Available online at www.sciencedirect.

com

Diamond & Related Materials 17 (2008) 180 184 www.elsevier.com/locate/diamond

HPHT synthesis of diamond with high concentration nitrogen using powder catalyst with additive Ba(N3)2
R.Z. Yu a , H.A. Ma a,, Z.Z. Liang a , W.Q. Liu a , Y.J. Zheng a , X. Jia a,b
a

National Lab of Superhard Materials, Jilin University, Changchun,130012,China b Henan Polytechnic University, Jiaozuo 454000, China

Received 1 July 2007; received in revised form 15 November 2007; accepted 3 December 2007 Available online 14 December 2007

Abstract In this paper, high quality green industrial diamond crystals were synthesized from the system of Fe70Ni30graphite with additive Ba(N3)2 in a china-type large volume cubic high-pressure apparatus (CHPA). FTIR spectra show that the highest nitrogen concentration in the synthesized diamond crystals is up to approximately 2400 ppm. The synthetic diamond crystals exhibit green or deep green color. The shape of synthetic crystals is mainly cub-octahedron. Partial strip crystals are also observed, which may be formed from the stretched cub-octahedron having elongated (100) and (111) crystal faces. It is also found that the synthesis conditions (temperature and pressure) increase with the increasing quantity of Ba(N3)2 additive. 2007 Elsevier B.V. All rights reserved.
Keywords: Diamond; HPHT; Nitrogen concentration; Strip shape

1. Introduction It is well known that diamond has many outstanding properties, such as extreme hardness, optical transmission over a wide range, high thermal conductivity and good insulator [13]. There has been a long history for people to make use of natural diamond, but it is still not very clear about the genesis of natural diamond. People have done much to investigate the forming process of natural diamond [48], which mainly includes the following two research routes. First is to simulate the forming environments of natural diamond. It is usually believed that natural diamond was formed in the magma of upper or lower mantle, where the conditions are both high pressure and high temperature (HPHT) [911]. Since diamond was successfully synthesized using transition metals as solventcatalyst in 1955 [12], it had provided a possibility to simulate the HPHT environments of natural diamond in laboratory. As we know, natural diamond is usually found in kimberlite, which contains many inorganic mineral, such as olivine,
Corresponding author. Tel./fax: +86 431 85168858. E-mail addresses: maha@jlu.edu.cn (H.A. Ma), jiaxp@jlu.edu.cn (X. Jia). 0925-9635/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.diamond.2007.12.014

picrite and phosphorite. So it is believed that diamond, just as natural diamond, can be synthesized using inorganic mineral catalyst, and provides valuable information about diamond nucleation and crystallization that bring us closer to the understanding of natural diamond formation process. So far many inorganic minerals have been chosen as catalysts to synthesize diamond, including carbonates, oxides, hydroxides, chlorides, phosphorus and numbers of other compounds [1317]. But the highest nitrogen concentration of diamond synthesized using inorganic mineral catalyst is only 700 ppm [18], which is much lower than the normal nitrogen concentration of natural diamond (2000 ppm) [7,8]. The other route is to synthesize diamond with the same high concentration of nitrogen as that of natural diamond. Diamond can be classified into types of Ia, Ib, IIa and IIb respectively, based on the concentration and forms of nitrogen and boron [19]. Nitrogen in types Ia and Ib diamond crystals are in the forms of aggregate (A center) and single substitution (C center), respectively. Most of natural diamonds is type Ia, containing more than 1000 ppm nitrogen; while the synthetic diamond, is mainly type Ib, whose nitrogen concentration is typically 200 300 ppm. Recent report indicated that the nitrogen in the type Ib

R.Z. Yu et al. / Diamond & Related Materials 17 (2008) 180184

181

doping (2400 ppm), which is higher than that of diamonds synthesized by Liang et al. of our group (2000 ppm). Besides normal cub-octahedral shape, the crystals exhibit a special strip shape which may be formed from the stretched cub-octahedron having elongated (100) and (111) crystal faces. It is also found that the crystal growth conditions (temperature and pressure) increase with the increasing quantity of Ba(N3)2 additive. This work might be helpful to the further study on the genesis of natural diamond. 2. Experimental
Fig. 1. The sample assembly for diamond synthesized by HPHT.

diamond can be transformed into the forms of type Ia under high pressure and high temperature conditions [20]. So it provided a means for fabricating diamond with the same nitrogen concentration and form as natural diamond. H. Kanda et al. have successfully synthesized diamond containing 12001900 ppm nitrogen using Na2SO4 as catalyst and hexagonal boron nitride as container at 7.7 GPa [7]. But the synthetic diamond exhibited aggregate form and irregular fracture surfaces. Y. Borzdov et al. also synthesized high nitrogen diamond in the system of Fe3NC at the conditions of 7 GPa and 15501850 C [8]. It is found that the twinning crystal is usually prominent. High nitrogen diamond crystals with cub-octahedral shape or octahedral shape have been synthesized by Liang of our group, in the system of Fe90Ni10C with 0.7 wt% additive NaN3, and the nitrogen concentration is 2000 ppm [21]. In this work, Ba(N3)2 as a newly discovered catalystadditive is disclosed for getting the highest level of nitrogen

In this work, diamond crystals were synthesized in a chinatype large volume cubic high-pressure apparatus (CHPA) (SPD6 1200) with sample chamber of 23 mm edge length at 5.0 ~ 5.7 GPa and 1500 ~ 1700 K for 800 s. The sample assembly for diamond synthesis is shown in Fig. 1. Crude scalelike graphite power and Fe70Ni30 alloy powder (200 mesh) were used as carbon source and solventcatalyst respectively. Ba(N3)2 (purity 99%) was used as additive. The graphite power and Fe70Ni30 alloy (1:1,weight ratio) were mixed with Ba(N3)2 additive for 4 h, and then were shaped with the form of pole for synthesizing diamond. A graphite tube was used as heater. The collected samples containing the synthetic diamond crystals were placed in a bottle of boiling mixture of H2SO4 and HNO3 to remove the remaining graphite and metal catalyst. Diamond crystals were observed by an optical microscopy and scanning electron microscope. The concentration of nitrogen in diamond was measured by a Fourier transform infrared (FTIR) spectrometer. For the infrared absorption measurements, a Bomen M110 Fourier transform infrared spectrometer fitted with a Spectra Tech IR-PLANTM microscope was used. The IR

Fig. 2. The relationship between the concentration of Ba(N3)2 and the minimum pressure and temperature for graphite/diamond conversion.

182

R.Z. Yu et al. / Diamond & Related Materials 17 (2008) 180184

FeNi alloy solventcatalyst may change at HPHT, which leads to the moving up of the V-shape regions. 3.2. Morphology, inclusion and color of synthetic diamond Fig. 4 shows the typical photographs of the diamond crystals synthesized from the powder catalystgraphite system. Most of crystals synthesized from the system of Fe70Ni30 and graphite without additive Ba(N3)2 (Fig. 4(a)) present a normal cuboctahedral shape, but a little amount of the crystals shows a shape which looks like a stretched cub-octahedron having elongated (100) and (111) crystal faces. The crystal color is yellow. Some of line and point inclusions can be seen in the crystals. The crystal size range is normal 0.2 mm to 0.3 mm. However, the diamond crystals synthesized with additive Ba(N3)2 (Fig. 4(b)) exhibit green or deep green color, and some of them even opaque. The crystal size varies from 0.2 mm to 0.5 mm. Some foggy inclusions can be seen in the diamond. Besides the normal cuboctahedral shape, the diamond crystals also exhibit a strip shape which looks like a stretched cub-octahedron having elongated (100) and (111) crystal faces, but the amount of this type of crystal is increased. The reason for the amount increase of this crystal type when Ba(N3)2 is added into the reaction system is still unknown. It needed more detailed research. 3.3. SEM photographs of the diamond crystals In order to analyze the surface characters of the diamond synthesized with additive Ba(N3)2 more carefully, we took some SEM photographs of synthetic crystals, which are shown in Fig. 5. Many strip shape crystals exhibit twinning structure, most of which look like a stretched cub-octahedron having elongated (100) and (111) crystal faces (Fig. 5(a) and (b)). Some accidented growth lines take place orderly on the surfaces of the diamond crystals synthesized with additive Ba(N3)2 (Fig. 5(c) and (d)). Fig. 5(d) is the photograph enlarged from the sections marked by ellipse in Fig. 5(c). The width of each line was about 0.53 m. However, no accidented line exists on the crystal surface synthesized without additive Ba(N3)2. Liang et al. also observed such lines on the surface of diamond synthesized with additive NaN3 [22]. We believe these results can be explained as follow. The solvent metals of FeNi alloy crystallized epitaxially on the diamond surface to form dendrites at the

Fig. 3. Scheme of the movement of diamond-forming V-shapes region when Ba(N3)2 was added into the reaction system. (a) the V-shape section of the diamond crystals synthesized without additive Ba(N3)2; (b) the V-shape section of the diamond crystals synthesized with additive Ba(N3)2.

beam size was limited to a 150 m square aperture so as to pass only the diamond particle. 3. Results and discussion 3.1. The V-shape region of diamond synthesized with Ba(N3)2 additive The relationship between the minimum synthesis conditions (pressure and temperature) for graphite/diamond conversion and the amount of Ba(N3)2 additive is shown in Fig. 2. It is found that the minimum pressure and temperature for diamond synthesis increase with an increase of the Ba(N3)2 additive. That is to say, the V-shape region moves up with the increasing quantity of Ba(N3)2 additive (seeing Fig. 3). It is well known that in the PT phase diagram of carbon, the district for diamond formation is a V-shape region bounded by the diamond graphite equilibrium line and the metaldiamond eutectic line, seeing Fig. 3. For different catalysts, the metaldiamond eutectic lines are different, so are the corresponding V-shape regions. When Ba(N3)2 is added into the reaction system, the property of

Fig. 4. Photographs of diamond crystals synthesized from the metalgraphite system. (a) without additive; (b) with additive Ba(N3)2.

R.Z. Yu et al. / Diamond & Related Materials 17 (2008) 180184

183

Fig. 5. SEM images of diamond crystals synthesized with additive Ba(N3)2. (d) is the photograph enlarged from the sections marked by ellipse in (c).

eutectic temperature of the metalcarbon system in the quenching process [23]. Meanwhile, carbon atoms segregated from the liquid and precipitated as diamond in the dendrite arms on the diamond surface. When the Ba(N3)2 additive was added into the reaction system, the characteristics of epitaxial crystallization of solvent metals were changed. So the patterns on the surfaces of diamond synthesized with Ba(N3)2 additive are different from that without additive Ba(N3)2.

3.4. FTIR spectra and nitrogen concentrations Typical FTIR spectra of diamond synthesized with FeNi alloy and different content additive Ba(N3)2 are shown in Fig. 6. The nitrogen impurities are determined to be in substitutional form (type Ib) based on the shape of spectra in one phonon region (8001400 cm 1). These spectra show that the absorption intensities in one phonon region increase with the increase

Fig. 6. FTIR spectra of diamond crystal synthesized from FeNiC system with different content additive Ba(N3)2. (a) 0 wt%; (b) 0.3 wt%; and (c) 0.5 wt%.

184

R.Z. Yu et al. / Diamond & Related Materials 17 (2008) 180184

Table 1 The concentration of nitrogen in diamond synthesized with different content Ba(N3)2 Sample Ba(N3)2 (wt%) Type of diamond Concentration of nitrogen (ppm) 1 2 3 0 0.3 0.5 Ib Ib Ib 200400 14001800 16002400

References
[1] G. Davies, in: P.L. Walker Jr., P.A. Thrower (Eds.), Chemistry and Physics of Carbon: the Optical Properties of Diamond, Dekker, New York, 1977, p. 51. [2] R.H. Wentorf Jr., J. Phys. Chem. 75 (1971) 1833. [3] H.M. Strong, R.M. Chrenko, J. Phys. Chem. 75 (1971) 1838. [4] Shinubo Yamaoka, M.D.Shaji Kumar, H. Kanda, Minoru Akaishi, Diamond Relat. Mater. 11 (2002) 118. [5] Yu.N. Pal'yanov, A.G. Sokol, Yu.M. Borzdov, A.F. Khokhryakov, A. Shatsky, N.V. Sobolev, Diamond Relat. Mater. 8 (1999) 1118. [6] M. Akaishi, S. Yamaoka, J. Cryst. Growth 209 (2000) 999. [7] H. Kanda, M. Akaishi, S. Yamaoka, Diamond Relat. Mater. 8 (1999) 1441. [8] Yu. Borzdov, Yu. Pal'yanov, I. Kupriyanov, V. Gusev, A. Khokhryakov, A. Sokol, A. Efremov, Diamond Relat. Mater. 11 (2002) 1863. [9] H.O.A. Meyer, Am. Miner. 70 (1985) 344. [10] H.O.A. Meyer, in: P.H. Nixon (Ed.), Mantle Xenoliths, Wiley, Chichester, UK, 1987, p. 502. [11] F.R. Byod, J.J. Gurney, S.H. Richardson, Nature 315 (1985) 387. [12] F.P. Bundy, H.T. Hall, H.M. Strong, R.H. Wentorf Jr., Nature 176 (1955) 51. [13] M. Akaishi, H. Kanda, S. Yamaoka, J. Cryst. Growth 104 (1990) 578. [14] M. Akaishi, H. Kanda, S. Yamaoka, Jpn. J. Appl. Phys. 29 (1990) 1172. [15] Y. Wang, H. Kanda, Diamond Relat. Mater. 7 (1998) 57. [16] M. Akaishi, H. Kanda, S. Yamaoka, Science 259 (1993) 1592. [17] T. Taniguchi, D. Dobson, A.P. Jones, R. Rabe, H.J. Milledges, J. Mater. Res. 11 (1996) 2622. [18] Yu. Pal'yanov, Yu. Borzdov, I. Kupriyanov, V. Gusev, A. Khokhryakov, A. Sokol, Diamond Relat. Mater. 10 (2001) 2145. [19] G. Davies, in: P.l. Walker Jr., P.A. Thrower (Eds.), Chemistry and Physics of Carbon, vol. 13, Marcel Dekker, New York, 1977, p. l. [20] A.T. Collins, H. Kanda, H. Kitawaki, Diamond Relat. Mater. 9 (2000) 113. [21] Z.Z. Liang, H. Kanda, X. Jia, H.A. Ma, P.W. Zhu, Q.F. Guan, C.Y. Zang, Carbon 44 (2006) 913. [22] Z.Z. Liang, X. Jia, P.W. Zhu, H.A. Ma, C.Y. Zang, J.M. Qin, Q.F. Guan, Diamond Relat. Mater. 15 (2006) 10. [23] H. Kanda, M. Akaishi, N. Setaka, S. Yamaoka, O. Fukunaga, J. Mater. Sci. 15 (1980) 2743. [24] Z.Z. Liang, X. Jia, H.A. Ma, C.Y. Zang, P.W. Zhu, Q.F. Guan, H. Kanda, Diamond Relat. Mater. 14 (2005) 1932.

of additive Ba(N3)2. The concentration of nitrogen was determined using the FTIR spectra and the method as follow: A 1130cm1 A 1290cm1 A 1370cm1 =0:31 A 2120cm1 40 A 2030cm1 87 A 2160cm1 =127 A 2120cm1 Nitrogen concentration (ppm) =(1130 cm 1)/(2120 cm 1) 5.525, where and A are absorption intensity and recorded values of absorbance, respectively [24]. Types and concentration of diamond crystals synthesized with different content of Ba(N3)2 are shown in Table 1. It can be seen that the nitrogen concentration increases with the increase of Ba(N3)2 additive. The highest nitrogen concentration is 2400 ppm, which is the highest nitrogen concentration reported so far. 4. Conclusion Diamond crystals with high nitrogen concentration up to 2400 ppm were successfully synthesized in the system of Fe70Ni30C with additive Ba(N3)2 at 5.0 ~ 5.7 GPa and 1500 ~ 1700 K. The synthetic diamond crystals exhibit green or deep green color. Besides normal cub-octahedral shape, the diamond crystals present a strip shape which looks like a stretched cub-octahedron having elongated (100) and (111) crystal faces. The nitrogen concentration increases with the increase of Ba(N3)2 additive. It is found that the V-shape region moves up with the increasing quantity of Ba(N3)2 additive. Acknowledgement This work is supported by the National Science Foundation of China under Grant No. 50572032.