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An effective method to improve the growth rate of

large single crystal diamonds under HPHT
Open Access Article. Published on 09 October 2019. Downloaded on 3/23/2025 10:48:07 AM.

Cite this: RSC Adv., 2019, 9, 32205

processes: optimized design of the catalyst
geometric construction
Yadong Li,a Chunxiao Wang,b Liangchao Chen,b Longsuo Guo,b Zhuangfei Zhang,c
Chao Fang c and Hongan Ma *b

In this work, we presented the influence of catalyst geometric construction on temperature distribution,
flow structure, the transport processes of the carbon atoms, and the resulting diamond growth in the
process of HPHT diamond synthesis. Several catalyst geometry models were tested, and the
experimental results of growth rates were compared with numerical simulations. We revealed that
Received 7th August 2019
Accepted 26th September 2019
increasing the protrusion diameter of the convex-shaped catalysts could significantly improve the
growth rate of diamonds. The diamond growth rate was improved from 1.6 mg h 1 to 4 mg h 1 when
DOI: 10.1039/c9ra06126f
the protrusion diameter was enlarged by 2 mm. These results will be discussed through the
[Link]/rsc-advances characteristic distributions of the temperature and convection fields in the process of diamond growth.

the effect of the geometric size of the catalyst on the growth of

Introduction diamonds has not been claried. It is of great signicance to
High pressure and high temperature (HPHT) processes make it clarify the inuence of the catalyst geometric size on the
possible to produce high-quality large single-crystal diamonds, temperature and convection characteristics and on the result-
which can be used in a wide variety of industrial and ing diamond growth in order to improve crystal quality and
commercial applications such as ultra-precision machining, optimize the diamond growth process.
electronics, optics, quantum processes and jewelry.1–16 The In this study, we established several convex catalyst geometry
growth of large diamonds by the temperature gradient method models with different protrusion diameters to explore the
(TGM) using HPHT processes occurs in solvent/catalyst envi- inuence of the catalyst geometric size on diamond growth. The
ronments. Using TGM, the temperature gradient of the catalyst temperature and convection distribution characteristics of the
provides the main driving force for diamond growth, while the catalyst were simulated by the nite element method (FEM). By
carbon atoms in the catalyst can be transported to the seed analyzing the temperature and convection numerical results, we
crystal by convection ow.17–22 Thus, the temperature gradient revealed that increasing the protrusion diameter of the convex
and convection distribution of the catalyst are signicant catalyst could signicantly improve the growth rate of the dia-
factors that determine the quality and growth rate of the syn- mond. The experimental results indicated the same conclu-
thesised diamond. sions as those of the numerical simulations. The ndings of this
The geometric construction (shape and size) of the catalyst study are expected to lead to further improvements in the
can effectively improve the temperature distribution and production level and yield of large single crystal diamonds
convection structure of the catalyst. In ref. 20, the effect of the using the HPHT process.
catalyst geometry shape on diamond growth was investigated. It
was found that tabular and convex-shaped catalysts have
completely different temperature and convection distribution Simulation and experimental details
characteristics, which are suitable for the synthesis of cubic-
A 3D model of the high-pressure synthesis apparatus and the
shaped and tower-shaped diamonds, respectively. However,
sample assembly were established, as shown in Fig. 1a and b.
The multi-eld coupling analysis module of ANSYS soware was
a
College of Electronical Information Engineering, Yangtze Normal University,
used to complete the numerical simulation of the temperature
Chongqing 408100, China
b
and convection elds of the synthesis cavity. Three convex
State Key Lab of Superhard Materials, Jilin University, Changchun 130012, China.
E-mail: jlu_li1989@[Link] catalyst geometry models with different protrusion diameters
c
Key Laboratory of Material Physics of Ministry of Education, School of Physical were designed. The protrusion diameter of model A was set as 6
Engineering, Zhengzhou University, Zhengzhou 450052, China mm, model B as 7 mm and model C as 8 mm, while the height

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Fig. 1(a) High pressure apparatus used for diamond synthesis, (b)
diamond synthetic cavity assembly structure, (c) convex catalyst
geometry configurations with different protrusion diameters shown by
models A, B and C.

(6 mm) and bottom diameter (15 mm) were exactly the same in
all models, as shown in Fig. 1c. The three models used the same
voltage and thermal boundary conditions in the simulation
process, and the nite element model, material parameters and Fig. 2 Numerical simulation results of temperature and convection in
boundary conditions were obtained from our previous the initial phase of crystal growth. (a–c) Temperature distribution
reports.23,24 results of models A, B and C. (d–f) Convection distribution results of
Experiments on the diamond synthesis were carried out in models A, B and C.
a china type cubic high pressure apparatus (CHPA) with
a synthesis cavity of 42  42  42 mm3 at a pressure of 5.7 GPa
and temperature of 1300  C in all runs. High purity graphite position with the carbon source is the highest at about 1395  C
powder (99.9% purity) and Fe64Ni36 alloy were used as the (red color), where the carbon solubility is the highest, and the
carbon source and the catalyst, respectively. Synthetic diamond low-temperature zone is at the seed position. In addition, we
crystals (size about 0.6 mm) were selected as the seed crystals. can observe that the temperature distributions of the convex
The temperature was measured in each experiment using a Pt- part of the catalyst are obviously different. With the increase in
30% Rh/Pt-6% Rh thermocouple, whose junction was placed the protrusion diameter, the temperature is more slowly
near the crystallization sample. The pressure was estimated by transferred to the central position of the convex part, and a two-
the oil press load, which was calibrated by a curve that was stage temperature difference appears in the vertical direction of
established on the pressure-induced phase transitions of Bi, Tl, the catalyst. The temperature difference between the center of
and Ba. Aer the synthetic experiments, the diamond crystals the convex part of the catalyst and the seed location (pink arrow)
were treated by HNO3 and H2SO4 to remove the residual metal directly affects the vertical growth rate of the diamond. We
and graphite from the surface and we obtained clean crystals. found that with the increase in the catalytic protrusion diam-
An optical microscope (OM) was used to observe the eter, the vertical temperature difference of the catalyst
morphology, size and metal inclusions of the recovered dia- increased, changed from 50  C to 53  C to 55  C, and the
mond. Raman spectra were used to characterize the quality of horizontal temperature difference decreased from 65  C to 63  C
the diamond crystals. The acquisition of the spectra was per- to 60  C. The temperature difference varied by just 2 or 3
formed using a LabRam HR800 spectrometer (Horiba) with degrees when the protrusion diameter was increased by 1 mm.
excitation at 514 nm and a laser spot-size of 100 mm. The driving force for the diamond growth by TGM is
provided by the solubility difference resulting from the
temperature gradient in the catalyst. Therefore, the magnitude
Results and discussion of the temperature gradient directly affects the growth rate of
In this work, we only studied the growth mode of single crystal the diamond. According to the results of the temperature elds,
seeds. Due to the high thermal conductivity of diamonds, the we inferred that the temperature difference between the hori-
temperature and convection elds of the multi-seed growth zontal and vertical directions in the initial growth stage of the
mode were signicantly different from those of the single catalyst only changed by 2 or 3 degrees in the three models. The
crystal seed. Research on the multi-seed growth mode will be catalysts in models A, B and C had the same height and bottom
discussed in a future work. First, we simulated the temperature diameter: 6 mm and 15 mm, respectively; this indicated that the
and convection distributions for the initial growth phase of the temperature change of 2 to 3 degrees had only a slight impact
diamonds, as shown in Fig. 2. From the simulation results, we on the horizontal and vertical temperature gradients during the
can clearly see that the distributions of the temperature and initial growth stage of the diamond.
convection elds are symmetrical. Fig. 2a, b and c show the Fig. 2d–f show the convection distribution results of models
temperature distribution results of models A, B, and C, A, B, and C. We can observe that the maximum convection
respectively. We can see that the temperature at the contact intensity and velocity regions are near the diamond growth

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area, and the weak convection region is near the outer edge of the maximum growth rate compared with those in models B
the catalyst. Furthermore, at the contact position between the and A in the initial growth stage.
catalyst and the carbon source surrounded by the blue dotted In the process of diamond growth, the inuence of the
line, the convection velocity is obviously greater than that at the volume change in the catalyst and the grown diamond on the
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other contact positions, which indicates where the carbon temperature and convection distributions cannot be ignored.
source will be consumed rst. It is even more remarkable that as Therefore, we established a growth model within the grown
the protrusion diameter of the catalyst increased, the convec- diamond and obtained the temperature and convection simu-
tion intensity in the region above the seed was enhanced lation results, as shown in Fig. 4. According to the temperature
signicantly. Meanwhile, the peak values of convection velocity simulation results, the vertical and horizontal temperature
were 7.1  10 6 m s 1 for model A, 11.8  10 6 m s 1 for model differences gradually decreased, while the vertical temperature
Open Access Article. Published on 09 October 2019. Downloaded on 3/23/2025 10:48:07 AM.

B, and 17.8  10 6 m s 1 for model C, which indicated that the difference changed greatly (model A, 52  C; model B, 44  C;
convection velocity increased obviously with the increase in the model C, 28  C). This result indicated that the vertical and
protrusion diameter of the catalyst. To further study the varia- horizontal temperature gradients of the diamond decreased
tion trends of convection velocity in different models, we with the increase in the diamond volume. According to the
selected X and Y paths (Fig. 2d–f) to compare the convection convection simulation results, we can observe that the area
velocities in the three models. dotted with a blue line still represents the location where the
Fig. 3 shows the comparison results of the convection carbon source is rst consumed. More importantly, the regions
velocity on the X and Y paths in models A, B, and C. We can with the strongest convection velocity and intensity are located
observe that along the X and Y paths, model C has the highest around the grown diamond; the convection velocity and inten-
convection velocity, followed by model B and model A. From sity at each crystal surface of the grown diamond in model C are
Fig. 3a, it can be seen that in model C, the convection velocity in signicantly higher than those in models B and A. By observing
the horizontal direction from 2 mm to 6 mm exhibits little the velocity bar, we can also nd that the convection velocity in
change, while in models B and C, the convection velocity in the model C is still the largest (model A, 8.3  10 5 m s 1; model B,
horizontal direction at approximately 2 mm from the seed is 13.9  10 5 m s 1; model C, 14.4  10 5 m s 1).
signicantly enhanced; however, the change in the convection The temperature gradient and convection velocity in the
velocity in the horizontal direction at the 6 mm location occurs catalyst jointly determine the growth rate of the diamond.
just in a tight range. From Fig. 3b, we can see that the maximum Through the above numerical simulation results, it was found
convection velocity is located at 3 mm above the seed, while the that with the increase in the diamond volumes in models A, B
increase in amplitude is about 1.5 times the increase in the and C, the temperature gradient decreased gradually, while the
protrusion diameter. convection velocity and intensity increased. The decrease in the
In the process of crystal growth, convection is the main form temperature gradient represented a decrease in the growth rate,
of mass transport; thus, an increase in the convection velocity while the increase in the convection velocity represented an
and intensity in the catalyst means that more carbon atoms will increase in the growth rate. Therefore, the diamond growth
be transported from the carbon source to the seed diamond,
which indicates that the diamond growth rate will increase.
According to the convection and temperature eld results, we
found that the convection intensity around the seed diamond
and the convection velocity in the vertical and horizontal
directions increased signicantly by enlarging the protrusion
diameter of the convex-shaped catalyst, while the temperature
gradient changed very little in the horizontal and vertical
directions. Thus, we can infer that the growth rate of the dia-
mond in the vertical and horizontal directions will be obviously
improved with the increase in the protrusion diameter of the
convex catalyst. The synthetic diamond in model C exhibited

Fig. 4 Numerical simulation results of temperature and convection of

the catalyst within the grown diamond. (a–c) Temperature distribution
Fig. 3(a) Convection velocity on the X path in models A, B and C. (b) results of models A, B and C. (d–f) Convection distribution results of
Convection velocity on the Y path in models A, B and C. models A, B and C.

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Conflicts of interest
There are no conicts to declare.
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

Acknowledgements
This project was supported by the National Natural Science
Foundation of China (No. 11804305); sponsored by Natural
Fig. 5 (a) Diamonds synthesized on CHPA with an Fe–Ni catalyst at Science Foundation of Chongqing, China. (No. cstc2019jcyj-
5.7 GPa and 1300  C from (b) model A, (c) model B and (d) model C. (e)
Open Access Article. Published on 09 October 2019. Downloaded on 3/23/2025 10:48:07 AM.

msxmX0391); supported by Youth Project of Science and

Typical Raman spectra of the synthesized diamonds from models A, B
and C. Technology Research Program of Chongqing Education
Commission of China. (No. KJQN201901405).

rates in the later growth stage in models A, B and C may tend to

be consistent; the growth rate in each model depends on the
Notes and references
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