Synthesis and Crystal Synthesis and Crystal

Growth in the USGrowth in the US

Presented by:Presented by:

David Bliss, PresidentDavid Bliss, President

American Association for Crystal GrowthAmerican Association for Crystal Growth

US Crystal Growth ResearchUS Crystal Growth Research

�� IndustrialIndustrial -- 30% of members30% of members

�� SmallSmall--business business SBIRsSBIRs

�� Systems houses IR&DSystems houses IR&D

�� Equipment suppliersEquipment suppliers

�� Academic Institutions Academic Institutions -- 35% of members35% of members

�� Contractual with government or industryContractual with government or industry

�� Government LaboratoriesGovernment Laboratories -- 35% of members35% of members

�� Focused on mission applicationsFocused on mission applications

For Inorganic Materials

Crystal growth personnelCrystal growth personnel

�� Bulk crystal growth Bulk crystal growth –– 25% (20025% (200--300)300)

�� Melt growth Melt growth

�� Solution growthSolution growth

�� Hydrothermal growthHydrothermal growth

�� Physical vapor transportPhysical vapor transport

�� EpitaxialEpitaxial crystal growth crystal growth –– 75% (60075% (600--1000)1000)

�� Molecular beam Molecular beam epitaxyepitaxy (MBE)(MBE)

�� OrganometallicOrganometallic vapor phase (OMVPE)vapor phase (OMVPE)

�� Hydride vapor phase (HVPE)Hydride vapor phase (HVPE)

US Employment of R&D Scientists and Engineers

Bulk Crystal MarketsBulk Crystal Markets

�� Czochralski growthCzochralski growth

�� Silicon Silicon –– other than MEMC, entirely foreign owned other than MEMC, entirely foreign owned

�� Oxides Oxides -- many small business suppliersmany small business suppliers

�� Compound Semiconductors Compound Semiconductors –– weak US presenceweak US presence

�� Solution GrowthSolution Growth

�� Optical crystals Optical crystals –– Corporate and Corporate and Gov’tGov’t LaboratoriesLaboratories

�� Gemstones Gemstones –– Commercial companiesCommercial companies

�� Zone melting Zone melting

�� Specialty oxides Specialty oxides -- Academic sourcesAcademic sources

US Suppliers of Single Crystals

2020thth Century Success StoriesCentury Success Stories

�� Computers Computers -- SiliconSilicon

�� Global PositioningGlobal Positioning -- QuartzQuartz

�� Cellular Phones Cellular Phones -- Gallium arsenideGallium arsenide

�� LasersLasers -- Ruby, YAG, oxidesRuby, YAG, oxides

Technologies dependent on and driven by Crystal Growth

2121stst Century ChallengesCentury Challenges

�� Green Energy LightingGreen Energy Lighting -- Gallium NitrideGallium Nitride

�� Detectors for WMDDetectors for WMD -- ScintillatorsScintillators

�� InfraRedInfraRed OpticsOptics -- SemiconductorsSemiconductors

�� Space CommunicationsSpace Communications -- AntimonidesAntimonides

�� High Q Timing DevicesHigh Q Timing Devices -- LangasiteLangasite

Next Generation Technologies Requiring Crystal Growth

Who is paying the bill?

White Light CrystalsWhite Light Crystals

�� Gallium NitrideGallium Nitride--based based LEDsLEDs

�� No commercially available substrate No commercially available substrate GaNGaN crystalcrystal

�� Research using high pressure autoclavesResearch using high pressure autoclaves

�� Gov’tGov’t Labs in Poland and USLabs in Poland and US

�� No National Program for No National Program for GaNGaN crystal developmentcrystal development

�� Sporadic funding through Sporadic funding through SBIRsSBIRs

�� Japanese Industry/Japanese Industry/Gov’tGov’t funding Polish and UCSB effortfunding Polish and UCSB effort

Solid-State Replacements for Light Bulbs

Infrared DetectorsInfrared Detectors

�� HgCdTeHgCdTe -- based detector arraysbased detector arrays

�� No US vendor of Substrate CrystalsNo US vendor of Substrate Crystals

�� DoDDoD relies on foreign sourcesrelies on foreign sources

�� Indium Indium AntimonideAntimonide Focal Plane ArraysFocal Plane Arrays

�� Present day: 2Present day: 2--inch diameter growth technologyinch diameter growth technology

�� Mandate for scaleMandate for scale--up to 6up to 6--inch diameter wafersinch diameter wafers

�� Funded by Funded by SBIRsSBIRs

For IR Focal Plane Arrays

NextNext--generation generation PiezoelectricsPiezoelectrics

�� After quartz, what crystals will operate at higher After quartz, what crystals will operate at higher frequency?frequency?

�� LangasiteLangasite Crystals of high qualityCrystals of high quality

�� Cannot be grown by conventional meansCannot be grown by conventional means�� Solution growth Solution growth -- academic effort at UCFacademic effort at UCF

�� After Lead After Lead ZirconateZirconate, what crystals will give , what crystals will give higher power?higher power?

�� RelaxorRelaxor ferroelectrics ferroelectrics –– PMN alloy crystalsPMN alloy crystals�� Mainly funded through Mainly funded through SBIRsSBIRs

Crystals for Timing and Sonar

What future course of action?What future course of action?

�� What are US future needs?What are US future needs?

�� Is there a market?Is there a market?

�� What is the state of existing US technology?What is the state of existing US technology?

�� Corporate, Academic, and Government LabsCorporate, Academic, and Government Labs

�� What are the obstacles to crystal growth?What are the obstacles to crystal growth?

�� Technical challengesTechnical challenges

Crystal Growth OperationsCrystal Growth Operations

�� Over 100 US companiesOver 100 US companies

�� List of crystal suppliersList of crystal suppliers

�� Updated by AACGUpdated by AACG

�� Small businessesSmall businesses

�� Commercial vendorsCommercial vendors

�� Systems housesSystems houses

�� Captive suppliers Captive suppliers

Factory floor at CC Tech

State of Existing US TechnologyState of Existing US Technology

1.1. Conservative methodsConservative methods

�� Batch processes Batch processes –– conservation of massconservation of mass

�� Czochralski method (Czochralski method (CzCz, LEC, MLEC), LEC, MLEC)

�� Bridgman method (VB, HB)Bridgman method (VB, HB)

2.2. NonNon--Conservative methodsConservative methods

�� Continuous processes Continuous processes –– melt replenishmentmelt replenishment

�� Zone MeltingZone Melting

�� Traveling heater methodTraveling heater method

�� Continuous feeding methodsContinuous feeding methods

Where the jobs are

Obstacles to GrowthObstacles to Growth

�� NonNon--congruently melting crystalscongruently melting crystals

�� StoichiometryStoichiometry is difficult to achieveis difficult to achieve

�� Alloy segregation during growthAlloy segregation during growth

�� NonNon--Uniform composition of crystalUniform composition of crystal

�� MetastableMetastable phase formationphase formation

�� Cannot grow at melting temperatureCannot grow at melting temperature

�� Miscibility GapsMiscibility Gaps

�� Phase separation occursPhase separation occurs

New crystals require advanced crystal growth methods

NonNon--congruent crystalscongruent crystals

�� Congruent melting pointCongruent melting point

Differs fromDiffers from

�� Crystal Crystal StoichiometryStoichiometry

�� Examples:Examples:�� Lithium Lithium NiobateNiobate

�� LangasiteLangasite

�� Bismuth Bismuth TitanateTitanate

AB Compound

Lithium Tantalate Crystals

Congruent vs. StoichiometricCongruent vs. Stoichiometric

�� Lithium Lithium NiobateNiobate GrowthGrowth

�� Congruent crystalsCongruent crystals

�� Periodically poled LNPeriodically poled LN

�� (PPLN)(PPLN)

�� Poor properties in greenPoor properties in green

�� Stoichiometric CrystalsStoichiometric Crystals

�� Difficult to growDifficult to grow

�� Efficient PPLN in greenEfficient PPLN in greenLithium Niobate Crystals

Efforts to Control SegregationEfforts to Control Segregation

�� Major cause of nonMajor cause of non--uniformity in crystalsuniformity in crystals

�� Solution A: reduce melt convectionSolution A: reduce melt convection

�� DiffisionDiffision controlled regimecontrolled regime

�� Similar to microgravity conditionsSimilar to microgravity conditions

�� Solution B: increase stirringSolution B: increase stirring

�� Reduce boundary layer thicknessReduce boundary layer thickness

�� Melt replenishment neededMelt replenishment needed

Model for Magnetic StabilizationModel for Magnetic Stabilization

�� High pressure chamberHigh pressure chamber

�� Synthesize volatile meltsSynthesize volatile melts

�� Strong Magnetic FieldStrong Magnetic Field

�� Control turbulenceControl turbulence

�� 66--inch diameter crystalinch diameter crystal

�� Control shapeControl shape

�� Maintain crystal structureMaintain crystal structure

One recent example

Magnetic LEC Crystal PullerMagnetic LEC Crystal Puller

�� High pressure chamberHigh pressure chamber

�� 2kG Helmholtz Coil2kG Helmholtz Coil

�� MultiMulti--zone heaterszone heaters

�� 50kW power supply50kW power supply

For Synthesis and Growth of Indium or Gallium Phosphide

Magnetic StirringMagnetic Stirring

�� To induce melt stirring:To induce melt stirring:

�� Rotating fieldRotating field

�� Alternating fieldAlternating field

�� Traveling fieldTraveling field

�� For uniform compositionFor uniform composition

�� Alloy crystalsAlloy crystals

Another approach:

Crystal Growth under Applied FieldsCrystal Growth under Applied Fields

�� MagneticMagnetic

�� Electric Electric

�� GravitationalGravitational

�� Vibration frequencyVibration frequency

The state-of-the-

art in bulk crystal growth

Ongoing research efforts in:

Germany

France

Japan

MetastableMetastable Phase GrowthPhase Growth

�� Wrong Crystal Structure at Melting pointWrong Crystal Structure at Melting point

�� Equilibrium phase is not desiredEquilibrium phase is not desired

�� Cooling through phase changeCooling through phase change

�� Results in crackingResults in cracking

�� Examples:Examples:

�� Barium borate Barium borate -- β β phasephase

�� Quartz Quartz -- αα phasephaseβ − Barium Borate

Crystals with Miscibility GapsCrystals with Miscibility Gaps

�� Alloy composition is limited under equilibrium Alloy composition is limited under equilibrium

growth conditionsgrowth conditions

�� Examples: Examples:

�� InGaSbInGaSb -- IR detectors, mid IR lasersIR detectors, mid IR lasers

�� InGaNInGaN -- Green and Blue Lasers, Green and Blue Lasers, LEDsLEDs

�� Require nonRequire non--standard growth methodsstandard growth methods

�� High pressureHigh pressure

�� Low temperatureLow temperature

Lattice

matching

Crystal growth funding in the USCrystal growth funding in the US

�� CorporateCorporate

�� High market volume crystals: silicon, quartzHigh market volume crystals: silicon, quartz

�� Ownership is now offshoreOwnership is now offshore

�� Military market: defense contractorsMilitary market: defense contractors

�� No requirement for US materialsNo requirement for US materials

�� Telecom market: lasers and microwave devicesTelecom market: lasers and microwave devices

�� Fragmented post dotFragmented post dot--com boomcom boom

�� Niche markets: medical, spectroscopy, space, etc.Niche markets: medical, spectroscopy, space, etc.

�� Over 100 small companies, many Over 100 small companies, many SBIRsSBIRs

US Funding for Crystal Growth US Funding for Crystal Growth

�� AcademicAcademic

�� Focus has turned to Focus has turned to nanonano--technologytechnology

�� NASA’s microgravity program terminated 2004NASA’s microgravity program terminated 2004

�� Many groups have disintegratedMany groups have disintegrated�� Renewed funding at NSF may help reverse thisRenewed funding at NSF may help reverse this

�� Government LaboratoriesGovernment Laboratories

�� DoDDoD, DOE are highly focused on applied research, DOE are highly focused on applied research

�� NIST, NREL have primary missionsNIST, NREL have primary missions�� If budget is passed, the ACI initiative will helpIf budget is passed, the ACI initiative will help

Where is the potential support for Where is the potential support for

crystal growth?crystal growth?

�� US Basic research budgetUS Basic research budget

�� 6.1 6.1 DoDDoD basic researchbasic research

�� DOE basic energy science programDOE basic energy science program

�� NSF, NIST American NSF, NIST American CompetivenessCompetiveness InitiativeInitiative

�� SBIR Program SBIR Program –– 2% of 2% of gov’tgov’t procurementprocurement

�� Heavily competitive with device applicationsHeavily competitive with device applications

Can these funds be directed toward crystal growth?

Where do we go from here?Where do we go from here?

�� The US crystal growth community is ready for The US crystal growth community is ready for

changechange

�� Dispersed and diffuse, there is no single Dispersed and diffuse, there is no single

concentration of talentconcentration of talent

�� To the question; “Is there a market?”To the question; “Is there a market?”

�� We need to establish small “markets”We need to establish small “markets”

�� Sponsor advanced topics for crystal growth researchSponsor advanced topics for crystal growth research

�� Need a forum where Academic, Government, Need a forum where Academic, Government,

and Corporate participants can interactand Corporate participants can interact

““Who dominates materials Who dominates materials

dominates technology”dominates technology”

Prophetic saying of Dr. Prophetic saying of Dr. TadahiroTadahiro Sekimoto, Sekimoto,

Japanese businessman and scientist who rose to Japanese businessman and scientist who rose to

be the chairman of NECbe the chairman of NEC

List of Companies doing Crystal Growth in the US

Advanced Photonic Crystals—Hydrothermal KTP, vanadates and other oxides

Alfalight—Diode laser materials

Amberwave—Strained silicon and compound semiconductors

Apollo Diamonds—Gem quality diamonds

ASE Americas (now owned by Schott Solar)—Solar silicon

AXT, Inc.—GaAs, InP, Ge

BP Solar—Solar silicon

Ceres Crystal Industries—Skull melting of cubic zirconia

Ceramare Corporation—Crystal growth and fabrication

Cermet—Zinc oxide

Chatham Created Gems —Artificial gems

Cleveland Crystals—Nonlinear optical materials

Coherent Advanced Crystal Group—Nonlinear optical materials

Commercial Crystal Laboratories—Potassium tantalate and other oxides

Corning—Basic research in a variety of crystal growth areas, including III-V laser materials

Cree Research—Silicon carbide

Crystacomm Inc.—InP

Crystagon Inc.—Magnesium fluoride

Crystal Genesis—Top seeded solution growth of oxides

Crystal IS, Inc—AlN

Crystal Photonics—Crystals for scintillators

Crystal Specialties—GaAs

Crystal Systems, Inc.—Sapphire, silicon

Crystal Technology, Inc.—Lithium niobate, lithium tantalate, tellurium oxide

CTI PET Systems (Knoxville, TN) —Scintillator crystals

Deltronic/Isowave—Lithium Niobate, yttrium iron garnet

Diamond Innovations—Industrial and colored diamonds

Dow Corning Compound SemiconductorSolutions—Silicon Carbide

Emcore—Photovoltaics

Evident Technologies—Quantum dots

Evergreen Solar—Solar silicon

Galaxy Semiconductor—InSb and GaSb

General Electric—Industrial diamond, single crystal superalloys

Honeywell—Sapphire

Howmet (division of Alcoa)—Single crystal nickel-based superalloys for gas turbine

blades

HRL Laboratories—Lasers, nonlinear optics II-VI sensor materials

IBM—Basic research in a variety of crystal growth areas, including Si, SiGe,

nanocrystallization

II-VI, Inc.—II-VI compounds and wide bandgap semiconductors

VLOC (a subsidiary of II-VI) —YAG, fluoride laser hosts

eV Products, Inc. (a subsidiary of II-VI)—CdTe, CdZnTe

US Crystal Growth Companies (2)

Inrad—Nonlinear optical crystals

Integrated Photonics, Inc.—Garnets (mostly magnetooptic), perovskites, other oxide

materials

Intrinsic—SiC

IQE—Semiconductor wafer products

Isomet Corporation—Acousto-optic materials

ITT Night Vision—Epitaxial GaAs for image intensifiers

Keystone Crystal Corporation—CdTe

Kopin—Epitaxial GaAs for transistor applications

Laser Crystal Corp—Ruby

Laser Materials Corp—Nd:YAG

M/A-COM (Tyco Electronics)—GaAs and InP

MEMC—IC grade silicon

Microlink Devices—MOCVD of III-V materials

Northrop Grumman Space Technology—GaAs

Synoptics—Laser host crystals

Novalux—Display materials

Ocean Nanotech—Quantum dots

Philips-Lumileds—All sorts of LEDs

Princeton Lightwave—Epitaxial III-V films

US Crystal Growth Companies (3)

Quantum Dot Corporation—Quantum dots

Radiation Monitoring Devices—Radiation detection materials

Rubicon Technology, Inc.—Kyropoulos Sapphire

Saint Gobain

Formerly Saphikon—Sapphire

Formerly Bicron and Harshaw—Scintillation products

Photonic crystal products (Washougal, WA, formerly owned by Union Carbide)—

Sapphire, ruby, Ti:sapphire, doped YAG

Sarnoff Laboratories—Basic research in a variety of crystal growth areas, including

lasers and detectors

Sawyer Research Products, Inc.—Hydrothermal quartz

Scientific Materials (Bozeman, MT)—Electro-optic crystals

Semiconductor Technology Research—Epitaxial semiconductors

Sensors Unlimited (now owned by Goodrich Corporation)—InGaAs devices

Solaicx—Solar silicon

Spectrolab—Compound semiconductor and lighting products

Spire Bandwidth Semiconductor—Custom compound semiconductor epitaxy

Technologies and Devices International, Inc. (TDI, Inc.)—GaN

Triquint Semiconductor—Epitaxial GaAs

Trumpt Photonics—Diode laser materials

Uniroyal Optoelectronics—LED materials

Zia Laser—Quantum dots

US Crystal Growth Companies (4)