

QMS Scan Kr Calibration Data

0.00E+00 5.00E

‐ 04 1.00E

‐ 03 1.50E

‐ 03 2.00E

‐ 03 2.50E

‐ 03

0 2 0 4 0 6 0 8 0 1 0 0 1 2 0IonIntensity

Concentration of Added Kr m/e 84

Predicted

Figure 2 : Calibration of QMS response to Kr in nitrogen (right) using the ratio of 84 Kr + /N +

. Regression

analysis plot is shown on the left.

7

## 3. Results and Discussion

This section presents the results for measuring process dilution and scrubber dilution as well as

measurements of etchant specific DREs. First, etchant

‐ specific DREs are presented without wafer

processing for each etching tool. Then, etchant

‐ specific DREs are presented that were measured during

normal wafer processing. Finally, DREs are provided for the sequential single

‐ chamber method for FK15

and FE05 etch tools and for the simultaneous multi

‐ chamber method for FK15. Time constraints limited

testing the simultaneous multi

‐ chamber method to only FK15.



## 3.1 Process Dilution

Process dilution is defined as the dilution of a process gas or by

‐ product that occurs in the process

chamber and at the process vacuum pump resulting from the addition of N 2

. This dilution is

experimentally measured by flowing process gas through the chamber with the RF power turned off.

The dilution is calculated from the measured concentration and known flow rate. These data are used

to integrate process emissions during wafer processing and to measure dilution occurring across the

scrubber.

The dilution of each chamber on FK15 and FE05 was determined using CF 4 flows. Figure 3 shows the

process emission profile for each chamber on FK15. The concentrations were used to calculate total

flows through the exhaust from each of the four process chambers and process pump purge. Those

flows are provided in Table I. Also included in Table I are results for the same experiment conducted on

FE05. After completing chamber 4 flows, all 4 chambers were set to 200 sccm to provide the highest CF 4

flow challenge possible with the Mass Flow Controllers (MFCs) on FK15

8Concentration(ppmv)

FTIR Scan

Figure 3 : CF 4 emission profile from FK15 during flow calibrations on chambers 1

– 4.

Table I : Process dilution flow determined for chambers 1

‐ 4 on FK15 and FE05



### FK15 Chamber Total Flow

(slm) FE05

Chamber Total Flow

(slm)

1 52.3 1 47.3

2 45.0 2 54.0

3 45.5 3 52.7

4 47.3 4 48.5



## 3.2 Scrubber Dilution

There are several installation

‐ specific sources of scrubber dilution, which, while individually identifiable,

are difficult to measure reliably under fab conditions. Dilution can occur from effluents from other

chambers, combustion gases and by

‐ products added to and generated within the scrubber, vapors

added as the gas stream passes through the water scrubber portion of the system, in

‐ board leaks, and

9back diffusion from main headers. The method for measuring dilution in these tests was to observe the

effective dilution that occurred when a known flow of an inert (spiking) chemical—the analyte—was

added to the gas stream entering the scrubber. The measured concentration of the inert analyte, 

### C

an ,

leaving the scrubber provides the means to calculate the total scrubber flow, TF. A total flow from the

scrubber can be calculated from the measured concentration and the controlled spike

‐ gas flow rate, 

### S f

,

added to the process exhaust duct:



### TF = S f 

### /( C

an 

### X 10 ‐ 6 

### ) (Equation 1)

Where: the spike gas flow (S f ) is in liters, and the analyte concentration (C

an ) is in ppmv.

The experiment conducted to determine dilution for the scrubbers on FE05 and FK15 consisted of using

the calibration system, shown in Figure 1, to add calibration gas into the process effluent through the

FTIR sample line where process effluent was monitored. While calibration gas was being added, the

QMS was sampling the scrubber effluent. The flow of calibration gas was controlled with two 0

– 5 slm

Mass Flow Controllers (MFC) that were calibrated for nitrogen. Different flow rates were added to the

scrubbers. The concentration profile for 84 Kr determined from QMS data during spiking is shown in

Figure 4 for FE05. From these data total flow data were calculated for each flow rate using Equation 1

and are shown in Table II below. From these data a total flow of 850 ± 3 (95 percent confidence

interval) 2 slm was determined and used subsequently in all DRE calculations.

Table II: Kr spiking results for POU System on FEO5: Total flows calculated using Equation 1



### Total Calibrated Gas

Flow (slm) 84 

### Kr Concentration

(ppmv) Total Flow through Thermal

Processing Unit (TPU)

(sl)

8.34 98 ± 3 851

6.65 79 ± 2 841

4.98 59 ± 1 844

3.33 39 ± 1 853

1.67 20 ± 1 835

1.00 11 ± 1 909

0.70 8 ± 1 850

2 The mean value and confidence interval was estimated using the method of variance, which explains why the

figure 850 slm is not the simple mean of the figures given in Table II.

10

### Kr Concentration Determined in FE05 TPU Effluent for Various Spike

Flows of 1% Kr StandardConcentration(ppmv) 115

95

75

55

35

15

‐ 5 600 700 800 900 1000 1100 1200 1300 8.34 sl

6.65 sl

4.98 sl

3.33 sl

1.67 sl

1.00 sl 0.70 sl

QMS Scan

Figure 4: Concentration profile determined for Kr spiking of POU abatement system on FE05.

A similar experiment on FK15 yielded a total flow of 780 ± 3 (95 percent confidence interval) slm. Data

for this flow determination are shown in Table III. 3 This total flow was used for all subsequent DRE

calculations.

Table III: Kr spiking results for POU System on FK15: Total flows calculated using Equation 1)



### Total Calibration

Gas Flow (slm) 84 

### Kr Concentration

(ppmv) Total Flow through Thermal

Processing Unit (TPU)

(sl)

8.34 108 ± 3 772

6.65 87 ± 2 764

4.98 62 ± 2 803

3.33 44 ± 2 757

1.67 21 ± 2 795

3 See footnote 3, p.10 replacing Table II with Table III.

11 1400

## 3.2.1 Scrubber DRE While Measuring Process Dilution Determination—No Wafer

Processing

While measuring process dilution, scrubber PFC abatement performance may also be measured. These

measurements permit DRE measurements on each of the four chambers for each etchant. However,

because power to the plasma is turned off during these experiments, the gas mixture entering the

scrubber differs from the gas mixture during wafer processing.

Figure 5 shows the CF 4 emission profile from the scrubber on FK15 during the process dilution

experiments. The DRE was calculated as one minus the ratio of average CF 4 inlet concentration to the

corresponding dilution adjusted scrubber (emission) concentration. DREs and dilution factors for CF 4 for

each one of the four chambers and each tool are provided in Table IV. Results for SF 6 , which was used

on FE05, are also provided in Table IV. Note that chamber

‐ specific dilution factors varied by as much as

13 percent for FK15 and FE05 (17 percent for chambers 2 or 3 for FK15 vs. 15 percent for chamber 1.) It

is also interesting to note that when all four chambers were flowing maximum CF 4 flows of 200 sccm

each, an increase in DRE was observed relative to when CF 4 was flowed through the individual

chambers. This effect was more pronounced for the scrubber on FK15 than for the scrubber on FE05.

Other PFCs evaluated during the process dilution flow testing on FK15 included CHF 3 , CH 2 F 2 and CH 3 F.

CH 2 F 2 and CH 3 F were not detected in the scrubber effluent. A low concentration of CHF 3 was detected

in the scrubber effluent of FK15 during CHF 3 flows through the tool and scrubber. The CHF 3 DRE was

determined to be greater than 99 percent based on detecting 0.5 ppmv CHF 3 when flowing 100 sccm

through chamber 2.

12Figure 5: CF 4 emissions from scrubber on FK15 during process flow calibration experiments. The initial

high CF 4 concentration observed on chamber 1 was attributed to the scrubber being in low fire mode.

13Table IV: Scrubber DRE values for CF 4 and SF 6 during process flow calibrations on chambers 1

‐ 4 of each

etch tool. SF 6 was only available on FE05.



### Tool: Chamber Dilution Factor CF 4 

### DRE SF 6 

### DRE

FK15 #1 14.9 87.5 % Na

FK15 #2 17.3 63.1 % Na

FK15 #3 17.2 79.4 % Na

FK15 #4 16.5 77.4 % Na

All 4 Chambers 4.1 89.3 % Na

FE05 #1 18.0 84.5 % 99.0 %

FE05#2 15.7 82.2 % 98.9 %

FE05 #3 16.1 91.7 % 99.0 %

FE05 #4 17.5 96.0 % 99.0 %

All 4 Chambers 4.2 92.7 % Na



## 3.2.2 Etch Process Emissions and Scrubber DRE Measurements during Wafer Processing

In this section, measurements of DRE during actual wafer processing are presented for FK15 and then

FE05. For FK15, measured (integrated) CF 4 emission volumes are provided during wafer processing for

each etch process, each chamber, each wafer (and averaged over all wafers) together with the

corresponding measured (integrated) scrubber emissions of CF 4

. Using these measurements DREs for

CF 4 are calculated. For FE05, the same procedure was followed for both CF 4 and SF 6 measurements and

the average DRE over all wafers are provided for CF 4 and SF 6

. Process and scrubber dilutions are

reflected in the reported CF 4 and SF 6 gas volumes.

Process emissions on etch tool FK15 were monitored and emission volumes were determined for CF 4

process gases and by

‐ products. Effluent was monitored on chambers 1 and 3; these were the chambers

operating during production. CF 4 emission volumes were determined per wafer for two etch processes,

trench and via etch, on each chamber. Figure 6 shows the CF 4 emission profile observed for the

monitored Back End (BE) trench etch for several wafers monitored on each chamber. Integration of the

CF 4 emission peaks yielded volumes contained in Table V. The emission volumes from each chamber

were similar (0.184 sl vs. 0.186 sl).

14Concentration(ppmv)

FTIR Scan

Figure 6 : CF 4 emission profile observed for a back end trench etch process on FK15

Table V : Integrated CF 4 emissions from trench etch process run on FK15



### Trench Etch Chamber

1 Integrated CF 4



### Emissions (sl) Trench Etch Chamber

3 Integrated CF 4



### Emissions (sl)

Wafer 1 0.181 Wafer 1 0.188

2 0.183 2 0.188

3 0.183 3 0.188

4 0.185 4 0.187

5 0.185 5 0.182

6 0.187 6 0.184

Ave 0.184 Ave 0.186

A second etch process, a BE via etch, was also monitored on Chambers 1 and 3. The CF 4 emission profile

for this process is shown in Figure 7. From these data integrated emissions were determined for

chambers 1 and 3, and are shown in Table VI. A difference of 5 % in CF 4 emission volume was observed

between the chambers.

15Table VI : Integrated CF 4 emissions from via etch process run on FK15



### Via Etch

Chamber 1 Integrated CF 4



### Emissions (sl) Via Etch

Chamber 3 Integrated CF 4



### Emissions (sl)

Wafer 1 0.114 1 0.107

2 0.115 2 0.109

3 0.112 3 0.109

4 0.114 4 0.108

5 0.113 5 0.108

Ave 0.114 Ave 0.108Concentration(ppmv)

FTIR Scan

Figure 7 : CF 4 emission profile observed during BE Via etch on FK15 chambers 1 & 3.

16Process emissions for a Front End (FE) etch were monitored on etch tool FE05 to determine emission

volumes for PFC process gases and by

‐ products. Effluents from chambers 3 and 4 were monitored as

these were the chambers operating during production. The emission volumes were determined per

wafer for a single process on each chamber. Figures 8a

‐ b show the CF 4 and SF 6 emission profiles

observed for the etching of several wafers monitored on each chamber. Integration of the CF 4 and SF 6

emissions yielded volumes shown in Table VII. These data were used to calculate CF 4 and SF 6 loading on

the scrubber.

Table VII: Integrated CF 4 and SF 6 emissions from FE etch process run on FE05



### Chamber 4 CF 4 

### Emission

Volume (sl) SF 6 

### Emission

Volume (sl) Chamber 3 CF 4 

### Emission

Volume (sl) SF 6 

### Emission

Volume (sl)

Wafer 1 0.015 0.077 Wafer 1 0.015 0.081

2 0.016 0.078 2 0.015 0.085

3 0.015 0.078 3 0.015 0.085

4 0.015 0.077 4 0.015 0.085

Ave 0.015 0.078 Ave 0.015 0.085

17Figures 8a

‐ b : Emission profiles for CF 4 and SF 6 on Chambers 3 & 4 of FE05.

Table V, Table VI, and Table VII contain data that were used to calculate loading of CF 4 and SF 6 on the

scrubbers while simultaneously monitoring the scrubber effluent for CF 4 and SF 6

.

Figures 9a

‐ b show CF 4 emissions from the scrubber on FK15 during the BE trench and via etching.

Integration of emissions as indicated by the arrows provided emission volumes from the scrubber for a

set number of wafers processed. These volumes were used to calculate the CF 4 DRE for the scrubber

during each process. The total volume of CF 4 loading on the scrubber was determined from the product

of the total number of wafers monitored and the CF 4 emission volume per wafer. For the trench etch,

180.185 sl CF 4 was emitted from the process per wafer yielding a total loading for 25 wafers of 4.63 sl (= 25

X 0.185). The via etch emitted 0.11 sl CF 4 per wafer yielding a total loading of 2.20 sl for the 20 wafers

processed (= 20 X 0.11).

The DRE was calculated from the ratio of CF 4 scrubber emissions to loading volumes. DRE values of 83

percent and 85 percent for the trench and via etch, respectively, were consistent with the average of

the CF 4 DRE determined for chambers 1 and 3 during CF 4 process flow calibrations (see Table IV; using

CF 4 DREs for chambers 1 and 3 gives an average DRE of 84 percent [= {88 + 79}/2]). In this instance,

scrubber performance appears robust over the different gas mixtures entering the scrubber.

The FE etch process ran on FE05, using chambers 3 and 4, produced CF 4 and SF 6 emissions which were

detected in the scrubber effluent. The emission profiles for CF 4 and SF 6 from the scrubber are shown in

Figures 10a

‐ b. These emission profiles correspond to the process emissions shown in Figures 8a

‐ b.

Scrubber emissions were integrated over 20 wafers and the volumes were divided by the corresponding

process emission volumes to determine the CF 4 and SF 6 DRE. These data, presented in Table IX, indicate

a CF 4 DRE of 90 percent and an SF 6 DRE of greater than 99 percent. These results are also consistent

with the scrubber performance during the process dilution flow experiments when wafers were not

being processed. Using a simple average from the process flow experiments for chambers 3 and 4 gives

an average DRE of 94 percent (see Table IV for chambers 3 and 4) compared to the 90 percent DRE

obtained during actual wafer processing. For SF 6 , the process flow experiments for chambers 3 and 4

gives an average SF 6 DRE of 99 percent (see Table IV, chambers 3 and 4).

19Table VIII: Scrubber CF 4 DRE determined for BE trench and via etch on FK15

Total # Wafers

Monitored CF 4 Loading on

Scrubber

(sl) CF4 Scrubber

Emissions

(sl) CF4 DRE

(%)

Trench Etch 25 4.63 0.81 83

Via Etch 20 2.20 0.34 85

Table IX : Scrubber CF 4 and SF 6 DRE determined for FE etch on FE05

Total #

Wafers

Monitored CF 4 loading

on Scrubber

(sl) CF 4 Scrubber

Emissions

(sl) CF 4 DRE

(%) SF 6

loading

on

Scrubber

(sl) SF 6

Scrubber

Emissions

(sl) SF 6 DRE

(%)

FE Etch 20 0.300 0.029 90 1.64 0.004 > 99

20Concentration(ppmv)Concentration(ppmv)

FTIR Scan

FTIR Scan

Figures 9a

‐ b : CF 4 emissions from scrubber during trench etch (top) and via etch

21Figures 10a

‐ b : CF 4 and SF 6 emission profiles from scrubber on FE05 during FE etch



## 3.3 Multiple Inlet Experiment—Simul taneous Multi-chamber Monitoring

During Wafer Processing

An experiment was conducted to determine the efficacy of sampling a combined slip stream from each

chamber running process on FK15, while simultaneously monitoring the outlet concentration of the

scrubber (Method 2b). The purpose of this experiment was to determine if it is possible to get a sample

representative of the actual gas composition in the scrubber. The experiment consisted of drawing

controlled flows of process emissions from each operating chamber (1 and 3) from FK15, and combining

these into a common sample line, which pumps them through the FTIR gas cell. (See Figure 11 for

illustration of the experimental set

‐ up used to conduct this experiment.) The Mass Flow Controllers

(MFCs) were used to measure the sample flow from each chamber’s exhaust. Needle valves were used

to control the flow. The ratio of sample flow was set equal to the ratio of process dilution for each

chamber. For this experiment, the ratio of process flow for chambers 1 and 3 was 1.15 (52 slm chamber

1, 45 slm chamber 3, cf. Table I). The sample flows were adjusted to 210 sccm and 240 sccm for

chambers 1 and 3 respectively. These flows were combined and drawn through the FTIR gas cell using

0.25” unheated Teflon tubing.

Data were collected for several processed wafer lots during testing. The CF 4 process and scrubber

emission profiles observed for one lot are shown in

22Figures 

### 12 a

‐ b. It is evident that the scrubber emission profile was significantly different than the inlet

profile observed for the combined streams. It was determined that chamber 2 was running in addition

to chambers 1 and 3 during the time these data were collected. Because of the confounding influence of

the operation of chamber 2, these data could not be used for measuring CF 4 DRE for FK15.

Figures 13a

‐ b show emission profiles for CF 4 when only chambers 1 and 3 were running process. These

emissions were integrated to yield CF 4 loading and scrubber emission volumes. The CF 4 DRE was

calculated from the ratio of these integrated volumes. Integration of process emissions from chambers

1 and 3 required using the total flow through both chambers, which was 98 slm. The CF 4 emitted during

16 wafers processed was 0.881 sl. The corresponding CF 4 scrubber volume was 0.133 sl of CF 4 yielding a

DRE of 85 percent, which compares favorably to the DREs measured during the process flow

experiments (84%, Table IV for chambers 1 and 3) and process emissions experiments (83% and 85% for

the trench and via etch processes, respectively).

The data shown in Figures 14a

‐ b were averaged in order to compare DRE values obtained from the ratio

of dilution corrected emission concentrations with those obtained via emissions integration described in

the previous paragraph. Averages may constitute a simpler method for processing concentration data

under relatively simple, highly repetitive process and scrubber emissions profiles.

Two methods of averaging were used. The first consisted of averaging just the emission peaks observed

in both inlet and outlet profiles, as indicated in Figures 14a

‐ b. The CF 4 DRE obtained via peak

‐ averaging

was 87 percent. The second method averaged the CF 4 concentration over the entire collection period

from the start of the first peak to the conclusion of the last peak in the emission profiles. This method

gave 85 percent. These results indicate that for this process with two chambers running simultaneously

it is possible to determine CF 4 DRE using concentration averaging or integrated emission volumes.

Table X : Comparison of CF 4 DRE values obtained for differing methods of data analysis during the

multiple inlet experiment



### Method CF 4 

### In CF 4 

### Out Dilution

Adjusted CF 4 

### Out CF 4 

### DRE

(%)

Integrated

Emissions 0.881 sl 0.133 sl na 85

Average of Peaks 1094 ppmv 18.3 ppmv 146 87

Average of

Emission Profile 381 ppmv 7.3 ppmv 58 85

23One important comment about safety is required concerning the multiple sample inlet experiment. In

these tests, etch emissions from different chambers were mixed together and pulled through the FTIR

gas cell with a metal bellows pump. It was safe, in these tests, to mix effluents from these processes.

Other processes, such as CVD processes, should be carefully reviewed prior to executing this type of

procedure to ensure that mixing gases at various stages within the process cycle will not lead to an

unsafe condition in the sample system. One example would be mixing deposition gas, such as silane,

from one chamber with effluent from another chamber being cleaned and containing potentially high

levels of molecular fluorine. The incompatibly of these gases could lead to a rapid exothermic reaction,

potentially presenting a safety risk.

Figure 11 : Sampling scheme used to monitor process and scrubber emissions on FK15 during multiple

inlet experiment.

24Figures 12a

‐ b : CF 4 emission profile for combined effluent of chambers 1 & 3 on FK 15 (left) and

scrubber effluent (right). Note: chamber 2 was also processing wafers (see text).

25Figures 13a

‐ b : CF 4 emission profile from combined process flows on chambers 1 &3 (left) and from

scrubber (right) during wafer processing on FK15. Note: These data were used to determine the

scrubber CF 4 DRE.

26Figures 14a

‐ b : Expanded view of process and scrubber CF 4 emissions during multiple inlet experiment.

Note: Peak concentrations were individually averaged and used to calculate DRE.



## 3.4 NDIR-FTIR Comparison

One objective of these tests was to benchmark the performance of a Non

‐ Dispersive Infrared (NDIR)

analyzer for continuously monitoring F

‐ gas scrubber emissions. NDIR is a relatively cost

‐ effective means

for continuously monitoring scrubber emissions and performance. It may also indicate, for example, the

onset of changing CF 4 destruction which, in turn, may indicate process change(s), need for scrubber

repair/maintenance or both. These tests were accomplished by sampling scrubber effluent with FTIR

and NDIR simultaneously. Extractive techniques were employed for both instruments and each had a

separate sample port as shown in Figure 1. The NDIR was configured to measure only CF 4

concentrations.



## 3.4.1 NDIR Data Collected on FK15

Carbon tetrafluoride concentrations monitored with both FTIR and NDIR from the FK15 scrubber during

wafer processing, are shown in Figures 15a

‐ b. Inspection of the concentration profiles for the NDIR

(Figure a) and FTIR (Figure b) provides a qualitative indication of close agreement in the measured

concentration profiles for the NDIR and FTIR. Note the different scales in Figures 15a and 15b.

A quantitative comparison of the two monitoring systems was accomplished by integrating the NDIR and

FTIR profiles over identical periods. The result is the measured total volume of CF 4 emitted over the

period of integration for each monitor. The integration was performed during a more complex wafer

processing sequence than shown in Figures 15a

‐ b, which shows two peaks of somewhat differing

magnitudes.

27The results of the integration are presented in Table VIII for two etching profiles, one comprised of three

peaks, which was repeated 13 times, and the second of a single peak, which was repeated 11 times. The

fractional difference [= (NDIR

– FTIR)/0.5 (NDIR + FTIR)] is +11 percent for both etching profiles, which

confirms the qualitative agreement evident in Figures 15a

‐ b. Note also that the NDIR was used as it was

received from the manufacturer, e.g., the manufacturer’s calibration was accepted.

The scrubber DRE can also be calculated using the measured (FTIR) influent volumes, 5.85 sl, during

these tests and the measured scrubber effluent volumes given in Table VIII for the NDIR and FTIR. The

DRE for the FTIR measurement is 85 percent, while the DRE based on NDIR measured scrubber effluent

is 83 percent.

Given the experimental errors of these tests, the results are considered equal. Furthermore, it appears

the NDIR may be considered a relatively cost

‐ effective means for monitoring CF 4 destruction in, as well

as CF 4 emissions from, these scrubbers. Additional trials would be needed to better evaluate suitability

for continuous monitoring over long periods.

Table XI : Comparison of measured NDIR and FTIR emitted CF4 volumes (sl) during wafer processing on

FE15



### Etching Profile NDIR, sl FTIR, sl Fractional difference,

%

Triple peaks 0.99 0.89 11

Single peak 0.46 0.41 11

28Figures 15a

‐ b : Comparison of FTIR vs. NDIR determined CF 4 emissions from FK15 scrubber during

wafer processing

. Note the difference scales in the two figures.



## 3.4.2 NDIR Data Collected on FE05

CF 4 

### emissions from FE05 were also monitored with the FTIR and NDIR during wafer processing.

Emission profiles for both instruments are shown in Figures 16a

‐ b



### . The CF 4 

### emission

concentrations were lower than those observed on FK15. As was the case with FK15, the

emission concentrations for FE05 were nearly identical, again demonstrating that NDIR is a

potentially viable alternative for scrubber emission monitoring.

29Figures 16a

‐ b : CF 4 emissions from scrubber on FE05 determined by FTIR (right) and NDIR during wafer

processing.



## 4. 

## Summary and Conclusions

The results of this study have shown that chemical spiking of POU abatement systems is an

effective method for reliably measuring the DRE of PFCs used during semiconductor

manufacturing. In these tests QMS was effectively combined with FTIR to measure the DREs of

PFCs used during normal semiconductor wafer manufacturing and normal scrubber operation.

The chemical spiking agent (Kr) was added at the inlet to the scrubber in one of the chamber

exhaust lines, and the concentration was determined at the outlet of the scrubber in the

combined effluent stream. The total effective flow through the scrubber was calculated from

these data, and used to correct for the dilution occurring across the scrubber.

It was also demonstrated that NDIR can be used to reliably monitor scrubber effluent CF 4



### concentrations during semiconductor manufacture. If this technology is subsequently shown to

be robust through longer term evaluations, it would provide a relatively cost

‐ effective method

for monitoring CF 4 

### (and other PFC) emissions.

30

### Scrubbers on two multi

‐ chamber etch tools were tested. Results gave DRE values of greater

than 98 percent for all PFCs except CF 4



### . The non

‐ CF 4 

### process gases included CHF 3 

### , SF 6 

### , CH 2 

### F 2



### and CH 3 

### F; the non

‐ CF 4 

### process by

‐ product gases included C 2 

### F 4 

### and C 2 

### F 6



### .

CF 4 

### had a sufficiently low DRE to serve as a prime example for protocol development and

validation. The DRE values for each etcher/scrubber pair were measured using two different

methods: comparing integrated emission volumes from the etcher during manufacturing, and

comparing the corresponding measured inlet and outlet CF 4 

### concentrations with no process or

plasma. Both methods yielded similar DRE values for CF 4



### . The measured CF 4 

### DRE for each

etcher/scrubber pair differed, with an average DRE across two etch processes and chambers for

FE15 of 84 percent and the corresponding value for FE05 of 90 percent.

An experiment was conducted to assess the performance of an alternative process sampling

procedure that continuously extracted and monitored gas concentration samples from multiple

inlet flows while simultaneously monitoring the corresponding scrubber effluent

concentrations. This alternative method drew slip streams from each process chamber from

their respective exhausts, combined them in the FTIR sample inlet line, and pulled that

combined flow through the FTIR gas cell for analysis. The potential advantage of this method is

that it allows direct determination of the actual process atmosphere entering the scrubber,

eliminating the need to know the PFC emissions for each chamber. This approach requires

measuring the individual process dilutions for each chamber, and employing additional

experimental controls on sample flow. The approach also requires assurance of the safety of

mixing chamber exhausts. Both sampling methods gave similar results for the DRE of CF 4



### .

These results, when coupled with the results obtained during prior studies 4 

### at two fabs with

different PFC

‐ based processes using the same experimental methodology, demonstrate the

robustness of the measurement procedures to accurately and precisely measure the

performance of POU abatement systems under operating fab conditions for PFCs, SF 6 

### and NF 3



### .

4 Ridgeway, R.G., and T. Strencosky (2008a) Developing a reliable method for estimating abatement system dilution

and DRE: Evaluation in an IC Mfg Environment (Fab A). Draft report prepared for the USEPA by Air Products &

Chemicals Inc. March 2008

Ridgeway, R.G., and T. Strencosky (2008b) Developing a reliable method for estimating abatement system dilution

and DRE: Evaluation in an IC Mfg Environment (Fab B). Draft report prepared for the USEPA by Air Products &

Chemicals Inc. March 2008

31