Synthesis of diamonds in Fe–C systems using nitrogen and hydrogen co-doped impurities under HPHT
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Sun Shi-Shuai, Xu Zhi-Hui, Cui Wen, Jia Xiao-Peng, Ma Hong-An. Synthesis of diamonds in Fe–C systems using nitrogen and hydrogen co-doped impurities under HPHT. Chinese Physics B, 2017, 26(9): 098101 
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Synthesis of diamonds in Fe–C systems using nitrogen and hydrogen co-doped impurities under HPHT
† Corresponding author. E-mail:
Project supported by the National Natural Science Foundation of China (Grant Nos. 11504267, 11504269, and 51172089), the Open Project of State Key Laboratory of Superhard Materials, Jilin University, China (Grant No. 201504), and the Doctoral Fund of Tianjin Normal University, China (Grant No. 52XB1518).
Abstract
In this study, we investigate the effect of nitrogen and hydrogen impurities on colors, morphologies, impurity structures and synthesis conditions of diamond crystals in Fe–C systems with C3N6H6 additives at pressures in the range 5.0–6.5 GPa and temperatures of 1400–1700 °C in detail. Our results reveal that the octahedron diamond nucleation in a Fe–C system is evidently inhibited by co-doped N–H elements, thereby resulting in the increase of minimum pressure and temperature of diamond synthesis by spontaneous nucleation. The octahedron diamond crystals synthesized from a pure Fe–C system are colorless, while they become green in the system with C3N6H6 additive. The surface defects of diamond will deteriorate when the nitrogen and hydrogen atoms simultaneously incorporate in the diamond growth environment in the Fe–C system. We believe that this study will provide some important information and be beneficial for the deep understanding of the crystallization of diamonds from different component systems.
1. Introduction
An increasing attention has been paid on the diamond growth under high pressure and high temperature (HPHT) during the last decades, owing to their exotic properties and demonstrated applications.[1–3] It has been established experimentally that catalyst/solvent is an important factor to affect the diamond nucleation and growth.[4–8] Although the studies of diamond crystallization in various catalyst/solvent systems provide further insight into the mechanism of diamond formation, many problems related to the general features and peculiarities of natural diamond remains open because the growth of natural diamond is a complex process.[9,10] Recently, adding impurities is found to be another key factor for controlling the crystallization, morphological characteristics, and optical properties of diamond crystals.[11–14] In order to perceive the mechanism of diamond nucleation and growth more clearly, and provide the potential possibility to synthesize diamonds with unique properties, considerable attention has been devoted on the synergistic effect of catalyst/solvent and impurity on diamond crystallization.
Considering the primary impurities of nitrogen and hydrogen in natural diamonds, the crystallization of diamonds from various catalyst/solvent systems with nitrogen or hydrogen impurity have been widely investigated. Experimental studies show that the nitrogen or hydrogen impurity introduced into catalyst/solvent system will induce drastic changes on the growth, morphology, and particularly the properties of diamonds.[15–17] Further, the simultaneous incorporation of nitrogen and hydrogen into diamond growth conditions is confirmed to be a reasonable approach for investigating the genesis of natural diamond.[18,19] In fact, many natural diamond crystals associated with the inhomogeneous distribution of defects and impurities are composed by {111} faces. Hence, investigating the crystallization of {111} octahedron diamond in the catalyst/solvent system co-doped with nitrogen and hydrogen impurities under HPHT conditions will be considerably beneficial for our further understanding of the genesis of natural diamond. In addition, among catalyst/solvent systems, Fe is a primary element in the earth crust and plays a significant role in the growth process of natural diamond. Simultaneously, the stable growth form of diamond synthesized from Fe–C system under HPHT is typically octahedron.[16] Hence, the study of the synthesis of diamond in the Fe–C system with nitrogen and hydrogen co-doped impurities will be beneficial for further revealing the formation of natural diamond. However, publication on this subject is scarce.
In the present study, we investigated the diamond crystallization in the system of pure Fe catalyst with additive C3N6H6. The effect of simultaneous incorporation of nitrogen and hydrogen elements on colors, morphologies, impurity structures, and synthesis conditions of octahedron diamond crystals in the Fe–C system is investigated in detail. We believe that this study will provide some important information and be beneficial for the deep understanding of the crystallization of diamond from different component systems.
2. Experimental
The diamond crystallization experiments were conducted using a china-type large volume cubic high-pressure apparatus (CHPA) (SPD- 6 × 1200) with a sample chamber of 13-mm edge length. The design of the high-pressure cell for diamond synthesis is shown in Fig.
 | Fig. 1. (color online) High-pressure cell for diamond synthesis. |
After the experiment, the sample was dissolved in boiling H2SO4 and HNO3 for eliminating the remaining graphite and metal on the diamond surface. Then, the morphologies and the structures of the obtained sample were characterized by optical microscopy (OM), SEM, and Fourier transform infrared (FTIR).
3. Results and discussion
3.1. Diamond crystallization in Fe–C system with C3N6H6 additive
The diamond crystallization from a Fe–C system with and without C3N6H6 additive runs at 5.0–6.5 GPa and 1400–1700 °C conditions. Our results reveal that the minimum pressure and temperature for diamond crystallization in the Fe–C–C3N6H6 system (6.1 GPa, 1500 °C) is evidently higher than that without an additive system (5.5 GPa, 1400 °C). In order to illuminate the effect of C3N6H6 additive on diamond crystallization in the Fe–C system clearly, we draw the P–T diagram (Fig.
 | Table 1.
Partial experimental results of diamond growth in Fe–C systems. . |
 | Fig. 2. (color online) (a) P–T diagram of diamond synthesized in Fe–C system, A: without additive, B: with C3N6H6 additive; (b) OM photographs of diamond crystals synthesized from Fe–C system; (c) OM photographs of diamond crystals synthesized from Fe–C system with 0.1 wt.% C3N6H6 additive. |
The optimal synthetic conditions for high quality diamond growth from different systems are shown in Table
| Table 2.
Synthetic conditions for high quality diamond growth from Fe–C systems. . |
3.2. FTIR spectra of synthesized diamonds
where μ(1130 cm−1) and μ(2120 cm−1) represent the absorption intensities of 1130 cm−1 and the dip at 2120 cm−1, respectively, the calculated concentration of nitrogen impurities are 325 ppm for the synthesized diamond from Fe–C–C3N6H6 system. Simultaneously, the samples also exhibit some absorption peaks related to hydrogen impurity at 2850 and 2920 cm−1, corresponding to a –CH2– group.[17–19] The FTIR results reveal that the nitrogen and hydrogen atoms simultaneously incorporated into diamond growth conditions will significantly affect the inner structure of the diamond.
In order to clarify the states of impurities incorporated into the diamond structure, the FT-IR absorption is used for quantitative measurements. Typical FTIR spectra of the synthesized diamond from the Fe–C system with and without C3N6H6 additive are shown in Fig.
 |
 | Fig. 3. (color online) Typical FTIR spectra of synthesized diamond from Fe–C system: (a) with C3N6H6 additive; (b) without C3N6H6 additive. |
3.3. Surface characters of synthetic diamond crystals
The SEM photographs for diamond crystals synthesized from Fe–C system are shown in Fig.
 | Fig. 4. (color online) SEM photographs of diamond crystals synthesized from Fe–C system under 5.5 GPa, 1450 °C. |
 | Fig. 5. (color online) SEM photographs of diamond crystals synthesized from Fe–C system with C3N6H6 additive under 6.1 GPa, 1534 °C. |
 | Fig. 6. (color online) SEM photographs of diamond crystals synthesized from Fe–C system with C3N6H6 additive under 6.1 GPa, 1620 °C. |
 | Fig. 7. (color online) SEM photographs of diamond crystals synthesized from Fe–C system with C3N6H6 additive under 6.1 GPa, 1650 °C. |
The surface texture of the most natural octahedron diamonds is diverse, which is similar to the observed above-mentioned phenomenon. Analysis of the data on the interior structure of natural octahedron diamonds, it can be found that the nitrogen and hydrogen are typically the primary impurities. Hence, the color and surface morphology of natural octahedron diamonds are related to the incorporation of nitrogen and hydrogen impurities into the diamond growth environments, which is similar to the phenomenon in our experiments. Therefore, it should be noted that the states of nitrogen and hydrogen impurities in our produced octahedron diamonds are still evidently different from natural octahedron diamonds. In fact, a longer time is essential for the formation of natural diamonds, while only more than 1 min is required for manmade diamonds.[21,22] Hence, although the nitrogen and hydrogen are easily incorporated into the diamond structure, more stable states of these impurities, such as the aggregated nitrogen forms and the structure of >C=CH2 (located at 3107 cm−1), require further evolution.
4. Conclusion
In this study, we successfully synthesized diamond crystals with octahedron shape from Fe–C systems with and without C3N6H6 additive under HPHT conditions. Our results revealed that the diamond nucleation in a Fe–C system is evidently inhibited by co-doped N–H elements, thereby resulting in the increase of minimum pressure and temperature of diamond synthesis by spontaneous nucleation. Moreover, the color and surface morphology are evidently changed when C3N6H6 is added into the Fe–C system. The results of FTIR studies on synthesized diamonds indicate that the concentration of nitrogen impurity in diamond crystals with C3N6H6 additive is higher than that of the system without additive. Simultaneously, the hydrogen atoms can enter the diamond lattice when N–H co-doped into diamond growth environments. We believe that our study will be considerably beneficial for further investigation on the genesis of natural diamond.
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