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Synthesis of large diamond single crystals under

high pressure and high temperature through
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Cite this: CrystEngComm, 2018, 20,

4127 effective utilization of the synthesis cavity
Yong Li, a Yadong Li,*b Ying Wang,a Jie Zhang,a Mousheng Song,a
Yanchao Shea and Xiaozhou Chenc

Received 14th May 2018,
Accepted 22nd June 2018
DOI: 10.1039/c8ce00786a
rsc.li/crystengcomm
To make maximal use of the synthesis cavity and improve the production efficiency, we designed the dou-
ble seed bed method to synthesize large diamond crystals under high pressure and high temperature
(HPHT) conditions, and the results were both theoretically calculated and verified by experiments. The the-
oretical and experimental results were compared with those of the traditional single seed bed method. Fur-
thermore, the obtained diamond crystals were characterized by Raman spectroscopy and Fourier infrared
spectroscopy (FTIR). The designed method can shed light on the commercial production of synthetic dia-
monds. Additionally, the surface defects formed during the crystal growth process were noticed, and the
formation mechanism of the {100}-oriented surface defects was discussed.

1. Introduction
In view of the exceptional qualities of diamond, it is exten-
sively used in industrial engineering, science and technology,
national defense, jewelry making and other fields.1–4 At pres-
ent, the temperature gradient growth (TGG) method under
HPHT conditions and chemical vapor deposition (CVD) are
considered as the most effective diamond synthesis technolo-
gies, especially HPHT technology. Graphite carbon sources
can achieve direct conversion to diamond at a pressure of 12–
25 GPa and temperature of 1800–2300 °C.5 However, due to
such extremely harsh synthesis conditions and the require-
ment of sophisticated equipment, it is not possible to pro-
mote industrialized production. Additionally, the synthesized
diamonds usually exhibit polycrystals at HPHT conditions,
employing inorganic nonmetallic materials as catalysts, and
these diamonds are difficult to meet the actual demands.6–10
However, these conditions of diamond synthesis can be im-
proved by using about 5–7 GPa and 1260–1500 °C, which are
accompanied with a decrease in the production cost when
metal catalysts are used. Previously, Hu et al. studied the
multiseed method for achieving high-quality sheet cubic dia-
monds synthesis to improve the commercial production.11 Li
et al. published that the growth defects during diamond syn-
thesis could be eliminated by adjusting the catalyst thickness.
Furthermore, temperature and convection fields in the syn-
a
Physical and Applied Engineering Department, Tongren University, Tongren
554300, China
b
College of Electronical Information Engineering, Yangtze Normal University,
Chongqing 408100, China. E-mail: yznu_lyd@163.com
c
JiaoZuo Sino-Crystal Diamond co., LTD., JiaoZuo 454001, China
thesis system were analyzed using the finite element method
(FEM).12–14 Nevertheless, these investigations are all
established basing on the single seed bed method; as is well-
known, it is an effective solution for commercial production
to enlarge the synthesis cavity. However, the synthesis cavity
cannot be enlarged indefinitely because of the limitations of
the equipment and the sintering process of tungsten carbide.
Therefore, it is of great practical significance that scientific re-
search and commercial production of diamonds are restricted
by space, existing equipment conditions and sintering tech-
nology of tungsten carbide.
In this study, we designed a double seed bed method to
synthesize large diamond crystals under HPHT conditions by
employing Fe64Ni36 as the catalyst. The temperature and con-
vection fields of the catalyst in the cavity were simulated by
FEM. We believe that this study will be helpful for improving
the commercial production rate and reducing the cost of dia-
mond crystallization.
2. Experimental details
Diamond crystallization experiments were run on a China-
type large volume cubic high-pressure apparatus with a syn-
thesis cavity of volume 42 × 42 × 42 cm3, as shown in Fig. 1.
Synthetic diamond crystals (size about 0.6 mm) were selected
as the seed crystals. Graphite powders with a purity of 99.9%
were used as the carbon source for diamond growth. It must
be pointed out that the raw graphite powders were pressed
into a carbon ring before the HPHT treatment. Fe64Ni36 alloy
was employed as the catalyst. To synthesize type-IIa diamond
crystals, Ti(Cu) was employed as a nitrogen getter, and the

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Fig. 1 (a) Schematic of the traditional synthesis cavity with single seed bed and only one seed crystal embedded on it. (b) Schematic of the
synthesis cavity designed with double seed beds and two seed crystals embedded on the bottom and top seed beds, respectively.
addition ratio of Ti(Cu) was 1.9 wt%. The experimental tem-
perature was calibrated through the Pt-30% RH/Pt-6% Rh
thermocouple. The pressure was estimated by an oil press
load, which established the corresponding relations between
the pressure-induced phase transitions of Bi, Tl and Ba. After
synthesis, the diamond crystals were treated with HNO3 and
H2SO4 to clear the impurities including catalyst and graphite
on the diamond surfaces.
Due to the extreme physical conditions, it was difficult to
directly monitor the temperature and convection fields of the
growth cell during the diamond crystallization. Hence, FEM
was used to simulate the temperature and convection fields;
the 3D model of the prototype was established using the
SOLIDWORKS software and imported into the ANSYS soft-
ware for calculation and analysis. Herein, only the synthesis
cavity and the tungsten carbide anvil were considered for cal-
culation and analysis. We selected Fluid 142 element and
Solid 69 element for the thermal–electrical–fluid analysis of
the meshing models. The growth cavity was plane symmetric
with the symmetric loadings. To minimize calculations, a
quarter of the model was used. The raw material parameters
and boundary conditions for finite element theory calcula-
tions were derived from previous reports.14–17
3. Results and discussion
3.1. Diamond synthesis using single seed bed
Diamond synthesis using a single seed bed was the tradi-
tional technology to obtain single diamond crystals under
HPHT conditions. In this study, diamond crystallization was
Fig. 2 Optical images of the diamonds obtained with single seed bed
(a) without additives and (b) with Ti(Cu) additives in the synthesis
system.
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established in the Fe64Ni36–C system at the pressure of 6.0
GPa by TGG, and the synthesis cavity is displayed in Fig. 1(a).
The graphite source ring was placed at the high-temperature
region, and the seed crystal was embedded at the low-
temperature region. When the cell assembly was fixed, the
temperature gradient in the cell was stable. The value of tem-
perature gradient in the cell could be adjusted by changing
the assembly. We believe that the graphite was broken, and it
transformed to a diamond structure under the effect of the
catalyst. The obtained diamond structure was continuously
dissolved in the molten catalyst to form a solution of carbon
at HPHT. The driving force for diamond growth was provided
by the temperature gradient in the reaction cell. Then, the
carbon element reached the surface of the seed crystal, and it
formed the diamond structure. The optical morphology of
the synthesized diamond crystals is shown in Fig. 2. It can be
clearly seen that diamond (a) exhibited a typical yellow color
with its dominant {100} faces and minor {111} faces. The yel-
low color resulted from the nitrogen impurity in the diamond
lattices. The diameter and weight of the crystal (a) were 7.8
mm and 2.25 ct, respectively. To obtain a high purity dia-
mond, a certain amount of Ti(Cu) was added as a nitrogen
getter into the synthesis system, and the synthesized dia-
mond is displayed in Fig. 2(b); the {100} face of the crystal
was dominant, and the {111} face was minor. This sample
was colorless and transparent, and its weight was 0.72 ct with
a size of 4.5 mm.
Generally, the growth rate of diamond crystals is in direct
proportion to the temperature gradient of the synthesis sys-
tem. However, surface defects are probably generated at a
Fig. 3 Defects of the obtained diamond {100} surface: (a) diamond
synthesized without any additive; (b) schematic diagram for the
diamond.
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Fig. 4 Schematic of the growth step formation process for a single

screw dislocation on the crystal interface.

higher growth rate. As shown in Fig. 3(a), spiral steps were

found on the surface of the diamond crystal synthesized
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without any additive; this may indicate dominant spiral

growth during the diamond crystallization process. The well-
known spirals are generally believed to terminate at screw
dislocation.18,19 In the early growth stage, a spiral was pro-
duced on the crystal interface when there was a vertical screw
dislocation. The spirals moved along the interface as a result
of carbon atom deposition at each step, thereby achieving
crystal growth. The growth rate of the interface was deter-
mined by the moving rate of the spiral step. The step ad-
vanced at an equal speed along the vertical direction. The an-
gular velocity of step rotation reduced at the same rate as
that of the step movement when its distance from the dislo-
cation center increased. Therefore, the spiral as shown in
Fig. 4, provided a steady stream of growth steps.
Furthermore, the final morphology of the diamond sur-
face exhibited structure defects. Additionally, because of the
existence of screw dislocation, the formation of critical crystal
nucleus was not necessary on the growth interface of the dia-
mond crystal. When the length of the steps produced by
screw dislocation on the growth interface was larger than that
Fig. 6 The vertical direction temperature of the catalyst for the single
and double seed bed synthesis cavities.
of the two-dimensional critical nucleus, carbon element in
the molten catalyst was transported to the step. Then, the
step spread forward at a limited rate. However, the step could
only take the spiral expansion centered at the tip of a screw
dislocation, because one end of the step was fixed to the tip
of the screw dislocation.
3.2. The distributions of temperature and convection fields
in single seed and double seed beds
To explore whether the synthesis cavity designed with double
seed beds was feasible or not, the distributions of

Fig. 5 (a) The distribution of temperature field for single seed bed; (b) the distribution of convection field for the single seed bed; (c) the
distribution of temperature for double seed beds; (d) the distribution of convection field for double seed bed.

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temperature and convection fields in the catalyst with the
single seed bed and double seed beds were simulated by
FEM, as shown in Fig. 5.
We could see from the simulation results that the distribu-
tions of temperature and convection fields in the catalyst while
using a single seed bed were very similar to those of the double
seed beds. Hence, the cavity designed with double seed beds is
probably a feasible option for diamond synthesis, considering
the theoretical calculation results. For the temperature field,
the temperature gradually decreased from the edge to the cen-
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ter along the horizontal direction. Furthermore, the tempera-
ture of the position located at the bottom seed was the lowest.
Along the vertical direction, the temperature at the center was
higher, and the temperatures at the two endpoints (the posi-
tion of the two seed crystals) were relatively lower. Hence, the
temperature gradients generated from the center to the two
endpoints along the vertical direction acted as the driving
forces, prompting the growth of diamond crystals. Additionally,
it was observed that the temperature gradient belonging to the
bottom seed was greater than that of the top seed (Fig. 6).
For the convection fields, the region with the strongest
convection was located near the bottom seed bed, as
displayed in Fig. 5(b) and (d). Correspondingly, the convec-
tion intensity near the top seed bed was relatively weak.
3.3. Diamond synthesis with double seed beds
The traditional synthesis technology for obtaining large dia-
mond single crystals is carried out using only the bottom
seed bed under HPHT conditions. In our study, the cavity
was designed with the double seed beds in an attempt to
make effective use of the restricted space. As shown in
Fig. 1(b), the seed crystals were respectively inlayed at the top
seed bed and bottom seed bed for diamond synthesis at the
pressure of 6.0 GPa. In the designed cavity, two temperature
gradients were generated from the center to the top seed crys-
tal and the bottom seed crystal along the vertical direction.
The two temperature gradients acted as the driving forces
and prompted the dissolved carbon in the molten catalyst to
be transported to the top and bottom seed crystals. The car-
bon element crystallized on the seed crystals when it reached
the surfaces of the seed crystals to realize homoepitaxy
growth of the large single diamond crystals. As displayed in
Fig. 7, crystals (A) and (a) were obtained from the system
without Ti(Cu) additives, and the crystals exhibited yellow
Fig. 7 Optical images of the diamond crystals produced with double
seed bed, (A) crystallization from the bottom seed bed and (a)
crystallization from the top seed bed.
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color. Diamond (A) exhibited cubic morphology with the
dominant {100} faces and minor {111} faces. The weight and
diameter of crystal (A) were 2.34 ct and 8.1 mm, respectively.
Sample (a) displayed an octahedral shape with the dominant
{111} faces, and the {100} faces almost disappeared. The
weight and diameter of crystal (a) were 0.92 ct and 4.4 mm,
respectively. It was observed that the growth rate of diamond
crystallization from the bottom seed bed had an advantage
over that of the crystal synthesized from the top seed bed,
which could be due to the corresponding temperature gradi-
ents of the two crystals. Based on the theoretical calculations
of the distribution of temperature for the double seed beds,
it could be seen that the temperature gradient of the bottom
seed was larger than that of the top seed. Additionally, the
intensity of the convection field for the double seed bed was
stronger around the bottom seed bed than that of the top
seed bed, which made it easier to transport the carbon atoms
to the bottom seed crystal.
As shown in Fig. 8, crystals (a) and (c) were prepared from
the system with Ti(Cu) additives at the pressure of 6.0 GPa
with the double seed beds. Diamond (a) exhibited cubic mor-
phology, and it was colorless and transparent. In principle, it
is more beneficial for the crystallization of diamond growth
when the temperature gradient at the location of seed crystal
is low. However, the visible inclusions in {100}-oriented dia-
mond (b) crystallized at the top seed bed were noticed. A
probable explanation could be as follows: the density of TiN
impurity (5.43 g cm−3) generated from the combination reac-
tion of N and Ti was inferior to that of Fe64Ni36 alloy (about
8.3 g cm−3). Therefore, the TiN impurity floated in the molten
catalyst and got around the crystal (b). Therefore, other impu-
rities along with TiN were trapped, and they entered into the
diamond in the form of visible inclusions during the dia-
mond crystallization process, which revealed the limited abil-
ity of the growing diamond to expel impurities. However, visi-
ble inclusions were absent when the {111}-oriented seed
crystal was placed at the top seed bed, as shown in Fig. 8(c).
The experimental result proved that the high temperature re-
gion was suitable for the {111}-oriented crystal growth.
3.4. FTIR and Raman spectra of diamonds synthesized with
double seed beds
Raman and FTIR spectra measurements are considered as ef-
fective non-destructive techniques to investigate
Fig. 8 Optical images of the diamond crystals grown with double
seed beds (N getter was added), (a) crystallization from the bottom
seed bed, (b) and (c) crystallization from the top seed bed.
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Fig. 9 Raman peaks of the obtained crystals with the double seed beds. (a) Ib type diamond, (b) IIa type diamond.
Fig. 10 FTIR peaks of the obtained crystals with the double seed beds. (a) Ib type diamond, (b) IIa type diamond.
crystallization quality and impurities in diamond
structures.20–22 The typical diamond crystals synthesized
using double seed beds were characterized by FTIR and Ra-
man spectroscopies. As shown in Fig. 9, the characteristic
peaks were located at 1331.75 cm−1 and 1332.02 cm−1. Addi-
tionally, the bottom areas of the Raman spectra were very
flat, and the peaks were sharp, indicating that the obtained
diamonds exhibited high quality.
The typical FTIR spectra of the diamond crystals synthe-
sized with the double seed beds are presented in Fig. 10. The
absorption peaks located at 1130 cm−1 and 1344 cm−1 in the
FTIR spectra could be assigned to substitutional N impurity,
which is common in synthetic diamonds, as shown in
Fig. 10(a). Furthermore, the concentration of N impurity was
approximately 310 ppm, which was evaluated according to
Fig. 11 The diamond crystals synthesized using double seed beds
processed into jewelry, (a) Ib type diamond, (b) IIa type diamond.
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the following formula Nc = [μ(1130 cm−1)/μ(2120 cm−1)] × 5.5
× 2.5.23 It is clearly seen from curve (b) that the absorption
peaks located at 1130 cm−1 and 1344 cm−1 resulting from N
impurity disappeared, indicating that the N concentration of
the corresponding diamond was less than 1 ppm. Addition-
ally, absorptions at 2850 and 2920 cm−1 corresponding to sp3-
CH2-antisymmetric vibrations and sp3-CH2-symmetric vibra-
tions were noticed.22,24 As displayed in Fig. 11, the diamond
crystals synthesized with double seed beds were processed
into jewelry.
4. Conclusions
A diamond crystal synthesis cavity with the double seed bed
method was designed. The distributions of temperature and
convection fields for these double seed beds were compared
with those of the single seed bed, indicating that the
designed method was feasible. Furthermore, diamond crys-
tallization experiments were successfully carried out using
the designed cavity under HPHT conditions, and the
obtained diamond crystals were characterized by FTIR and
Raman, indicating that the obtained diamond crystals with
the double seed beds presented high quality. Additionally,
the formation mechanism of the {100}-oriented surface de-
fects was discussed, which indicated the spiral growth on the
{100}-oriented surface.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Project supported by the National Natural Science Foundation
of China (11604246), Open Project of State Key Laboratory of
Superhard Materials (Jilin University 201610), and Natural Sci-
ence Foundation of Guizhou Province (KY[2017]053,
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[2018]1163 and LH[2017]7311).
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