Ocean Optics LIBS2500plus User Manual

Laser-Induced Breakdown Spectroscopy
LIBS2500plus

Installation and Operation Manual

Document Number 166-00000-000-02-0110

Offices:

E-mail: [e-mail] (General sales inquiries)

Ocean Optics, Inc. World Headquarters

830 Douglas Ave., Dunedin, FL, USA 34698

Phone [phone]

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000-00000-000-02-A

Additional
Offices:

Regional Headquarters

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73760 Ostfildern

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Ocean Optics Asia

666 Gubei Road, Kirin Tower, Suite 601B, Changning District, Shanghai,
PRC. 200336

Phone [phone]

Fax [phone]
E-Mail [e-mail]

Ocean Optics EMEA

Sales and Support Center
Geograaf 24, 6921 EW DUIVEN, The Netherlands

Phone [phone]

Fax [phone]
E-Mail

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Copyright © 2010 Ocean Optics, Inc.

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, by any means, electronic,
mechanical, photocopying, recording, or otherwise, without written permission from Ocean Optics, Inc.
This manual is sold as part of an order and subject to the condition that it shall not, by way of trade or otherwise, be lent, re-sold, hired out or
otherwise circulated without the prior consent of Ocean Optics, Inc. in any form of binding or cover other than that in which it is published.

Trademarks

All products and services herein are the trademarks, service marks, registered trademarks or registered service marks of their respective owners.

Limit of Liability

Every effort has been made to make this manual as complete and as accurate as possible, but no warranty or fitness is implied. The information
provided is on an “as is” basis. Ocean Optics, Inc. shall have neither liability nor responsibility to any person or entity with respect to any loss or
damages arising from the information contained in this manual.

Important Safety Notices

WARNING

The Ocean Optics LIBS System uses a Class 4 laser. When operated as designed and
with the sample chamber closed, this system is equivalent to a Class 1 laser device
and so requires no special precautions. Exposure to a Class 4 laser can cause eye
and skin damage. Although the LIBS System incorporates numerous safety
features, due care is required when using a laser to prevent injury. Never operate
this system without all safety covers in place and sample interlock chamber
functioning.

1. Use laser safety glasses rated for Nd:YAG laser applications (OD6+ @ 1064) at all times when
operating the laser.

2. Only permit properly trained and certified personnel to operate the laser.

3. Read all the instructions that accompanied your laser.

166-00000-000-02-0110 i

Important Safety Notices

ii 166-00000-000-02-0110

Table of Contents

About This Manual......................................................................................................... vii

Document Purpose and Intended Audience..............................................................................vii

Document Summary..................................................................................................................vii

Product-Related Documentation ............................................................................................... vii

Upgrades....................................................................................................................... viii

Chapter 1: Introduction......................................................................1

Product Overview .......................................................................................................... 1

How the LIBS2500plus Works...................................................................................................1

Advantages of Broadband LIBS Techniques ............................................................................ 1

LIBS Emission ID....................................................................................................................... 2

Applications................................................................................................................... 3

LIBS Components ......................................................................................................... 3

LIBS Spectrometers .................................................................................................................. 4

Laser Requirements for LIBS2500plus ..................................................................................... 5

LIBS Sample Chamber..............................................................................................................6

LIBS Imaging Module ................................................................................................................6

OOILIBSplus Software .............................................................................................................. 6

Other Required Equipment........................................................................................................7

Additional Recommended Equipment .......................................................................................7

Chapter 2: Installing the LIBS System .............................................9

Overview ....................................................................................................................... 9

Hardware Set-up ........................................................................................................... 9

Software Installation ...................................................................................................... 12

Hardware Cabling.......................................................................................................... 12

Other Software Installation ............................................................................................ 15

Imaging Module Camera Driver ................................................................................................ 15

Crossfire Camera Driver............................................................................................................15

System Start-up............................................................................................................. 15

Assigning Spectrometers........................................................................................................... 15

Loading the Element Library ..................................................................................................... 18

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Table of Contents

Chapter 3: Operation .........................................................................19

Overview ....................................................................................................................... 19

Configuration ................................................................................................................. 19

Set Q-Switch Delay ................................................................................................................... 19

Setup Options ............................................................................................................................21

Set up Radiometric Information ................................................................................................. 22

Initial Testing ................................................................................................................. 23

Using OOILIBSplus Software Modes............................................................................. 24

Pixel Correlation Mode .............................................................................................................. 24

Pixel Correlation Procedure ..................................................................................................25

Element ID Mode.......................................................................................................................27

Elemental ID Procedure ........................................................................................................ 27

Peak Analysis Mode .................................................................................................................. 28

Lines to Analyze Options ...................................................................................................... 28

Lines Information...................................................................................................................29

Peak Analysis Procedure ...................................................................................................... 29

Performing Correlation in OOILIBSplus ......................................................................... 30

Accessing the Correlation Window............................................................................................30

Adding Samples to the Correlation Library................................................................................31

Saving the Correlation Library ................................................................................................... 33

Correlation Tips .........................................................................................................................33

Chapter 4: Troubleshooting..............................................................34

Overview ....................................................................................................................... 34

HR2000+ Connected to PC Prior to OOILIBSplus Installation ....................................... 34

Remove the Unknown Device from Windows Device Manager................................................ 34

Remove Improperly Installed Files ............................................................................................ 35

Laser Troubleshooting................................................................................................... 36

Problem .....................................................................................................................................36

Probable Cause.........................................................................................................................36

Solution...................................................................................................................................... 36

Spectrometer Troubleshooting....................................................................................... 36

Continuous Beeping from System ............................................................................................. 36

Problem .................................................................................................................................36

Probable Cause .................................................................................................................... 36

Solution .................................................................................................................................36

System Prompts for ezusb.sys or an .inf File ............................................................................ 37

Problem .................................................................................................................................37

Probable Cause .................................................................................................................... 37

Solution...................................................................................................................................... 37

Verifying Device Setup .............................................................................................................. 37

Problem .................................................................................................................................37

Solution .................................................................................................................................37

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Table of Contents

OOILIBSplus Software Troubleshooting ........................................................................ 38

Program Keeps Freezing or Locking Up ...................................................................................38

Problem .................................................................................................................................38

Probable Cause .................................................................................................................... 38

Solution .................................................................................................................................38

Appendix A: Specifications..............................................................39

Appendix B: User Interface...............................................................41

Menu Bar....................................................................................................................... 41

File Menu ...................................................................................................................................41

Save Sub-Menu .................................................................................................................... 42

Export Sub-Menu ..................................................................................................................43

View Menu .................................................................................................................................43

Overlay Sub-Menu ................................................................................................................44

ScanType Menu ........................................................................................................................ 44

Mode Menu................................................................................................................................ 45

Background Menu ..................................................................................................................... 45

Background | Mode Menu ..................................................................................................... 46

Library Options Menu ................................................................................................................ 46

Library Options | Element ID Menu ....................................................................................... 46

Library Options | Correlation Menu ....................................................................................... 47

Tools Menu ................................................................................................................................47

Stage Menu ...............................................................................................................................48

Tool Bar......................................................................................................................... 48

Dialog Bar...................................................................................................................... 48

Status Bar ..................................................................................................................................49

Graph Window............................................................................................................... 50

Index ................................................................................................... 51

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Table of Contents

vi 166-00000-000-02-0110

About This Manual

Document Purpose and Intended Audience

This document provides the user of the LIBS2500plus for setting up, calibrating and performing
experiments with their system.

Document Summary

Chapter Description

Chapter 1: Introduction

Chapter 2: Installing the LIBS

System

Chapter 3: Operation

Chapter 4: Troubleshooting

Appendix A: Specifications

Appendix B: User Interface

Contains descriptive information about the LIBS2500plus
system. It also provides laser requirements and shipment
components.

Provides installation and configuration instructions.

Contains instructions for operating the LIBS2500plus System.

Contains recommended steps to isolate and correct common
problems.

Provides product specification data.

Contains a quick reference guide to the OOILIBSplus user
interface features.

Product-Related Documentation

You can access documentation for Ocean Optics products by visiting our website at

http://www.oceanoptics.com. Select Technical → Operating Instructions, then choose the appropriate

document from the available drop-down lists. Or, use the
of the web page. You can also access operating instructions for Ocean Optics products from the

and Technical Resources

our website at

Technical → Engineering Docs.

CD that ships with the product. Engineering-level documentation is located on

Search by Model Number field at the bottom

Software

Other Ocean Optics documentation related to your LIBS system includes the following:

 LIBS Imaging Module Installation and Operation Instructions located at

http://www.oceanoptics.com/technical/LIBS Install.pdf

 Correcting Device Driver Issues located at

http://www.oceanoptics.com/technical/engineering/correctingdevicedriverissues.pdf

166-00000-000-02-0110 vii

About This Manual

Upgrades

Occasionally, you may find that you need Ocean Optics to make a change or an upgrade to your system.
To facilitate these changes, you must first contact Customer Support and obtain a Return Merchandise
Authorization (RMA) number. Please contact Ocean Optics for specific instructions when returning a
product.

viii 166-00000-000-02-0110

Chapter 1

Introduction

Product Overview

The Ocean Optics LIBS2500plus Laser-induced Breakdown Spectrometer is a detection system that
permits real-time, qualitative measurements of trace elements. This broadband, high-resolution instrument
allows for spectral analysis from 200-980 nm, with resolution of ~0.1 nm (FWHM). Sensitivity has been
reported to parts-per-billion and picogram levels.

The LIBS 2500plus consists of 1 to 7 spectrometer channels and operates with any 32-bit, USB­compatible Windows PC. We provide OOILIBSplus Application Software with spectral-saving and data­logging capabilities for operating the LIBS2500plus and for firing the laser. Correlation Software
provides instant material identification when using the LIBS2500plus and a spectral library consisting of
2500 atomic emission lines from the NIST (National Institute of Standards and Technology) tables for
elemental identification.

The LIBS Imaging Module is available for use with the LIBS system to enable you to precisely adjust the
laser to focus on the exact spot on the sample that you wish to analyze. The LIBS Imaging Module also
comes with special software for the camera to capture high quality images on your PC.

How the LIBS2500plus Works

A high-intensity, 10 nanosecond-wide laser pulse beam is focused on the sample area. When the laser is
fired, the high temperature of the laser ablates the surface of the sample and creates a plasma. As the
plasma decays or cools, excited atoms in the plasma emit light of characteristic wavelengths distinct to
the elements present. All elements have emission spectra in the 200-980 nm region. The detection system
uses up to seven of our HR2000+ High-resolution Miniature Fiber Optic Spectrometers, each with a
2048-element linear CCD array. All spectrometers are triggered to acquire and read out data
simultaneously. The detectors in the broadband (200-980 nm) LIBS2500plus collect the signal; software
included with the system displays and identifies the emission spectrum.

Advantages of Broadband LIBS Techniques

Many LIBS systems have a small spectral range. The LIBS2500plus is the first to provide broadband
spectral analysis. Because the system is noninvasive, you can perform real-time measurements
hostile industrial, chemical and biochemical environments with little or no sample preparation.

in situ, in

166-00000-000-02-0110 1

1: Introduction

LIBS Emission ID

The reason we at Ocean Optics have designed a broadband high-resolution spectrometer is to be able to
both see and resolve all the lines from all the elements. The spectral resolution is ~0.1 nm, less than this
in the UV-blue and a bit higher in the red-IR. Because the LIBS-generated lines are stark broadened to
about 0.2 nm or so in the UV and about 0.3 nm in the IR, the system can resolve everything that is
possible to measure.

The laser-induced plasma begins life as very hot 15,000 degree K plasma emitting a large bremsstrahlung
continuum. Depending on the sample matrix, most emission analysis is performed for a few microseconds
after the initial plasma generation so the continuum will not mask the line structure. During this time, the
higher order transitions decay away, leaving mostly I and II atomic emissions. These are the ones that are
identified.

Also entering into the emissions from the elements in the interrogated plasma are the collision dynamics
of the plasma. Rate equations can be used to analyze the target, but emission signatures, sample-standards
and correlation techniques are preferred to identify materials with the OOILIBSplus Software.

Elemental analysis and identification are very important in understanding content, and in some cases are
used for quantitative analysis. To perform analysis and identification, you must use an element catalog to
help determine when a particular element is present.

We use a catalog that was derived from the NIST and other wavelength tables. It consists of the persistent
lines of the elements from spark spectra and is the closest to a complete catalog of the brightest lines
around the temperature of the decayed plasma.

How can we be sure that the identified elements are actually present? OOILIBSplus software contains
two rating mechanisms:

 The first rating mechanism indicates how many lines of those in our persistent line set are

present. Thus, if 5 of 7 possible have been identified, you can be fairly certain that this particular
element is present. If one of 7 is present, could it be something else? Perhaps a line that is not in
our catalog from another species?

 For the second analysis technique, the emission lines have an appearance value based on

experimental observation. It could be that this single line is the brightest of those from this
element and the others are weak. So, we rate the element using a formula based on these
appearance levels. If only the weakest line of the 7 appears, it is ranked very low and indicates
that this is from one of the unknowns. If it is the strongest line, it will be rated high, allowing you
to be certain that it was present. If you have the highest 5 of the 7 in the table, the rating will be
extremely high.

OOILIBSplus software allows you to call any number of spectral libraries you wish to use. The present
library has greater than 2000 lines available. There are no overlaps, but as we advance to more
sophisticated libraries, there certainly will be. The full NIST catalog has so many lines (>100,000) that
everything would be identified many times over, even though the probability of appearance may be small
to zero. That is why we have not included it.

Refer to
work. For a list of the persistent lines of spark spectra, consult one of the CRC manuals (Handbook of
Chemistry and Physics). Even the old publications are quite accurate.

http://physics.nist.gov/PhysRefData/contents-atomic.html to print lists and observe the latest

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1: Introduction

LIBS2500plus Spectra of Anthrax SurrogatesBC (Bacillus Cereus), BG (Bacillus Globigii), BT

(Bacillus Thuringiensis)

Applications

The LIBS technique is useful in areas such as:

 Environmental monitoring (soil contamination, particulates, sediments)

 Materials analysis (metals, plastics, slag, glass)

 Forensics and biomedical studies (teeth, bones)

 Military and safety applications (explosive particles, chemical and biological warfare agents)

 Art restoration/conservation (pigments, precious/ancient metals)

 Metrology (silicone wafers, semiconductor materials)

 Bioresearch (plants, grains)

LIBS Components

Ocean Optics’ LIBS functionality can be purchased as a complete system, including the spectrometers
and related fibers, laser, LIBS Imaging Module, and OOILIBSplus software. The system is also
completely customizable. The modular nature of the LIBS2500plus system allows you to purchase just
the spectrometer. Users can then provide their own fixtures and/or Q-switched laser. You can specify the
number of spectrometers (1–7), as well as their gratings, lenses, slits and filters. Contact an Ocean Optics
Application Scientist for more information on customizing your LIBS System.

166-00000-000-02-0110 3

1: Introduction

LIBS Spectrometers

As lower-cost options, LIBS2500plus Systems are available with fewer than seven channels (see table
below), with a narrower wavelength range for element-specific analyses. Depending on the range of your
analyses, you may require a system (LIBS2500plus-1) at a significantly lower cost.

You can turn your HR2000+ Spectrometer into a 1-channel LIBS System (LIBS2500-1PLUS) with the
LIB2500plus Controller and the following equipment:

 LIBS Sample Chamber (LIBS-SC)

 LIBS Laser (200mJ or 50 mJ)

 LIBS Imaging Module (LIBS-IM-USB)

 LIBS Controller Cables

Contact Ocean Optics to return your HR2000+ to the factory for a firmware upgrade and the required
LIBS equipment to upgrade your HR2000+ Spectrometer to a LIBS2500-1PLUS.

Fiber Bundles

LIBS Fiber Bundles

Item LIBS System Description Optical Fiber

Bundle

LIBS2500-7PLUS 7-channel LIBS System, includes all channels (A-G) LIBS-BUN-7

LIBS2500-6PLUS 6-channel LIBS System, choose 6 channels from A-G LIBS-BUN-6

LIBS2500-5PLUS 5-channel LIBS System, choose 5 channels from A-G LIBS-BUN-5

LIBS2500-4PLUS 4-channel LIBS System, choose 4 channels from A-G LIBS-BUN-4

LIBS2500-3PLUS 3-channel LIBS System, choose 3 channels from A-G LIBS-BUN-3

LIBS2500-2PLUS 2-channel LIBS System, choose 2 channels from A-G BIF600-2-UV/VIS

LIBS2500-1PLUS 1-channel LIBS System, choose 1 channel from A-G P600-2-UV/VIS

LIBS2500plus­CNTRL

OOILIBSplus

1-channel controller assembly for HR2000+
Spectrometer

LIBS System Software

(includes elemental emission lines library)

P600-2-UV/VIS

N/A

4 166-00000-000-02-0110

LIBS Spectrometer Channels (A-G)

Channel Description

LIBS-CH-A Spectrometer channel with 200-305 nm wavelength range

LIBS-CH-B Spectrometer channel with 295-400 nm wavelength range

LIBS-CH-C Spectrometer channel with 390-525 nm wavelength range

LIBS-CH-D Spectrometer channel with 520-635 nm wavelength range

LIBS-CH-E Spectrometer channel with 625-735 nm wavelength range

LIBS-CH-F Spectrometer channel with 725-820 nm wavelength range

LIBS-CH-G Spectrometer channel with 800-980 nm wavelength range

Note: Channels do NOT have to be consecutive

1: Introduction

Laser Requirements for LIBS2500plus

You can supply your own Q-switched laser (from our certified list), or you can purchase one through
Ocean Optics. Laser requirements include a low-divergence laser beam (a tight focus is required to
achieve a spark), an active electro-optic Q-switch, and external triggering and synchronization capability
for the laser flashlamp and Q-switch.

We recommend the ULTRA CFR Nd:YAG laser from Big Sky Laser Technologies

www.bigskylaser.com/compactseries.html). The ULTRA CFR was used when testing prototypes of the

(
LIBS2500plus. The rugged and field-portable ULTRA CFR delivers Q-switched pulses at 1.06 µm, with
variable repetition rates from 1 to 20 Hz. At 1.06 µm, the laser has a pulse stability of ±3%.

We also offer the Crossfire™ double-pulsed laser system in which two laser pulses are used with very
short (0.1–5 µs) inter-pulse spacing. The Crossfire is the backbone of a flexible LIBS system that can be
configured for single or dual pulse operation, quickly and with high repeatability. This enables users to
apply and compare both analytical methods and to reproduce many set-ups referenced in existing
publications. Timing between laser pulses is controlled via Crossfire software or through the
spectrometer(s). Imaging and targeting of samples is supported by means of the on-board video
microscope and electronics controlled via the Crossfire software. (See

machines.com for more information.)

http://www.photon-

166-00000-000-02-0110 5

1: Introduction

LIBS Sample Chamber

The LIBS-SC Sample Chamber is a key component of the Ocean Optics LIBS system and is designed to
perform various functions safely and in clear view. The chamber houses a manually controlled x-y stage.
The chamber is made of an eye-protective polymer that provides a clear view of a sample. The laser focus
lens and spectrometer probe mounting hardware is easily adjustable to accommodate samples varying in
height. The sample chamber also includes an exhaust system to evacuate any particulates created by the
ablation process and an inert gas induction port for ablation area purge. The chamber door is magnetically
latched and interacts with the safety-interlock that prevents the laser from firing when the door is open. A
12 Volt DC power supply is included for chamber lighting and exhaust fan power.

LIBS Imaging Module

The LIBS-IM-USB Imaging Module directly attaches to the LIBS-SC Sample Chamber, which enables
users to magnify a sample image and to establish a laser ablation target on the sample. The camera is also
useful for adjusting the laser focus above or below the sample surface. The LIBS-IM-USB is in the same
focal plane as the sample surface; when the image is in focus, the laser is focused to the surface of the
sample, enabling precise, rapid, and convenient laser focus. The USB-enabled color camera captures pre­and post-ablation images of the sample and provides up to 1280 x 1024 pixel resolution.

OOILIBSplus Software

The Windows-based OOILIBSplus Analysis Software operates the LIBS2500plus spectrometer system,

fires the laser and identifies the element being analyzed. There are five main features in the software:

 Element Identification: The Element Identification feature compares the sample spectrum

against a spectral library to find possible matches. The software will provide a rating of any
matches found based on the number of identical lines. Currently, OOILIBSplus comes with a
library of "persistent lines of spark spectra." We are investigating other spectral library packages.

 Reference Correlation -- by Full Pixel: The Reference Correlation feature allows for real-time

matching of a complete spectrum with spectra in a user-generated library. You can compare the
full spectrum produced by your sample to those in the library and the software instantly provides
the match with the closest composition, the correlation coefficient and a list of all other close
matches. The reference full-pixel library is limited to a specific LIBS2500plus spectrometer
channel.

 Reference Correlation -- by Spectral Line: This version of the Reference Correlation feature is

wavelength-based, not pixel-based. You can set various parameters to identify the presence of a
specific line or lines for wavelength matching. The spectral library can be shared among many
spectrometers, even those with different ranges.

 Line Tracking Over Multiple Samples: This feature allows you to track the height from one to

thousands of chosen lines over many spectra and perform statistical analysis for identifying and
tracking various elements in samples.

 Time Dependent Analysis: This feature performs analysis of the time decay of the plasma. The

spectrometer takes a set of data while delaying the point in which the spectrometer looks at the
plasma after the laser fires. You can then plot progressive decay or differential decay.

6 166-00000-000-02-0110

1: Introduction

 Additional Features: Control of when to sample the plasma during its decay, radiometric

calibration of the spectrometers, and method-saving features to set and perform procedures for an
entire sample test.

NOTE

At the present time, there are only qualitative methods for obtaining percentage
composition of the elements.

Other Required Equipment

 Personal computer – With Windows 98/Me/2000/XP operating system

Additional Recommended Equipment

 Inert Gas Tank and Cable – Supplies inert gas to the LIBS Sample Chamber for ablation area

purge.

 Laser Safety Glasses – Although the LIBS Sample Chamber is constructed of special safety

glass to protect you from the laser, it is recommended that you purchase laser safety glasses rated
for Nd:YAG laser applications (OD6+ @ 1064) to use whenever you are working with a Class 3
or above laser.

166-00000-000-02-0110 7

1: Introduction

8 166-00000-000-02-0110

Chapter 2

Installing the LIBS System

Overview

In general, installing the LIBS2500plus involves the following steps:

► Procedure

1. Unpack and set up the LIBS2500plus components. See Hardware Set-up.

2. Install the OOILIBSplus software on the PC you intend to use with your LIBS2500plus System,
and then restart the PC. See

Software Installation.

3. Connect the cables to the appropriate connectors on the LIBS2500plus equipment (see

Cabling).

4. Test that the LIBS2500plus System is operational (see

Note

Consult the instructions provided with the LIBS Imaging Module and the laser being
used for complete installation and operation instructions for those products. General
guidelines are provided in this manual, but may not cover all the information that you
need to install and operate these components of your LIBS System.

System Start-up).

Hardware

Hardware Set-up

Set up your LIBS2500plus System in the configuration shown in the following figure. Do NOT connect
any of the cables until you have installed the OOILIBSplus Software.

166-00000-000-02-0110 9

2: Installing the LIBS System

LIBS2500plus Hardware Set-up Using Single Laser

LIBS2500plus Hardware Set-up Using Dual Laser

► Procedure

1. Remove the LIBS2500plus components and laser from their packaging.

2. Place the sample chamber or Crossfire system and the rack of spectrometers on a clean, flat

surface.

10 166-00000-000-02-0110