Diamond & Related Materials 14 (2005) 1916 – 1919

www.elsevier.com/locate/diamond

High pressure–high temperature growth of diamond crystals using

split sphere apparatus
Reza Abbaschian a,*, Henry Zhu b, Carter Clarke b
a
Mechanical Engineering, University of California, Riverside, CA 92521, USA
b
Gemesis Corporation, 7040 Professional Parkway East, Sarasota, FL 34240, USA

Available online 24 October 2005

Abstract

An overview of the application of crystal growth fundamentals in the high pressure – high temperature production of diamond by solvent/
catalyst technique is presented. The process, also called temperature gradient process, makes use of a molten catalyst to dissolve carbon from a
source (graphite or diamond powder) and transport the dissolved carbon to a growth site where they precipitate on a diamond seed. The
pressure and temperature requirements for the process are generally around 5.0 – 6.5 GPa and 1300 – 1700 -C, depending on the chemistry of
the solvent used and the desired crystal geometry. In spite of major progress in the science and technology of diamond growth, large scale
commercial production of diamonds single crystals for jewelry or electronic applications has not been feasible until recently. This has been
mainly due to the substantial cost associated with the presses needed, and the difficulties in controlling the growth parameters and catalyst
chemistry. The recent developments in the commercial production of diamond single crystals utilizing the Split Sphere pressurization apparatus
are discussed.
D 2005 Published by Elsevier B.V.

Keywords: Diamond growth; High pressure – high temperature growth; Diamond crystals

1. Introduction tion, however, remains the high cost of manufacturing,

particularly for large monocrystals.
Diamond possesses many unique physical and chemical Since it was first developed by Bundy et al. at GE in 1955
properties. It is the hardest, least compressible and stiffest [1], high pressure –high temperature (HPHT) technology via a
substance. It also has high dispersion, reflectance and index temperature gradient process has been widely used to produce
of dispersion of any transparent materials. In addition, type Ib and IIa an IIb single crystals. The pressure and
diamond is chemically inert to most acids and alkalis. While
diamond has remarkable thermal conductivity, it is also an
excellent electrical insulator. Moreover, with a band gap of
5.49 eı́, diamond has better semiconducting properties than
silicon for many electronic applications, particularly for high
temperature and high power electronics. These unique
properties make diamond material of choice for a variety of
applications from Jewelry to surgical blades, grinding and
polishing to wire drawing dies, and electronic heat sinks to
infrared windows. The demand for producing man-made
diamonds with tailored properties has been increasing
throughout the years. The main challenge in wider produc-

Fig. 1. Schematic diagram of ‘‘split sphere’’ apparatus; 1—split sphere pressure

* Corresponding author. chamber, 2—safety clamps, 3—large dies, 4—small dies, 5—core, 6—power
E-mail address: rabba@eng.ucr.edu (R. Abbaschian). inlet, 7—rubber membrane, 8—oil inlet, 9—cooling water.

0925-9635/$ - see front matter D 2005 Published by Elsevier B.V.

doi:10.1016/j.diamond.2005.09.007
 R. Abbaschian et al. / Diamond & Related Materials 14 (2005) 1916 – 1919
Fig. 2. Photograph of the split sphere apparatus.
temperature required for the process, generally around 5 –6.5
GPa and 1300 –1700 -C, depend on the chemistry of the
solvent used and the desired crystal geometry. The temperature
gradient process has been used to grow type Ib and IIa an IIb
single crystals. The most commonly used machines for
producing diamond have been Belt, cubic, tetrahedral or
toroidal machines [2 – 4]. The catalysts used for growing
monocrystals involve alloys of Fe, Ni, Co and Mn – C,
with other elements such as Ti, Al, B, Cu, and Ge added to
getter nitrogen impurities for producing colorless or blue
diamonds [4 –10]. Non-metallic solvents have also been
used for a limited extent as catalysts [11,12]. However, the
growth rates and crystal sizes seem to be more limited. The
growth rates using metallic catalysts are in the range of 2 –
15 mg/h, with the largest single crystal grown reported as
34.80 carats [5].
Regardless of the composition of the catalyst used, the
most critical requirement for producing quality crystals is
the precise control of the temperature and pressure through
the entire growth process. Moreover, the temperature
difference between the source materials and growth location
Growth region of high-quality type Ib diamond crystal
8.0
7.5
100
7.0
Pressure (GPa)
6.5
1 2
6.0
5.5
5.0
4.5 Solvent/Carbon Eutectic Melting Line
4.0
1250 1300 1350
Temperature (°C)
Fig. 3. Diamond/graphite phase diagram showing growth region for type Ib yellow diamond crystals.
1917
must also be controlled properly to allow for an optimum
growth rate. Excessive rates cause entrapment of inclusions
and morphological instability at the solid – liquid interface.
Faster growth rates also cause strains and excessive point or
line defects.
2. Split sphere HPHT growth chamber
In spite of major progress by the diamond powder growers
in the science and technology of diamond growth, large scale
commercial production of diamond single crystals for jewelry
or electronic applications has not been feasible until recently.
This has been mainly due to the substantial cost associated with
the capital and operational costs of hydraulic presses to deliver
the required growth pressures. The situation has changed
recently with the introduction of split sphere, or BARS type,
growth apparatus [13,14]. The apparatus, as schematically
shown in Fig. 1, consists of two spherical halves held together
with steel clamps. Pressurized oil is pumped into the cavity
between the inner surface of the spherical chamber and a
rubber membrane, which surrounds eight truncated octet
shaped anvils. The latter anvils in turn transfer the pressure
into the tetragonal growth cell via six pyramid shaped WC – Co
anvils.
Unlike the belt or other similar presses, the split sphere
apparatus is rather compact, as pictured in Fig. 2, and is
capable of maintaining pressure for matter of days by using a
small mechanical pump. It should be noted that the
hydrostatic pressure in the growth cell is intensified by a
factor approximately equal to the ratio of the surface area of
the membrane to that of the growth cell. As such,
approximately 2.5 Kbar of oil pressure in needed to generate
5.0– 6.5 GPa pressure in the growth chamber. Moreover,
because of the special design of the gaskets, an active oil
pressurization program can be utilized to adjust the pressure
within growth cell at a constant level. This is particularly
important for growing large crystals, and for compensation of
100 + 111
111
Points 3-6: Region for
best quality diamonds
3 4 5 6
Diamond/Graphite Equilibrium Line
1400 1450 1500
1918 R. Abbaschian et al. / Diamond & Related Materials 14 (2005) 1916 – 1919

3.5

3.0
Stone Mass (ct)

2.5

2.0

1.5

1.0

0.5

0.0
0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 Fig. 6. (a) A typical rough type Ib yellow diamond crystal; (b) finished about 1
Time (hr) carat yellow diamonds for jewelry applications.

Fig. 4. Mass vs. time curve for type Ib yellow diamond crystals.
ture; {100} planes are dominant at lower temperature (points
1– 2 in Fig. 3), while {111} planes are dominant at higher
the volume reduction upon conversion of graphite to
temperature (points 3– 6 in Fig. 3). Also, it was found that
diamond.
higher growth temperatures, i.e., {111} region in diamond/
graphite phase diagram, yield better quality crystals and more
3. Growth of type Ib crystals
intense colors. It should be noted that the quality of the crystals
also depends on the atomistic processes (dislocation-assisted
Diamonds grown using graphite source and binary Fe– Ni
versus dislocation-free growth) taking place at the diamond–
catalysts generally contain nitrogen impurity atoms. These
solvent interface [16]. Variations in local interfacial kinetics
diamonds are conventionally classified as type Ib, in that the
and morphology can lead to the entrapment of impurities and
majority of nitrogen atoms occupy isolated substitutional sites
particles at the interface.
(C –centers). The level of the nitrogen impurity incorporated in
Mass and size versus growth time curves for type Ib
diamond strongly depends on the purity of the starting
diamond crystals are shown in Figs. 4 and 5. It can be seen that
materials. Diamonds produced from high purity starting
in the early stages of growth (less than 40 h), the mass growth
materials have intense yellow color and contain around 30
rate is about 4 mg/h, while in final stage of the cycle, the mass
ppm nitrogen whereas those produced from low purity
growth rate can be as high as about 20 mg/h. In contrast, the
materials have higher nitrogen and have yellow-orange
deposition rate per unit area (mm/h) remains approximately
coloration. It should noted that type Ia diamonds, which make
constant during the later stages of growth cycle, while it is
up around 98% of mined diamonds, may contain up to 3000
much higher in the early stage of growth. Consequently, the
ppm of nitrogen. However, the nitrogen atoms in type Ia
increase in the mass accumulation rate is mostly due to the
diamonds occupy, mostly in an agglomerated state of either
surface area increase of the growing crystal. Based on these
pairs (A-centers), clusters of four nitrogen atoms (B-centers), or
findings, high quality yellow diamond crystals with a mass up
mixtures thereof.
to 5 carats can be grown in less than 100 h.
Fig. 3 shows the pressure and temperature regions for
The grown crystals typically have truncated octahedral
growing high-quality type Ib diamond crystals using high
shape dominant with {111} planes, frequently modified with
purity graphite source material and Fe –Ni alloy catalysts in the
minor {110}, {113} and {100} planes [13]. Examples of as
split sphere apparatus. At 6 GPa pressure, high quality yellow
grown crystal together with finished diamonds are shown in
diamonds can be produced in a temperature region from 1350
Fig. 6. Color zoning also exists in these diamonds as the
to 1450 -C. The stable growth range is much broader than
those reported for Fe – Co catalysts by Sumiya et al. [15]. The
crystal morphology strongly depends on the growth tempera-

9
8
7
6
Size (mm)

5
4
3 Width
Length
2
Height
1
0
0 10 20 30 40 50 60 70 80 90
Time (hr)
Fig. 7. 2.0 carat type IIb blue diamond crystal grown with Fe – Co – Ti alloy
Fig. 5. Size vs. time curve for type Ib yellow diamond crystals. catalyst.
 R. Abbaschian et al. / Diamond & Related Materials 14 (2005) 1916 – 1919
minor growth sectors look near colorless in yellow and
orange-yellow diamonds [13]. The zoning could be attributed
to the differences in the incorporation of impurities, partic-
ularly nitrogen, in different growth sectors. In general, the
nitrogen concentration in minor growth sectors such as {110}
and {113} is much lower than that in {111} plane sectors. It
should be noted that zoning characteristics also depend on the
growth rate and the catalyst chemistry. The recent works by
Babich et al. [17,18] and Kiflawi et al. [19] indicate that the
growth rate has strong effect on yellow diamond growth when
Fe –Ni and Fe –Co solvent catalyst are used. Notwithstanding,
the exact nature of the zoning and impurity incorporation are
not clearly understood yet. Kiflawi et al. [19] have reported
that a faster growth rate causes an increase in the concentra-
tion of Ni and Co impurities, which is manifested in growth
sector boundaries; when the Ni and Co concentration
increases, the N concentration decreases. Babich et al.
[17,18] on the other hand, indicate that the difference in
concentration of single substitutional nitrogen atoms (C-
centers) and nitrogen pairs (A-centers) throughout the growth
sectors result in color zoning. They reported that the
concentration of C-centers increases substantially from seed
area to the surface of the crystal, which is believed to be due
to the annealing and transfer of C-centers to A-centers during
the growth cycle.
4. Growth of type IIa and IIb diamond crystals
Colorless type IIa diamonds are produced by the elimina-
tion of nitrogen impurities with the addition of nitrogen getter
materials such as Ti and Al and B. The latter additive also
imparts blue color to the crystals, making it type IIb. For both
colorless and blue diamond crystals, the growth rates to
prevent entrapment of inclusions are found to be appreciably
slower than that of yellow diamonds. The rates are typically
one quarter of those for yellow diamonds. Moreover, the
temperature and pressure windows for growing high quality
type IIa and IIb diamonds are much narrower than those for
type Ib diamonds. Therefore, more precise control of
temperature and pressure throughout the entire growth cycle
are required for the production of high quality type IIa and IIb
diamond crystals. An example of as-grown 2 carat blue
diamond is shown in Fig. 7. The Color intensity is controlled
by the amount of B added to the catalyst; varying from 15
ppm for light blue to around 500 ppm for dark blue, and 1000
ppm for black diamonds. For the crystal shown in the Fig. 7,
the boron addition was 120 ppm.
1919
5. Summary
High quality Type Ib, IIa and IIb diamond crystals have
been successfully produced using split sphere apparatus. The
apparatus allow for commercial production of high quality
crystals at 6 GPa and 1350 to 1450 -C. Better quality crystals
are grown in the (111) region in diamond/graphite phase
diagram. The growth rate for 5 carat type Ib crystals using Fe –
Ni as catalyst reaches as high as about 20 mg/h towards the end
of 100 h growth cycle. For type IIa and IIb diamonds, the
growth rate necessary for the production of high quality
crystals is much lower than that of type Ib.
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