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HAZOP Analysis and Debottleneck for Laboratory Operation in

the Semiconductor Industry



Tianxing Cai
Dan F. Smith Department of Chemical Engineering
Lamar University, Beaumont, TX 77710, USA
tcai@lamar.edu

Qiang Xu
Dan F. Smith Department of Chemical Engineering
Lamar University, Beaumont, TX 77710, USA
qiang.xu@lamar.edu


Copyright 2010 by Tianxing Cai All rights reserved.

Prepared for Presentation at
American Institute of Chemical Engineers
2013 Spring Meeting
9th Global Congress on Process Safety
San Antonio, Texas
April 28 May 1, 2013


UNPUBLISHED



AIChE shall not be responsible for statements or opinions contained
in papers or printed in its publications
GCPS 2013 __________________________________________________________________________


Copyright 2010 by Tianxing Cai All rights reserved.

No part of this publication may be reproduced, distributed, or transmitted in any form or by any
means, including photocopying, recording, or other electronic or mechanical methods, without
the prior written permission of the authors, except in the case of brief quotations embodied in
critical reviews and certain other noncommercial uses permitted by copyright law. For
permission requests, write to the authors.
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HAZOP Analysis and Debottleneck for Laboratory Operation in the
Semiconductor Industry

Tianxing Cai
Dan F. Smith Department of Chemical Engineering
Lamar University, Beaumont, TX 77710, USA
tcai@lamar.edu

Qiang Xu*
Dan F. Smith Department of Chemical Engineering
Lamar University, Beaumont, TX 77710, USA
qiang.xu@lamar.edu

Keywords: HAZOP Analysis, Semiconductor Industry, Laboratory Hazards, Operation
Debottleneck

Abstract

Unlike the semiconductor manufacturing process with fully automatic equipment, the laboratory
operation in the semiconductor industry will still involve multiple types of manual handling for
chemical analysis, reliability test, material characterization and failure analysis. The test
operators or lab engineers have different levels of exposure to a lot of chemicals and physical
hazards in multiple phases. This paper will describe the straightforward HAZOP (Hazard and
Operability Study) process to identify the hazards and assess the risks of laboratory operations.
The analysis will be deployed in the ways of manpower, machine, materials, method and
environment. The analysis output can be regarded as the aid to safer laboratory design, operator
training and real-time fault diagnosis. This will help to debottleneck and achieve operation
safety and occupational health in the semiconductor industry.











______________________________________________________________________________
For presentation at AICHE 2013 Spring Meeting ,9th Global Congress on Process Safety.
* All correspondence should be addressed to Prof. Qiang Xu (Phone: 409-880-7818; Fax: 409-
880-2197; E-mail: Qiang.xu@lamar.edu).

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1. Introduction

Semiconductor industry revenue in 2012 is expected to reach $323.2 billion, up a slight 3.3
percent from last years revenue of $312.8 billion, according to an IHS iSuppli Global
Manufacturing Market Tracker report from information and analysis provider IHS.
Based on the professional estimation, the growth in the semiconductor industry from 2013 to
2015 will average between a more encouraging 6.6 to 7.9 percent, as shown in the figure below,
with total semiconductor revenue by 2015 rising to some $397.7 billion. In the coming several
years, the strong semiconductor growth can be seen.



Figure 1: Worldwide Semiconductor Industry Revenue Forecast

Coupled with the fast development, the semiconductor employment has globally stretched. In
USA, recently on Dec 11th, 2012, the Semiconductor Industry Association (SIA) announced that
U.S. semiconductor industry jobs stretch across almost every region of the country and into the
majority of states, according to an analysis of government data. California leads all states with
47,100 semiconductor jobs, followed by Texas (28,800), Oregon (23,400), Arizona (18,800),
Massachusetts (10,100) and New York (7,600). According to BLS, the U.S. semiconductor
industrys workforce grew by 3.7 percent over the previous year. In comparison, jobs throughout
the broader U.S. economy increased by 1.2 percent over the same time period.

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Figure 2: Semiconductor Industry Employment by State

Ever since the invention of transistor by the Bell Telephone Laboratories in 1948, the
semiconductors industry has expanded greatly. The continuous fast development and
innovations have expedited the increase of the semiconductor industry employment, which has
further invoked an unavoidable concern of occupational safety to the semiconductor
manufacturing operation.
Unlike the semiconductor manufacturing process with fully automatic equipment, the laboratory
operation in the semiconductor industry will still involve multiple types of manual handling for
chemical analysis, reliability test, material characterization and failure analysis. These
operations will involve the handling of advanced and complex equipment or instruments such as
Gas Chromatography (GC), Gas Chromatography-Mass Spectrometry (GC-MS), Fourier
Transformed Infra Red Spectroscopy (FT-IR), Ultraviolet Visible Spectroscopy (UV/Visible),
Liquid Chromatography (LC), Thermal and Elemental Analysis (TEA). Furthermore, due to
rapid changes in this industry, manufacturing processes and their associated hazards may change
completely every few years. These changes make hazard assessments more difficult to complete
and require that they be conducted more often. Common hazards may include exposure to
solvents, acid and caustic solutions, toxic metals, and radiation. Below Table 1 has listed the
typical hazardous chemicals with their roles in the manufacturing process and potential health
problems linked to the exposure. The test operators or lab engineers have different levels
exposure to a lot of chemicals and physical hazards in multiple phases.






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Table 1:Hazardous Chemicals in the Semiconductor Industry

In order to mitigate the potential risk during the chemical process operation, HAZOP study is
always conducted. A hazard and operability study (HAZOP) is a structured and systematic
examination of a planned or existing process or operation in order to identify and evaluate
problems that may represent risks to personnel or equipment, or prevent efficient operation. The
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HAZOP technique was initially developed to analyze chemical process systems, but has later
been extended to other types of systems and also to complex operations and to software systems.
A HAZOP is a qualitative technique based on guide-words and is carried out by a multi-
disciplinary team (HAZOP team) during a set of meetings.
This paper will describe the straightforward HAZOP process to identify the hazards and assess
the risks of laboratory operations. The analysis will be deployed in the ways of manpower,
machine, materials, method and environment. The analysis output can be regarded as the aid to
safer laboratory design, operator training and real-time fault diagnosis. This will help to
debottleneck and achieve operation safety and occupational health in the semiconductor industry.

2. General Methodology

Several tools and methodologies are adopted to deploy the HAZOP Analysis and debottleneck
for laboratory operation in the semiconductor industry. This has included Laboratory Operation
Flow Diagram (LOFD), HAZOP Meeting, Parameters and Guide Words

2.1 Laboratory Operation Flow Diagram (LOFD)

The method applies to existing or planned laboratory operation for which design information is
available. Similar with the commonly used process flow diagram, this commonly includes a
laboratory operation flow diagram, which is examined in small sections, such as individual items
of laboratory test instruments, glassware or chemicals between them. For each of these, a
operation design intention is specified. For example, in a failure analysis laboratory, a standard
solution of aqua regia (the combination of HNO
3
and HCl with the volume ratio of 1:3) may
have been used. The intention to remove gold layer in the integrated circuit so that the further
visual inspection can be conducted to check the failure mode. The HAZOP team then
determines what are the possible significant deviations from each intention, feasible causes and
likely consequences. It can then be decided whether existing, designed safeguards are sufficient,
or whether additional actions are necessary to reduce risk to an acceptable level. Besides the
operation safety, HAZOP can also give the detailed instruction on the opinion whether the
potential deviation will affect the quality of experiment or test analysis result.

2.2 HAZOP Meeting

When HAZOP meetings were proceeded by the involved laboratory engineers, technicians and
operators, they were generally scheduled for one to two hours per day. For a medium-sized
laboratory where the total number of test items to be considered is 600 (items of equipment and
pipes or other transfers between them), about 20 such meetings would be needed.

2.3 Parameters and Guide Words

The key feature is to select appropriate parameters which will apply to the design intention. The
general words used in the laboratory operation are usually solution concentration, solution
temperature, sampling volume, and instrument detection limit. In the above example, it can be
seen that variations in these parameters could constitute deviations from the design intention of
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experiments. In order to identify deviations, a set of guide words is applied to each step of the
experiment process. The current standard Guide Words are as follows:

Table 2: Guide Words for HAZOP Study of Laboratory Operation in the Semiconductor
Industry
Guide Word Meaning
NO OR NOT Complete negation of the design intent
MORE Quantitative increase
LESS Quantitative decrease
AS WELL AS Qualitative modification/increase
PART OF Qualitative modification/decrease
REVERSE Logical opposite of the design intent
OTHER THAN Complete substitution
EARLY Relative to the clock time
LATE Relative to the clock time
BEFORE Relating to order or sequence
AFTER Relating to order or sequence


2.4 HAZOP Software

Various software programs are now available to assist in HAZOP meetings. Even though they
are always used in the chemical industry, the principles will be quite applicable to laboratory
operation in the semiconductor industry.

2.5 HAZOP Team

HAZOP is normally carried out by a team of people with roles as follows

Table 3: Team Members for HAZOP Study of Laboratory Operation in the
Semiconductor Industry
Name Position Role
HAZOP Group
Leader
Lab Manager
someone experienced in HAZOP and laboratory
operation, to ensure that the method is followed
carefully
Recorder Lab Engineer 1
someone to ensure that problems are documented and
recommendations passed on
Designer Lab Engineer 2
someone to explain any design details or provide
further information
User Lab Operator
someone to consider it in use and question its
operability, and the effect of deviations
Specialist Lab Engineer 3 someone with relevant technical knowledge
Maintainer Lab Technician someone concerned with maintenance of the process.
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3. HAZOP Management System

For the purpose of effective implementation of the HAZOP management policy and solid
application of introduced general methodology, the laboratory HAZOP system should be set up.
The system has coupled general management policy (operation specification and work
instructions), environment control (temperature and humidity), operation safety (chemical
storage, hazards assessment, chemical identification and MSDS), equipment management (PM,
calibration, MSA), chemical control (data analysis and shelf life time control), training and
certification (orientation, OJT, regular qualification). The whole system has covered multiple
layers of analysis factors. The first layer will include manpower, machine, materials, method and
environment.



Figure 3: HAZOP Management System for Laboratory Operation in the Semiconductor
Industry


These factors can be expanded with below fishbone diagrams so that the second layer of factors
will be included into HAZOP matrix system: for example, sample collection and sample
preparation will be considered in the material part; training, parallax, reproducibility, practice
and ergonomics will be considered in the manpower part; samples, test methods, workmanship
and standards will be considered in the method part; discriminations, repeatability, bias, linearity
and calibration will be considered in the instrument part; vibration, lighting, temperature and
humidity will be considered in the method part.

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Figure 4: Fish Bone Diagram for HAZAP Study for Laboratory Operation in the
Semiconductor Industry

Next, these practices can form a closed PDCA (Plan, Do, Check and Act) loop for continuous
improvement of HAZOP activity. The close loop include four phases: plan, do, check and act.
In the first phase of planning, the procedures and schedules to conduct the study should be
identified and the input data should be collected. Then, the deviation should be identified by the
application of key words and the causes and consequences should also be determined in the
second phase. Next, the improvement actions need to be followed up. It is better to restudy the
necessity of current HAZOP system. After the verification of the above items, the study report
needs to be generated. Then the activity of HAZOP study should be evaluated to confirm
whether the current scope, objective and responsibility need to be updated. Furthermore, the
team should decide whether they need more team members to cover a larger scope.

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Figure 5: PDCA (Plan, Do, Check and Act) Diagram for HAZAOP Study for Laboratory
Operation in the Semiconductor Industry

The analysis output can be regarded as the aid to safer laboratory design, operator training and
real-time fault diagnosis. This will help to debottleneck and achieve operation safety and
occupational health in the semiconductor industry.

4. Application Illustration

To demonstrate the efficacy of the developed systematic methodology, one case study has been
conducted as the illustration of the methodology application in the real practice of plating bath
monitoring of wafer bumping in the semiconductor industry. Wafer bumping is an advanced
packaging technique that attaches solder spheres or gold bumps to the bond pads on a selected
die. Gold bumping is generally used for Tape Automated Bond (TAB) assembly or Anisotropic
Conductive Film (ACF) flip-chip assembly. Solder bumping is primarily used for reflow flip-
chip assembly which unites the components face down, directly with the substrate or board
through conductive bumps on the bond pads. These bumps deliver the electrical, mechanical and
thermal interconnection which provides direct contact between the chip package and the device.
Another process is called stud-bumping. Unlike gold and solder bumping, this process can be
done at the die level. Wafer bumping also known as flip chip has traditionally been used for
high-end niche applications. However in the last few years it has gone mainstream to include a
wider range of consumer applications geared towards both the performance driven market and
the form factor driven market.
Wafer bumping provides the electrical and mechanical connection between a die and substrate,
which is one of the most critical elements of any flip chip package structure. Predominantly lead-
tin and lead-free solders at the present time, these connections - or bumps - must exhibit superior
adhesion to the die, minimal resistance, and result in high assembly yields. Solder bumps are
formed by using either thin film metal deposition or ball loading techniques. Currently the
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advanced semiconductor assembly and test company such as Amkor offers state-of-the-art
capability in electroplated solder technologies including the electroplating capability to support
fine pitch bumping and copper pillar structures.
Wafer bumping utilizes thin film deposition, photolithography and plating techniques to place
solder or gold onto IC (Integrated Circuit) lead pads. The wafer solder bump process is to
produce the solder bumping of the wafer pad. Then it is going to melt the bumping by heat in
assembly. This technology can substantially reduce IC size and have the advantages such as high
density, low sensitivity, low cost and effective heat dissipation. This bumping process is suitable
for flip chip assembly for LCD, memories, microprocessors, and microwave RF ICs applications.
The process includes sputter UBM (under Bump Metallurgy), Photolithography, Plating and
Etching etc., This bumping is suitable to apply on TAB, Flip Chip. The detailed process flow
chart has been illustrated in below flow chart.


Figure 6: Process Flow Chart for Wafer Bumping Process

One of the key test item for wafer bumping operation is the electroplating bath monitoring and
composition control of solder materials and additives. Plating solutions must be routinely
analyzed in order to maintain the recommended bath formulation and to preempt the occurrence
of problems related to improper levels of bath constituents. Contaminant levels in the solutions
must also be monitored. Manufacturers of plating systems establish optimum specifications to
ensure maximum solution efficiency and uniformity of deposits. The various factors that cause
the concentrations of bath constituents to deviate from their optimum values are as follows: 1.
drag-out; 2. solution evaporation; 3. chemical decomposition; and 4. unequal anode and cathode
efficiencies. Regular analysis of plating solution becomes the responsibility of process
engineering and quality control group.
The techniques employed for the quantitative analysis of plating solutions are classified as
volumetric (titrimetric), gravimetric, and instrumental. Volumetric and gravimetric methods are
also known as wet methods. The analyst must select the method that is best suited and most
cost effective for a particular application. The wet methods outlined here are simple, accurate,
and rapid enough for practically all plating process control. They require only the common
analytical equipment found in the laboratory, and the instructions are sufficiently detailed for an
average technician to follow without any difficulty. The determination of small amounts of
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impurities and uncommon metals should be referred to a competent laboratory, as a high degree
of skill and chemical knowledge are required for the determination of these constituents.
Instrumental methods differ from wet methods in that they measure a physical property related to
the composition of a substance, whereas wet methods rely on chemical reactions. The selection
of an instrument for the analysis of plating solutions is a difficult task. Analysts must decide if
the cost is justified and if the analytical instrument is capable of analyzing for the required
substances with a high degree of accuracy and precision. Instruments coupled to computers can
automatically sample, analyze, and record results. Mathematical errors are minimized and
sample measurements are more reproducible than with wet methods. Instrumental methods are
also extremely rapid when compared with wet methods. Analytical instruments frequently used
in the analysis of plating solutions can be categorized as spectroscopic, photometric,
chromatographic, and electro-analytical. Spectroscopic methods (flame photometry, emission
spectrometry, X-ray fluorescence, mass spectrometry, and inductively coupled plasma) are based
on the emission of light. Photometric methods (spectrophotometry, colorimetry, and atomic
absorption) are based on the absorption of light. Chromatographic methods (ion
chromatography) involve the separation of substances for subsequent identification. Electro-
analytical methods (potentiometry, conductometry, polarography, amperometry, and
electrogravimetry) involve an electric current in the course of the analysis. The instrumental
methods, comprehensively reviewed below, are most applicable to plating environments.
Here, the manual titration procedures to determine copper concentration in the sample plating
bath is used as illustration because the manual titration will have more potential safety concerns
compared with the instrument analysis methods. Below is the procedure of the test.
PROCEDURE:
1. Preparation of EDTA (Ethylenediaminetetraacetic Acid) (0.01M). Dry EDTA for 2
hours at 80

C. GMW = 372.2., or check the reagent bottle. Dissolve needed grams in a

500 ml vol. flask. Store in a conditioned polyethylene container. EDTA solutions attack
glass and deteriorate after 1 or 2 days.
2. Preparation of known copper solution. Place 0.2 g to 0.25 g of pure Cu. wire (or shot)
(weighed on an analytical balance) in a 100 ml beaker. Add 15 ml conc. HNO3 and 1 ml
conc. H2SO4. Place a watch glass over the beaker. Boil until dense white fumes of
SO3 cease. Transfer carefully to a 200 ml vol. flask. Remember to rinse the watch glass.
Dilute to the mark.
3. Preparation of unknown copper solution. Weigh 0.5 to 0.6 grams of unknown into a
200 ml vol. flask. Add 30 ml of 1:5 nitric acid. Heat until all particles are dissolved.
Dilute to the mark.
4. Titration with EDTA - murexide indicator. Do this step for 4 samples of known and 4
samples of unknown.

KNOWN: Place 10 ml of Cu known solution (step 2) in 250 ml Erlenmeyer flask. Add pH buffer
drop-wise until the solution turns completely blue and the precipitate first formed dissolves. Add
about 100 ml. Add more buffer if solution becomes cloudy. Add 1 tablet of murexide indicator
and titrate with EDTA until color changes from yellow (green) to deep violet. If the volume of
EDTA is less than 10 ml, repeat using 25 ml liquid of Soln. 2.

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UNKNOWN: Place 25 ml of Cu unknown solution (step 3) in 250 ml Erlenmeyer flask. Add pH
buffer drop-wise until the solution turns completely blue and the precipitate first formed
dissolves. Add 1 tablet of murexide indicator and titrate with EDTA until color changes from
yellow (green) to deep violet. If the vol. of EDTA solution is less than 10 ml. use a larger liquid
of Soln. 3.
Remarks: The copper-murexide complex is pure yellow, but the color at the starting point of the
titration is greenish depending on the amount of copper present. The green is the mixture of
yellow (indicator complex) and blue (copper-tetramine complex). As the titration proceeds the
tetramine complex is transformed to the less intensely colored EDTA complex and the yellow of
the indicator complex becomes permanent.
CALCULATION: Calculate the molarity of the EDTA. Calculate percent copper in the sample
using the value of the Molarity of the EDTA found. Include the spread sheet for the calculation.

Based on the available procedures to determine the copper concentration in the sample solution
of plating bath, HAZOP factors can be expanded so that the second layer of factors will be
included into HAZOP matrix system: for example, sample collection and sample preparation will
be considered in the material part; training, parallax, reproducibility, practice and ergonomics
will be considered in the manpower part; samples, test methods, workmanship and standards will
be considered in the method part; discriminations, repeatability, bias, linearity and calibration
will be considered in the instrument part; lighting, temperature and humidity will be considered
in the method part. These factors are listed as the column. Then, the HAZOP guide words will
be listed as the row. The related information of the deviation stored in LOD(Laboratory
Operation Database) and HPD(HAZOP Project Database) can be selected into the blank spaces
from the drop-down list box in the above expanded table. Next, the data record of regular
monitor results will be proceeded into data analysis to validate the impact of the above deviation .
The data analysis result will couple with the expanded HAZOP table to quantitatively identify
the potential deviation of operation safety and test accuracy.

5. Conclusion

The laboratory operation in the semiconductor industry will have more possibilities of manual
handling for chemical analysis, reliability test, material characterization and failure analysis.
Therefore higher attention should be paid to the laboratory operations. As illustrated in this
paper, the methodology of HAZOP study procedure can be applied to identify the potential
deviations in both experiment accuracy and operation hazards. Multiple layers of factor
consideration by the application of 4M1E (Man, Machine, Material, Method and Environment)
will help the brainstorm to give the aid to safer laboratory design, operator training and real-time
fault diagnosis. This will help to debottleneck and achieve operation safety and occupational
health in the laboratory operation semiconductor industry.






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6. Reference

[1] Chepesiuk, R., Where the Chips Fall: Environmental Health in the Semiconductor
Industry. Environmental Health Perspectives, Volume 107, pp.452-457, 1999

[2] Swann, C. D., & Preston, M. L., "Twenty-five years of HAZOPs", Journal of Loss
Prevention in the Process Industries, Volume 8, No 6, pp.349-353, 1995

[3] Amkor Technology Wafer Bumping Service Introduction, http://www.amkor.com
/go/turnkey-services/wafer-bumping
(accessed Jan. 5, 2013)

[4] Nolan, D.P., "Application of HAZOP and What-If Safety Reviews to the Petroleum,
Petrochemical and Chemical Industries". William Andrew Publishing/Noyes, 1994

[5] Lawley, H. G., "Operability studies and hazard analysis", Chemical Engineering
Progress, Volume 70, No 4, pp.45, AIChE,1974

[6] Chemical Industries Association., "A Guide to Hazard and Operability Studies", 1977

[7] IHS iSuppli Research., "Semiconductor Industry Revenue to Ensure Slow Growth in
2012",http://www.isuppli.com/Semiconductor-Value-Chain/News/Pages/Semiconductor-
Industry-Revenue-to-Endure-Slow-Growth-in-2012.aspx
(accessed Jan. 5, 2013)

[8] U.S. Bureau of Labor Statistics (BLS) Data Report,2011

[9] Semiconductor Industry Association, http://www.sia-online.org/
(accessed Jan. 5, 2013)

[10] Bolmen, Richard A., "Semiconductor Safety Handbook: Safety and Health in the
Semiconductor Industry", Noyes Publications, 1998