Selenium in Infrared Technology

a presentation to the Selenium-Tellurium Development Associations Symposium

Funsho Ojebuoboh

19 May 2015 Hamburg, Germany

A Vital Materials Co.

HIGH-PURITY SPECIALTY MATERIALS FOR ELECTRO-OPTICS REPLACEMENT OPTICS FOR CO2 LASERS

ZnSe Focusing

Lenses Flat Mirrors Phase Retarders

Phoenix Infrared Corporation 3 Foundry Street Lowell, MA 01852 Ph: (978) 458-8328

A Vital Materials Co.

The Electromagnetic Spectrum The electromagnetic spectrum is vastuntil about 150 years ago we had no idea that nearly all of it even existed. Our eyes see only a tiny portion of the information that the universe continually sends usin fact, Our eyes are sensitive to about a thousand billionth of one percent of what is actually there.

www.physicsinfo.co.uk

http://r.search.yahoo.com/_ylt=AwrTcYDNuUJVwjYA0aejzbkF;_ylu=X3oDMTBxNG1oMmE2BHNlYwNmcC1hdHRyaWIEc2xrA3J1cmwEaXQD/RV=2/RE=1430465101/RO=11/RU=http:/www.physicsinfo.co.uk/?page=view&id=1695/RK=0/RS=SdXsRf2LBj2rZgXcM332niZVPvs-

The Electromagnetic Spectrum

What are our eyes for? Well, it depends who you ask! 1. Biologist: to gather information about the world around us.

2. Physicist: to reduce the information we receive from the world

around us to a manageable level. The latter perspective informs the work of optics and electro-optical materials!

On Directivity of Light

About Coherence

A. Ordinary Light Source No Fixed Relationship in waves

B. Laser Beam Collimated; i.e., waves are in phase

Coherence - another view

IR Materials for Lenses and Windows

Germanium (Ge) Silicon (Si) Gallium arsenide (GaAs) Magnesium fluoride (MgF2) Aluminum oxynitride (ALON) Sapphire (Al2O3)

IR Materials for Lenses and Windows Zinc sulfide (ZnS), trade name

Cleartran Zinc selenide (ZnSe) Arsenic tri-sulfide (As2S3) IG2, IG4, IG6, Amtir-1As40Se60, Ge33

Si12Se55 (Vitron*) Gasir-1 (Umicore*) Thallium bromo-iodide (KRS-5) Fluorides of light metals (LiF, CaF2) and

others

*Noted only for reference

Zinc Selenide, ZnSe

One of 2 major IR materials by the CVD Process (other is ZnS)

Superior IR Optical Quality

Excellent IR Laser Window (b/c of its low absorption coefficient)

However, a soft material & not durable in erosion environment

Selenium is used in the form of the acid, hydrogen selenide, a very toxic gas. PEL = 50ppb (0.2mg/m3)

CVD; Chemical Vapor Deposition: High level of purity, homogeneity & chemical and oxidation resistance

ZnSe deposit (on mandrel)

H2Se(g) or

Schematic of CVD reactor for making ZnSe (after D. C. Harris, 2007)

via Vacuum pump to scrubbers

ZnSe Processing Fabricated & Coated

Plano Convex Positive Meniscus

Assembled Optics

Other Shapes Galvo Mirrors Prisms, Domes, Brewster Windows,Lenses

CO2 Lasers FLIR:

Night Vision devices Night Vision weapon sights

IR Spectroscopy IR Domes

Absorption & Hardness Profile Of ZnSe vs. Other IR Materials

Bulk Absorption Coefficient @ 10.6m

Knoop Hardness, kg/mm2

Density, g/cm3

Transmission (% ) at 10.6 m

GaAs

Hydrogen Selenide

Poison/toxic Gas, Flammable Gas

Producers Air Products and Chemicals, Inc. ( Solkatronics business) Matheson Tri-Gas (?Scientific Gas Products, SGP) & in 2009 for CIGS PV Taiyo Nippon Sansa Corp. (owns Matheson Tri-Gas) Vital Materials Co. Ltd. Strategic shifts

1) ZnSe Producers have integrated production of H2Se 2) Se (shot) Producer integrated downstream

Recycling ZnSe For Se

Inadvertent H2Se Release

The Chronological story of Zinc Selenide

Objective: Long Wavelength Infra-Red (LWIR) Windows; 8 - 14 um Driver: US Department of Defense Materials Advisory Board

Attributes: Optical uniformity, Sharp Imaging & flexible processing

1964 Charles Townes awarded the Nobel Prize in Physics

Shared with 2 others for the contribution to field of Lasers

1970 U.S. Air Force Avionics Lab initiate work with Raytheon Corp. for CVD of IR materials. Subsequently, work extended for low-absorption ZnSe at 10.6um

1974 ZnSe commercial roll out. Immediately replaced CdTe for lasers manufacturers.

1975 II-VI began development effort to produce ZnSe. Co. already in existence since 1971

1980 CVD Inc. formed by former workers of Raytheon Research.

1986 II-VI began ZnSe production for internal consumption in own laser business.

1987 Morton Thiokol (later Morton International) acquired CVD and relocates operations to Weeks Island, Louisiana

1990 Raytheon exits ZnSe & ZnS business. Phoenix Infrared acquires abandoned Raytheon furnace & begins ZnSe business. II-VI fully self-sufficient (with 4 furnaces) sells ZnSe to others Japan (Sumitomo) began production in mid 90s.

1999 Rohm and Haas acquired Morton International and consequently owned the CVD Inc. production capacity

2000 II-VI acquired LPO (Laser Power Optics) and Union Miniere subsequently withdrew from ZnSe

2009 DOW Chemical purchased Rohm and Haas.

2010 - Several non-US based producers evolve

?Threat of ZnSe Sunset or new opportunities ?Producers

% Share of ZnSe Production

Company II-VI Inc. DOW Chemical

Sumitomo Electric, SEI (JAPAN) Others:

Phoenix Infrared Crystaltechno (RUS) RAI'N (RUS) Phoenix Tek (KOR) Vital Materials Misc.---Guojing (CHI), etc.

II-VI Inc. DOW Chem SEI

Others

Sheet1

Company% Production

II-VI Inc. 45

DOW Chemicals35

Sumitome Electric15

Phoenix Infrared

Crystaltechno

RAI'N (RUS)

Phoenix Tek

Vital Materials

Misc

Company% Production

II-VI Inc. 45

DOW Chemical35

Sumitome Electric15

Others 5

Company

II-VI Inc.

DOW Chemicals

Sumitome Electric

Others:

Phoenix Infrared

Crystaltechno

RAI'N (RUS)

Phoenix Tek

Vital Materials

Misc

II-VI Inc.

DOW Chem

SEI

Sheet2

Sheet3

Sumitomo Electric Industry 2012

Mirrors: Cu, Mo, Si

Lenses: Plano-convex & Meniscus. All ZnSe highly transparent to CO2 Laser light

The CO2 Laser

IPG Photonics, Oxford, Mass. 13 Jan 2015

Fiber Laser Processing Machine (IPG Photonics Corp.)

Cameras & FLIR Quick Disconnect Lens

IR Lens ~25mm

Germanium Good mechanical properties, non-hygroscopic

Sapphire Hard, durablehigh pressure, high power apps. Zinc Selenide

Preferred for medical imaging, high power. Excellent thermal shock resistance & Low absorption coeff.

And so; what does this mean for Se? H2Se Production US _ Merchant Air Products Matheson TriGas US _ Internal II-VI Dow (Rohm and Haas)

Japan_Merchant Matheson TriGas (parent:

Taiyo Nippon Sanso Corp. Group)

Japan-Internal ?Sumitomo Russia ?? China Vital Foshan Huate Gases Co., Ltd CIGS ?? Included in Merchant

*KG Selenium (via H2Se)

ZnSe Consumption

210,000

CIGS Consumption

40,000

Total 250,000 *Industry Estimate; 2013 calendar year.

Se in IR: UPSIDE/DOWNSIDE STORY! 3-5 YEARS

FIBER LASER DISPLACEMENT OF CO2 LASER Downside. Challenge to CO2 Laser. Effect already evidentwill reduce ZnSe in the mid - long term

IR CAMERAS NEW APPS Upside. Preferred lens material not clear yet. Likely split depending on camera end-use. ZnSe will benefit

A Vital Materials Co. Thank You!

Moments in Aurora, Colorado. Our eyes see only a tiny portion of the information that the universe continually sends usRejoice. We see the beautiful part of the spectrum!

Selenium in Infrared TechnologySlide Number 2The Electromagnetic SpectrumThe Electromagnetic SpectrumSlide Number 5Slide Number 6On Directivity of LightAbout CoherenceCoherence - another viewIR Materials for Lenses and WindowsIR Materials for Lenses and WindowsZinc Selenide, ZnSeSlide Number 13ZnSe ProcessingSlide Number 15Absorption & Hardness Profile Of ZnSe vs. Other IR MaterialsSlide Number 17Recycling ZnSe For SeSlide Number 19% Share of ZnSe ProductionSlide Number 21Slide Number 22Slide Number 23Slide Number 24And so; what does this mean for Se?Slide Number 26