Single-Crystal Diamond: - Geophysical Laboratory

Single-Crystal Diamond: 

NEW DEVELOPMENTS 

AND APPLICATIONS 

Russell J. Hemley 

Geophysical Laboratory 

Carnegie Institution of Washington 

Washington, DC 

AIRAPT-23 International Conference 

Mumbai, India, Sept. 27, 2011

Diamond and India 

KOH-I-NOR 

From Mogul 

Dynasty to 

the British 

Crown 

The earliest known reference to diamond is a 

Sanskrit manuscript, the Arthasastra ("The 

Lesson of Profit") by Kautiliya, a minister of the 

Mauryan dynasty in 320-296 BCE: 

“A diamond that is big, heavy, capable of bearing 

blows, with symmetrical points, capable of 

scratching from the inside a glass vessel filled 

with water, revolving like a spindle and brilliantly 

shining is excellent." 

HOPE 

From 

Golconda, 

India to 

Washington 

D.C. 

2

Diamond Properties: Early Measurements 

Diamond has the lowest 

compressibility of any known 

substance …intimately related 

to its low expansion coefficient 

and its high atomic 

frequency.. 

L. H. Adams, Compressibility of 

Diamond, J. Wash. Acad. Sci. 11, 

45 (1921). 

C. Ramaswamy, 

“Raman Effect in 

Diamond, Nature. 

Wash. Acad. Sci. 

125, 704 (1921).

Diamond Physical Properties are Unique 

SINGLE CRYSTAL 

DIAMOND 

• High hardness/strength 

• Transparency 

• Low friction 

• Low adhesion 

• High thermal conductivity 

• Low thermal expansion 

• High refractive index 

• Chemical inertness 

• Biocompatibility 

• Radiation hardness 

• Electrical insulator 

• Electronic properties

The Rich 

Polymorphism 

of Carbon 

Predicted 

[Hemley, 

Crabtree 

& Buchanan, 

Physics Today 

(2009)]

OUTLINE 

1. Introduction 

2. Diamond Synthesis 

3. Enhancing Properties 

4. Applications 

5. Outlook and Perspectives

There is a need to expand current high-pressure 

technology to tackle a broad range of new problems 

H 2 

[Ichimura, Phys. Rep. (1995)] 

Carnegie Institution

There is a need to expand current high-pressure 

technology to tackle a broad range of new problems 

• Reach higher pressures (e.g., 1 TPa range) and 

temperatures (>1 eV) 

• Larger sample volumes needed (neutron, x-ray 

inelastic scattering, THz spectra, NMR) 

• Further improve accuracy/precision applications 

of multiple simultaneous measurements 

Ø Not available nature: dan we synthesize 

the needed material? 

CVD homoepitaxial growth 

1.7mm 

3.5mm 

7.5mm 

16.2mm 

0.025 ct 0.25 ct 2.5 ct 25 ct 


Synthesis of Diamond 

High-pressure, high-temperature (HPHT) synthesis 

HPHT Synthesis of 

Diamond at General 

Electric, Co. (1954); 5-6 

GPa, >1000 K, catalysts 

HPHT Diamond Anvils 

• Ultrahigh purity possible 

• Sizes to

Synthesis of Diamond 

Low-pressure, metastable synthesis: 

chemical vapor deposition (CVD) 

• Begun in early 1980’s 

• Polycrystalline films 

• Growth rates ~1 µm/hr 

CVD diamond is synthesized in metastable temperature and pressure 

conditions. Atomic hydrogen is key to diamond deposition. 

Microwaves 

H 2 + CH 4 

• Co-deposition (sp 2 , sp 3 ) 

• Etching (sp 2 , sp 3 ) 

H 2 

e-, Δ 

CH 4 + H CH 3 + H 2 

2 H 

CVD diamond 

Plasma is created 

H 

DIFFUSION 

H 

H 

substrate 

T s = 800 – 1000 o C 

10 10

CVD techniques have enabled new diamond technology 

Diamond Growing in a Plasma Reactor 

Microwave Plasma CVD: 

100-200 torr H 2 pressures 

[Yan et al., Proc. Nat. Acad. Sci. (2002)] 

“Designer Anvils” 

[Vohra & Weir, High 

Pressure Phen. (2002)] 

Production of regular 

diamond anvil 

• 2.45 mm high 

• 0.28 carats 

• Grown in 1 day 

[Yan et al. Phys. Stat. Sol. (2004)] 

[Ho et al., Industrial 

Diamond Rev. (2006)] 

Half-inch single crystal

High-pressure/high-temperature (HPHT) annealing 

can enhance optical properties and hardness 

• Colored CVD 

diamonds made 

transparent 

• Introduce new 

colors 

[Charles et al., 

Phys. Stat. Sol. (2004)] 

[Yan et al. Phys. Stat. Sol. (2004)] Carnegie Institution

[Meng et al., Proc. Nat. Acad. Sci. (2008)] 


Boron-doping of single crystal CVD 

diamond at high growth rates 

• Solid h-BN introduced 

into plasma (B, N codoping) 

4 ppm boron 

• Boron content from 

SIMS and IR spectra 

UV-Visible Spectra 

Synchrotron Infrared Spectra 

[Liang et al., J. Phys.: Condens. Matter (2009)] 


There is a significant drop in N-V center 

luminescence of the B-boron doped diamond 

[Liang et al., J. Phys.: Condens. Matter (2009)] 


Fracture toughness is dramatically enhanced 

by annealing and B-,N- codoping 

• Low-P, high-T annealing can improve SC-CVD diamond 

hardness by 50% without reducing fracture toughness 

• Boron/nitrogen co-doping can greatly increase fracture toughness 


Different MPCVD reactors 

are used and being 

developed 

2.45 GHz, 5-8 kW 

Modified Seki AX5400, AX6500 

2.45 GHz, 

10-15 kW 

New Design 

915 MHz, 75 kW 

Seki AX6600 

Multiple diamond growth (>100 pieces)! 

and large diamond! 

Cross section Electric field 

of CVD distribution 

chamber 

[Hemawan et al., in preparation]

Cutting/ 

Shaping 

Anvils 

l 

l 

l 

l 

Q-switched Nd:YAG Laser; robotic XYZ stage 

Rough diamond to 1 carat anvil in under an hour 

Final mechanical polishing/etching/annealing 

Sputtering/focused ion beam/fine laser cutting

Anvil surface characterization is essential 

for enhanced high P-T performance 

[Krasnicki et al., 

to be published] 

As measured by profilometer 

Three-dimensional view 

of culet segment 

Polished/etched in-house 

Commercial polish 

Nanometer smoothness 

of carefully polished/etched 

diamond 

Zygo New View 

optical profilometer 



CVD single-crystal 

diamond anvils 

[Meng et al., NDNC (2009)] 

2.3 carat 

0.3 carat 


Large high-purity CVD single crystal 

anvils are being produced 

[Meng et al., Phys. Status 

Solidi. A, in press] 

High-purity CVD single-crystal material 

has been grown at high growth rates 

(around 50 µm/h) in the absence of 

impurities (other than hydrogen) 

Transmittance 

1.0 

0.8 

0.6 

0.4 

0.2 

0.0 

This material has high optical quality and 

clarity without visible growth interface 

UV-VIS transmission 

high-purity CVD plate (0.5 mm) 

2.4 ct high-purity CVD anvil (4 mm) 

400 500 600 700 800 

Wavelength (nm) 

Second order Raman 

Intensity (normalized to diamond peak) 

1.0 

0.8 

0.6 

0.4 

0.2 

0.0 

Raman/Photolum 

First order Raman 



480 540 600 


Cathodoluminescence 

12000 

Raman scattering intensity 

10000 

8000 

6000 

4000 

2000 


0 

2100 2400 2700 

1.7mm 

3.5mm 

7.5mm 

Raman shift (cm -1 ) 

16.2mm 

Quality factor = 5 

0.025 ct 0.25 ct 2.5 ct 25 ct 


Spectroscopic characterization reveals origin of residual 

color and ways to further improve optical quality 

Photoluminescence 

Mapping 

Cathodoluminescence 

PL Intensity (normalized to diamond peak) 

2.0 

1.8 

1.6 

1.4 

1.2 

1.0 

0.8 

0.6 

0.4 

0.2 

0.0 



NV center 

480 540 600 


Excited by 457nm laser 

Measuring from culet to girdle 

The color due to unintentional 

leak of nitrogen 


High-purity electronic grade 

diamond can now be produced 

[Meng et al., in preparation] 

1 

Relative Intensity 

0.8 

0.6 

0.4 

0.2 

Quality factor QF = (F-B)/(R-B) 

B - Background 

Intensity 

1600 

1400 

1200 

1000 

800 

600 

400 

200 

0 

1800 2000 2200 2400 2600 2800 

Wavenumber (cm -1 ) 

514.532 

B 

F 

R 

Raman scattering intensity 

0 

0 1000 2000 3000 4000 5000 6000 7000 

12500 

Wavenumber (cm -1 ) 

10000 

7500 

5000 

2500 

QF = 0.04 

0 

1800 2000 2200 2400 2600 2800 3000 

Raman shift (cm -1 ) 


16.2mm 

1.6mm 

10.7mm 

Reaching megabar and multimegabar pressures 

Single-crystal CVD anvils 

can generate multimegabar 

B 

pressures 

2.8mmA 

[W. Mao et al., 

Appl. Phys. 

Lett. (2003)] 

seed 


G 

12.1mm 

H 

B 

9° 

! 

Composite 

anvil polishing 

As-grown CVD anvil 

[Zha et al., High Pres. Res. (2009)] 

Final polishing 

double bevel 


Next generation anvil technology: large and small 

• Single Crystal Diamond Belt Apparatus 

[Boehler and Guthrie,to be published] 

• Nanomachining 

intelligent devices 

[Matsui, to be published] 

• Laser machining 

• Focused ion beams 

• Lithography 

[Struzhkin et al., to be published]

Next generation high-pressure devices 

with larger sample volume 

[Strobel et al., 

in preparation] 

NEUTRON SCATTERING 

Spallation Neutron Source (SNS) 

 

D 2 :D 2 O, C 1 

(1 GPa, RT) 

0.08mm 3 

He: ice II 

structure R-3 

[Londono et 

al. Nature 332, 

141 (1988)] 

SNAP 

INSTRUMENT 

• A volume reduction of 1,000 relative to 

conventional cells (SNS flux) 

• On a path for increasing sample volume 

with larger, high-strength anvils

Single-crystal CVD diamond is an excellent window 

for small-angle x-ray scattering (SAXS) 

Diameter: 3.0 mm, Thickness: 0.5 mm 

The lack of strong cross-shaped scattering and large 

dimensions makes CVD diamond promising for high-pressure SAXS 

[Meng, Ando, Wang, Gruner 

et al., to be published]

Origin of high quality CVD diamond 

SAXS windows and test results 

[Meng, Ando, Wang, Gruner 

et al., to be published] 

{004} projection topography of CVD diamond 

Diameter: 3.0 mm, Thickness: 0.5 mm 

 

 

 

Tests: SAXS spectra of T4 

lysozyme mutants during 

pressure-induced folding 

and unfolding 

CVD diamond with nitrogen 

has stronger SAXS scattering 

!

These techniques are needed to understand the molecular 

basis of microbial viability at very high pressures 

E. coli viability at 2.5 GPa 

[after Bartlett, Sloan Workshop (2008)] 

Morphology changes 

in pressurized E. coli 

from 1 GPa 

[Griffin et al., 


[Sharma et al., to be published] 

Development of new diamondwindowed 

high-pressure apparatus 

for biology and soft matter

Optically Detected Magnetic Resonance 

[Struzhkin et al., 


3.4 

Pressure dependence 

of the ODMR transi9on 

First high pressure experiment 

3.3 

NaCl 

Ne 

NV - 

29 GPa 

Frequency (GHz) 

3.2 

3.1 

3.0 

2.9 

0 10 20 30 

Pressure (GPa)

Extending measurements of superconductivity 

 

 

 

 

 

 

 

 

 

 

3 

1 

2 

3 1 2 

[Chen et al., Nature (2009)]

Prospects for magnetic 

sensing with NV - centers 

PREDICTED SUPERCONDUCTING/ 

SUPERFLUID METALLIC HYDROGEN 

[Babaev et al., Phys. Refv. Lett. (2005)] 

NV - 

• ODMR NVmapping 

with 

pressure 

• Compression of 

nano-diamonds with 

single NV - centers – 

detection of small 

samples in DACs 

• Magnetic mapping using ensembles of NV - 

centers in DACs under pressure vortices, flux 

lines, domains on micron scales 

[Nature Nanotechnology, v.6, 358–363, 2011] 

Insert

Catalyst-free high P-T synthesis 

of nanopolycrystalline diamond 

New form of carbon: 

mesoporous diamond 

[Zhang et al., Proc. Nat. Acad. Sci. (2010)] 

Polynanocrystalline Diamond 

(Ehime Univ.) 

[Nakamoto et al., Rev. Sci. Instrum. (2011)] 

Polycrystalline graphite transforms 

to superhard nanopolycrystalline 

diamond at 20 GPa and 2300 °C. 

The technique has been extended 

to create mesoporous forms. 

TEM image reveal a 

mesostructure in the diamond

New transformation in sp 3 

carbon – ‘amorphous diamond’ 

[Lin et al., Phys. Rev., Lett., in press] 

• Conversion of glassy sp 2 carbon to 

all sp 3 carbon 

• No glassy carbon observed above 45 GPa 

• Reversible transformation

Probing carbon in new P-T regimes 

[Smith, Eggert, Braun, Jeanloz, Duffy, et al.] 

 

 

 

Diamond to 5 TPa 

1000 

LASER DRIVEN DYNAMIC 

COMPRESSION 

Distance (pixels) 

800 

600 

400 

14 

16 18 20 

Time (ns) 

22ns 

• Carbon and other materials at unprecedented compressions 

• Equations of state, phase transformations, structures, etc. 


iamond is needed for this new generation of static 

nd dynamic compression experiments 

 

 

 

Combined static/" 

dynamic compression" 

compression to probe " 

ʻcold compressionʼ and" 

planetary adiabats"

Applications beyond high-pressure science: 

large single crystal diamond in lasers and x-ray optics 

X-ray Topography 

TILT 

Stokes and anti- 

Stokes stimulated 

Raman spectra of 

~670-µm SC-CVD 

diamond with 

picosecond laser 

pumping at 0.532 µm 

and 1.064 µm. 

STRAIN 

[Kaminski et al., Laser Physics Lett. (2007)] 

• 400 rocking curves: 0.006º, 

(0.003º theoretical limit) 

• Separation of tilt and strain 

[Krasnicki et al., to be published] 380 µm 

X-ray lenses have been 

fabricated from 

polycrystalline CVD 

diamond. Single crystal 

material is needed for 

improved optical and 

mechanical properties. 

[Evans-Lutterrodt & 

Isakovic, to be published]

There are numerous other applications 

of single crystal diamond 

Tribological surfaces 

- bearing linings 

Electro-optical devices 

- field emitters 

Semiconductors 

- electrodes 

Thermal management 

- heat sinks/spreaders 

Optical gates 

- x-ray windows 

Acoustic vibrators 

- SAW filters 

Dielectric media 

- capacitor interlayer 

Nuclear detectors 

- particle sensors 

Chemical barriers 

- acid containers 

Precision cutting 

- nanomachining 

Non-linear optics 

- Raman shifter 

Fusion energy 

- ITER, NIF 

Thick Disk Laser 

Nd:GGG >100 kW 

>100 million 0 C, 500 MW fusion power. 

Mechanically strong low loss 

window and injection materials 

Microchannel Cooler 

Ø Convert from Cu to Diamond 

Ultrastrong nozzles for water jet machinining 

Wear resistant wire dies for ultrafine wire production

• What is the nature of carbon 

in extreme environments 

such as deep in the Earth 

• Where is the carbon in the 

Earth and how much is there? 

• How does carbon move 

between reservoirs? 

• Is there a deep source of 

organics? 

• What is the nature and extent 

of deep microbial life? 

Ø 

Ø 

Ø 

Major international 

academic/ government/ 

industrial collaboration. 

Funded by A. P. Sloan 

Foundation ($500 M over 

10 years). 

To join, visit: http://dco.ciw.edu

CONCLUSIONS AND PERSPECTIVES 

1. Diamond remains a ‘cornerstone’ of research on 

materials in extreme environments. 

2. Advances in CVD and other synthesis techniques are 

creating new kinds of diamond with an expanded 

range of physical properties. 

3. Applications of the diamond material in high-pressure 

research span the physical and biological sciences. 

4. New phases and transformations of carbon continue 

to be uncovered. 

5. Future prospects are bright with the development of 

new technology and new international programs.

ACKNOWLEDGEMENTS 

Collaborators 

CARNEGIE INSTITUTION 

Ho-kwang Mao Alexander Goncharov 

Timothy Strobel M. Somayazulu 

Viktor Struzhkin Ronald E. Cohen 

N. Subramanian Muhetaer Aihaiti 

Chih-shue Yan Changsheng Zha 

Reini Boehler Yufei Meng 

Yingwei Fei 

Stephen Gramsch 

Jinfu Shu 

Qi Liang 

Zhenxian Liu Yufei Meng 

Guoyin Shen Yue Meng 

Jerry Potter 

Carnegie Institution 

Financial Support 

DOE/NNSA, DOE/OS/BES, 

NSF, A. P. Sloan Foundation 


Deep 

Carbon 

Observatory 

OTHER INSTITUTIONS 

Amy Lazicki (Livermore) 

K. Litasov (Tohoku) 

Jon Eggert (LLNL) 

Rip Collins (LLNL) 

S. Gruner (Cornell) 

S. Ando (Cornell) 

E. Gregoryanz (Edinburgh) 

Y. Lin (Stanford) 

Wendy Mao (Stanford) 

Yusheng Zhao (LANL) 

Peter Lazor (Uppsala) 

Anurag Sharma (Boston) 

Adrienne Kish (Orleans) 

Burkhard Militzer (UCB) 

Neil Ashcroft (Cornell) 

Roald Hoffman (Cornell)


Thank you!

Single-Crystal Diamond: - Geophysical Laboratory

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