Diamond & Related Materials 19 (2010) 729733

Contents lists available at ScienceDirect

Diamond & Related Materials

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d i a m o n d

Fabrication strategies for diamond based ultra bright single photon sources
Igor Aharonovich , Steven Prawer
School of Physics, University of Melbourne, Parkville, 3010, Victoria, Australia

a r t i c l e

i n f o

a b s t r a c t
Color centers in diamond attract a major attention due to their potential use in quantum information processing. In this work several methodologies to fabricate diamond based single photon emitters are presented: Ion implantation of an impurity into diamond nanocrystals grown by CVD technique or incorporation of an impurity during the CVD growth. The fabricated single photon emitters are photostable and exhibit narrow emission lines in the near infrared. Using sapphire as the growth substrate, ultra bright single photon emitters, with a single photon emission rate of up to millions of photons per second were fabricated by incorporating Cr atoms from the sapphire substrate. The presented techniques open new avenues for fundamental physical and material science experiments which require solid state source of single photons. 2010 Elsevier B.V. All rights reserved.

Available online 4 February 2010 Keywords: Optical centers Cr center Single photon source PL CVD

1. Introduction Diamond is known to have more than a hundred optical centers arising from crystal defects, external impurities and vacancies [1]. Very few of these optical centers have the optical properties which allow the extraction of individual single photons on demand from the center, which is a key element for many quantum optical applications [24]. An ideal single photon source would be a photostable point emitter with a narrow bandwidth and a bright emission, preferably in the near infrared (NIR). In addition, for practical applications, such sources should be easily fabricated. For most of the above criteria, diamonds hosting single defects are perfect candidates. To investigate the fundamental photophysical properties using a confocal microscopy technique, well dispersed high quality diamond crystals with sub-wavelength size need to be controllably synthesized. The nanometer size of the crystals is necessary in order to overcome the geometrical limitation of large crystals which hinders the collection of the emitted light due to high refraction index of the diamond and internal reection [5]. Furthermore, reproducible methods for a controlled doping of the nanodiamonds to achieve the desired optical properties are requiredideally one defect per nanocrystal. To date, the most studied optical center in diamond is the nitrogen vacancy center which possesses unique properties relevant to aspects in quantum information processing (QIP) [68]. However, the NV center has a broad emission at room temperature, centered around 700 nm and strong coupling to phonons which results in only 4% of its total signal being emitted in the zero phonon line (ZPL) centered at 637 nm. For some applications such as quantum key distribution [2] these are negative characteristics, since for free space transmission under atmo-

spheric conditions the emission at 637 nm results in high absorption and the large width of the emission results in high dispersion in bred optical systems. Furthermore, for biological labeling, one may require a bright emitter in the NIR with a narrow spectral width to avoid any interference with the living cells [9,10]. Alternatively, a nickelnitrogen NE8 defect has shown a luminescence peak in the near infrared spectral region as well as a narrow spectral width and single photon behavior [11]. Indeed, nickel and other transition metals form a variety of optical centers in diamond in the NIR. Similarly, single photon emission was demonstrated from a silicon vacancy (SiV) complex [12]. However, these defects suffer from difcult fabrication methodologies which results in only limited number of the desired centers in addition to very poor uorescent intensities. Research into the fabrication and characterization of single photon emitters due to transition metals is still in its infancy. Our approach has been to rstly demonstrate a controlled synthesis of high quality diamond nanocrystals with sub-micron size well separated and dispersed on a substrate. Then, two methodologies to fabricate single photon centers in diamond are introduced: (1) a post implantation of impurity (e.g. nickel) followed by thermal annealing and (2) an incorporation of impurities during the chemical vapor deposition (CVD) growth. 2. CVD growth A microwave plasma CVD growth (Atex Inc) was used to grow the nanocrystals. Silica and sapphire are used as the growth substrates. 46 nm nanodiamonds (Nano Amor Inc) were sprayed on the substrate to serve as seeds for the diamond growth [13]. To suppress secondary and spontaneous nucleation as well as suppress the formation of sp2 carbon, the CVD diamonds were grown under high plasma density and high pressure (900 W, 150 Torr) with up to 5% methane diluted in hydrogen gas. A density of 25 crystals in 10 m2

Corresponding author. E-mail address: i.aharonovich@pgrad.unimelb.edu.au (I. Aharonovich). 0925-9635/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.diamond.2010.01.033

730

I. Aharonovich, S. Prawer / Diamond & Related Materials 19 (2010) 729733

with an average size of 500 nm was achieved, which is ideal for confocal microscopy. In addition, this crystal size is big enough to minimize surface effects, and small enough to allow most of the light out. 3. Fabrication of new center by ion implantation 3.1. Direct implantation into nitrogen containing bulk diamond crystal First, we attempted to generate the NE8 center in a bulk diamond. The NE8 center is a nickel nitrogen complex which consists of a nickel atom with four neighboring nitrogen atoms distorting the diamond crystal along the [110] crystallographic direction [14]. This defect is occasionally observed after high pressure high temperature (HPHT) annealing of diamonds grown from nickel catalysts and has also been observed in CVD diamond [15]. To fabricate this center in a controllable manner, ion implantation of nickel ( 1 1011 Ni/cm2) into rich nitrogen HPHT diamond (SUMITOMO Inc) through a metal template with micron sized holes and subsequent annealing to 1000 C was attempted. The HPHT diamonds contain a signicant amount of nitrogen ( 100 ppm), thus increasing the probability for the formation of NE8 which requires four nitrogen atoms for each nickel. A scan over the post-implanted and annealed region using a confocal microscope revealed bright uorescence squares originating from the optical centers created within the diamond by the nickel implantation (Fig. 1a). This method is an efcient way for creating a periodic matrix of optical centers in the diamond. As expected, the damage associated with the implantation created a signicant amount of NV centers, which dominants the detected emission from each square in the confocal map. In

addition to the NV centers, a nickel related complex centered at 883/ 885 nm were also formed due to the implantation Fig. 1b shows the nickel related PL recorded using a 514 nm excitation laser at liquid nitrogen temperatures (80 K). This nickel center is assigned to a Ni + ion in the center of a diamond di-vacancy in a diamond lattice [16] and has a trigonal symmetry. The nickel atom is probably not bonded to the neighboring carbon atoms. The PL doublet originates from a transition between an excited state and two ground states [17]. No NE8 centers were found after this procedure, most likely because the nitrogen atoms are not yet mobile at 1000 C. To enhance the mobility of the nitrogen atoms, higher annealing temperatures of up to 1600 C were applied, however, the NE8 complex was not found. A detailed study for the NE8 formation will be reported elsewhere [18]. The photon statistics of PL light from the 883/885 nm doublet was studied by measuring the normalized second-order time auto-correlation function, g(2)()= b I(t)I(t + )N/bI(t)N2, using the Hanbury Brown and Twiss (HBT) interferometer. Unfortunately, no single photon behavior was observed from the Ni related center (doublet at 883/885 nm). Even when the implantation dose was decreased down to ( 1 1010 Ni/cm2), the center did not exhibit any single photon emission. Lower doses of nickel could not be detected using a conventional confocal microscopy, which indicates that this center is relatively dim and may not be promising for various quantum optical or biological applications. 3.2. Implantation into CVD grown nanodiamonds To avoid the formation of NV centers which screen the possible PL from Ni related centers due to its broad emission and compete for the available vacancies, nanodiamonds grown by CVD were used. The crystals were grown to an average size of 500 nm on silica or sapphire substrates. This time, as the nickel source, we used a focused ion beam (FIB) technique. The use of a dual SEM/FIB allows imaging a specic crystal prior to implantation with a precise accuracy suitable for post processing and scalability [19]. This method allows fabrication of optical centers in a specic crystal of choice as well as in a given space without using any masking or lithographic techniques. This methodology leads to NV free crystals with narrow, sharp emission peaks in the near infrared, generally centered around 770 nm. No narrow PL was detected in the unimplanted regions, convincingly indicating that the origin of the signal is due to the FIB nickel implantation.

Fig. 1. (a) A confocal map of Ni implanted HPHT bulk diamond recorded using a 325 nm excitation. The red squares represent the implanted spots. (b) PL spectrum recorded using a 514 nm excitation laser at 80 K from one of the squares showing the Ni related doublet centered at 883/885 nm.

Fig. 2. Second-order auto-correlation function, g(2)(), recorded from a diamond crystal implanted with a dose of 1 1011 Ni/cm2 (red curve) showing two photon emission. The black curve recorded from a diamond implanted with a dose of 1 1010 Ni/cm2, showing single photon emission. Inset, is a SEM image of a diamond nanocrystal. Scale bar is 500 nm.

I. Aharonovich, S. Prawer / Diamond & Related Materials 19 (2010) 729733

731

Fig. 2 shows the recorded g(2)() with a clear dip at zero delay time, indicating non classical photon emission. For doses of 1 1011 Ni/cm2 the g(2)(0) reaches a value of 0.5 (red curve), indicates two photon emission while for lower doses of 1 1010 Ni/cm2, the g(2)(0) goes well below 0.15 indicating single photon emission (black curve). While the fabricated center is not the previously reported nickel nitrogen complex (NE8), it is likely that the emission is nevertheless associated with nickel. One hypothesis as to its origin is a complex containing silicon and nickel and/or vacancy. Indeed, silicon is easily incorporated into CVD grown diamonds, originated from the quartz chamber or from a silicon containing substrate. An incorporation of a few ppm of silicon into the diamond crystals during the growth is hence likely. Nevertheless, nickel introduced by implantation generates a signicant amount of vacancies, which are upon annealing can migrate and form optically active complexes with the impurity already presented in the crystal, such as SiV complexes [1]. 3.3. Implantation into substrate Ion implantation leaves the implanted ion in an unknown lattice location; it is during the annealing phase that vacancies and interstitials become sufciently mobile so the dopants can occupy lattice sites. Nevertheless, to cause the implanted atom to migrate within the stiff diamond lattice requires quite often extreme annealing conditions (higher than 1600 C for nitrogen to be mobile). Alternative routes of incorporating an external atom, while maintaining the desired optical properties are thus challenging. One approach to tackle this problem is to incorporate the impurity during the growth [20,21]. For HPHT process for instance, when nickel used as a catalyst, the nickel atoms can be incorporated into the diamond lattice during the growth. During CVD growth this is more challenging since the presence of Ni metal in the growth chamber tends to catalyze the growth of carbon nanotubes and other sp2 bonded structures; hence the simple addition of Ni metal into the growth chamber by coating the growth substrate is not an effective method for the incorporation of Ni into CVD grown synthetic nanodiamonds. In an alternative approach, one may implant the ions into the substrate on which the diamonds will be subsequently grown [21]. The plasma etches the substrate during the growth and thus exposes the implanted species (along with the substrate material) to the plasma ball and through gas phase diffusion the impurities are incorporated into the growing diamond crystals. This process, which is schematically depicted in Fig. 3, has the advantage over the implantation route since the introduced atom will sit in the atomistic site with minimum energy rather than being positioned in a random lattice location by a direct ion implantation. This is in a way analogue to a common problem of creating n-type diamond. Effective doping with phosphorus for instance, was available only via its incorporation during the growth in a gas phase [22]. However, while implanted into pure diamond, very poor n-type characteristic was recorded from these samples [23]. Ion implantation techniques generally require a post annealing step to release the residual damage due to the implantation. During the annealing, vacancies are mobile and can form complexes with the dopant (i.e. phosphorus-vacancy), which may result in poor electrical properties. Fig. 4 shows PL spectra recorded from individual diamond nanocrystals grown on nickel implanted substrate. The PL lines (red and black) correspond to different Ni related defects within the diamond
Fig. 4. PL spectra recorded from individual diamond crystals grown on Ni implanted silica showing two PL features in the NIR. The PL lines (red and black) correspond to different Ni related defects within the diamond lattice.

lattice. Statistically, in an area of 10 m2 out of approximately ten to fteen diamond crystals, one to two diamond crystals hosting optical nickel related centers could be found. Note that since there are a few different species present in the plasma (nickel, silicon, oxygen, and hydrogen), various nickel related optical centers with different PL lines are formed. These results are in agreement with previous nickel related PL measurements in the near infrared region which suggest a number of possible nickel related defects [24,25]. Photon statistics recorded from these PL lines showed a clear signature of single photon emission [21]. 4. Growth on sapphire Sapphire is particularly an interesting substrate to grow on for optical applications because it already hosts various elements such as Al, O, Cr, etc. which might be potential defects to generate single photon emission if embedded in diamond [26]. Chromium is especially interesting since it does have luminescent centers in the NIR in silicon [27], which has similar atomistic structure to diamond (but different lattice parameter). Fig. 5a shows a confocal raster scan of CVD diamonds grown on a sapphire substrate. Bright spots, correspond to diamond crystals hosting a particular chromium related color center (will be explained in detail below), are clearly seen. PL spectra recorded from the bright spots revealed narrow features in the region of 740770 nm. Fig. 5b shows an example of such a spectrum (red curve) while other crystals, which were not bright on the confocal map showed a wide band PL (Fig. 5b, black curve). When implementing such sources in quantum optical applications, such as quantum cryptography, a pulsed excitation is required. Fig. 5c shows a pulsed g(2)() measurement recorded from the emitter shown in Fig. 5b (red curve). The vanishing peak at zero delay time indicates that the uorescence output exhibits sub Poissonian statistics which demonstrate that a single color center can therefore be used as a true single photon source. In addition, the lifetime of the center can be

Fig. 3. Schematic illustration of the fabrication of Ni related optical centers by implantation of Ni into substrate, subsequent growth of nanodiamonds and annealing.

732

I. Aharonovich, S. Prawer / Diamond & Related Materials 19 (2010) 729733

Fig. 5. (a) A confocal map showing CVD grown nanodiamonds hosting chromium related color centers. (b) PL recorded from an individual CVD grown diamond crystal. The red curve showing a sharp PL line while another crystal shows only a wide PL. (c) Pulsed g(2)() recorded from a diamond nanocrystal hosting a Cr related defect with narrow PL line (similar to the red curved PL). The vanishing peak at zero delay time is indicative of single photon emission from this center. (d) PL recorded from a bare sapphire substrate. The doublet centered at 700 nm is known as R1 center, originated from a substitutional Cr3+ ion in sapphire.

estimated from this measurement. A lifetime of 3.5 ns is deduced for the emitter shown in Fig. 5b (red curve). The PL from diamond nanocrystals grown on sapphire shows a distribution of wavelengths in the region 740770 nm. Nevertheless, a single photon behavior is maintained for almost all crystals which exhibit a single narrow PL line, independent of the wavelength of the ZPL. Moreover, the lines with FWHM of 10 nm showed typically a two level characteristic behavior, without any observable bunching of the auto-correlation function when excited above saturation while on the other hand, the g(2)() function recorded from narrower lines, with FWHM of 4 nm, showed bunching behavior at short delay times, which can be well described by a three level model. The single emitting centers in the range of 740770 nm are believed to arise from chromium atoms within the diamond lattice as supported by the following evidences: Chromium related centers were observed in diamond in the same spectra region (740 770 nm) [1]. The sapphire substrate has signicant concentrations of Cr ( ppm). Fig. 5d shows a PL recorded from a bare sapphire substrate using a 514 nm laser. The strong doublet around 700 nm is attributed to a Cr defect in the sapphire lattice, and its structure, a substitutional Cr3+ and electronic levels are well known [28]. The Cr nds its way into the growing diamond crystal through gas phase diffusion from the sapphire substrate [26], similarly to the process discussed earlier. PL studies of nanodiamonds grown on silica substrate did not result in similar PL lines.

Although the chromium atoms incorporated homogeneously into the growing diamond crystals, only several crystals exhibit the narrow PL line (Fig. 5b, red curve) while other show the wide emission (Fig. 5b, black curve). This indicates that additional condition (such as Cr charge state, number of atoms, strain, etc.) is required to generate the optical center which provides narrow PL. The experimental and a theoretical work to understand these conditions are currently in progress. The fabricated single photon emitters are photostable and no bleaching or blinking was observed over the experimental time (hours). The photostability of emitters is extremely important for many applications including biological biomarking and quantum optical devices. Fig. 6 shows the uorescence intensity as a function of excitation power recorded from one of the Cr related centers. For comparison, on the same graph the intensities of the fabricated nickel related centers, described in the previous sections, are plotted. Emission in the MHz regime is recorded from the Cr related centers, while Ni related centers yielded slightly lower emission rate, 2 105 counts/s. Therefore, the narrow ZPL and the high brightness makes the Cr related centers very attractive to be used in practical quantum communication protocols or biological labeling. 5. Conclusions A controlled methodology to fabricate diamond based single photon emitters is presented. First, a controlled synthesis of high

I. Aharonovich, S. Prawer / Diamond & Related Materials 19 (2010) 729733

733

Fig. 6. Measured uorescence intensity as a function of excitation power for various single photon emitters described earlier. Red triangles represent the emitters produced by nickel implantation into substrate, blue circles represent the nickel implantation into grown CVD crystals and the black squares represent the Cr related centers formed within CVD crystals. The count rate at saturation is deduced from the t.

quality diamond crystals with sub-micron size via CVD technique is achieved. Then, two methodologies to fabricate single photon centers in diamond were examined: An implantation of an impurity into diamond crystals or incorporation of an impurity during the CVD growth. Finally, using sapphire as the growth substrate, ultra bright single photon emitters, emitting in the MHz regime were fabricated, most likely by incorporating Cr from the sapphire substrate. The presented techniques open new avenues for fundamental physical and material science experiments which require solid state source of single photons. Acknowledgements The authors are thankful to Dr S. Castelletto and A. Stacey for helpful discussions. This work was supported by the Australian Research Council, The International Science Linkages Program of the Australian Department of Innovation, Industry, Science and Research (project no. CG110039) and by the European Union Sixth Framework Program under the EQUIND IST-034368. IA acknowledges ARNAM and ARC for their nancial support. References
[1] A.M. Zaitsev, Vibronic spectra of impurity-related optical centers in diamond, Physical Review B 61 (2000) 12909. [2] A. Beveratos, R. Brouri, T. Gacoin, A. Villing, J.P. Poizat, P. Grangier, Single photon quantum cryptography, Physical Review Letters 89 (2002). [3] A.D. Greentree, B.A. Fairchild, F.M. Hossain, S. Prawer, Diamond integrated quantum photonics, Materials Today 11 (2008) 22.

[4] F. Jelezko, J. Wrachtrup, Single defect centres in diamond: a review, Physica Status Solidi AApplications and Materials Science 203 (2006) 3207. [5] A. Beveratos, R. Brouri, T. Gacoin, J.P. Poizat, P. Grangier, Nonclassical radiation from diamond nanocrystals, Physical Review A 64 (2001). [6] T. Gaebel, M. Domhan, I. Popa, C. Wittmann, P. Neumann, F. Jelezko, J.R. Rabeau, N. Stavrias, A.D. Greentree, S. Prawer, J. Meijer, J. Twamley, P.R. Hemmer, J. Wrachtrup, Room-temperature coherent coupling of single spins in diamond, Nature Physics 2 (2006) 408. [7] P. Neumann, N. Mizuochi, F. Rempp, P. Hemmer, H. Watanabe, S. Yamasaki, V. Jacques, T. Gaebel, F. Jelezko, J. Wrachtrup, Multipartite entanglement among single spins in diamond, Science 320 (2008) 1326. [8] C. Santori, P. Tamarat, P. Neumann, J. Wrachtrup, D. Fattal, R.G. Beausoleil, J. Rabeau, P. Olivero, A.D. Greentree, S. Prawer, F. Jelezko, P. Hemmer, Coherent population trapping of single spins in diamond under optical excitation, Physical Review Letters 97 (2006). [9] Y.R. Chang, H.Y. Lee, K. Chen, C.C. Chang, D.S. Tsai, C.C. Fu, T.S. Lim, Y.K. Tzeng, C.Y. Fang, C.C. Han, H.C. Chang, W. Fann, Mass production and dynamic imaging of uorescent nanodiamonds, Nature Nanotechnology 3 (2008) 284. [10] C.C. Fu, H.Y. Lee, K. Chen, T.S. Lim, H.Y. Wu, P.K. Lin, P.K. Wei, P.H. Tsao, H.C. Chang, W. Fann, Characterization and application of single uorescent nanodiamonds as cellular biomarkers, Proceedings of the National Academy of Sciences of the United States of America 104 (2007) 727. [11] T. Gaebel, I. Popa, A. Gruber, M. Domhan, F. Jelezko, J. Wrachtrup, Stable singlephoton source in the near infrared, New Journal of Physics 6 (2004). [12] C.L. Wang, C. Kurtsiefer, H. Weinfurter, B. Burchard, Single photon emission from SiV centres in diamond produced by ion implantation, Journal of Physics BAtomic Molecular and Optical Physics 39 (2006) 37. [13] A. Stacey, I. Aharonovich, S. Prawer, J.E. Butler, Controlled synthesis of high quality micro/nano-diamonds by microwave plasma chemical vapor deposition, Diamond and Related Materials 18 (2009) 51. [14] V.A. Nadolinny, A.P. Yelisseyev, J.M. Baker, M.E. Newton, D.J. Twitchen, S.C. Lawson, O.P. Yuryeva, B.N. Feigelson, A study of C-13 hyperne structure in the EPR of nickelnitrogen-containing centres in diamond and correlation with their optical properties, Journal of Physics-Condensed Matter 11 (1999) 7357. [15] J.R. Rabeau, Y.L. Chin, S. Prawer, F. Jelezko, T. Gaebel, J. Wrachtrup, Fabrication of single nickelnitrogen defects in diamond by chemical vapor deposition, Applied Physics Letters 86 (2005). [16] M.H. Nazare, A.J. Neves, G. Davies, Optical studies of the 1.40-eV Ni center in diamond, Physical Review B: Condensed Matter 43 (1991) 14196. [17] K. Iakoubovskii, G. Davies, Vibronic effects in the 1.4-eV optical center in diamond, Physical Review B 70 (2004). [18] J. Orwa, To be published, (2009). [19] I. Aharonovich, C.Y. Zhou, A. Stacey, J. Orwa, S. Castelletto, D. Simpson, A.D. Greentree, F. Treussart, J.F. Roch, S. Prawer, Enhanced single-photon emission in the near infrared from a diamond color center, Physical Review B 79 (2009). [20] M. Wolfer, A. Kriele, O.A. Williams, H. Obloh, C.C. Leancu, C.E. Nebel, Nickel doping of nitrogen enriched CVD-diamond for the production of single photon emitters, Physica Status Solidi AApplications and Materials Science 206 (2009) 2012. [21] I. Aharonovich, C.Y. Zhou, A. Stacey, F. Treussart, J.F. Roch, S. Prawer, Formation of color centers in nanodiamonds by plasma assisted diffusion of impurities from the growth substrate, Applied Physics Letters 93 (2008). [22] S. Koizumi, M. Suzuki, n-type doping of diamond, Physica Status Solidi AApplications and Materials Science 203 (2006) 3358. [23] J.F. Prins, in, 1995, pp. 580585. [24] A. Yelisseyev, S. Lawson, I. Sildos, A. Osvet, V. Nadolinny, B. Feigelson, J.M. Baker, M. Newton, O. Yuryeva, Effect of HPHT annealing on the photoluminescence of synthetic diamonds grown in the FeNiC system, Diamond and Related Materials 12 (2003) 2147. [25] A. Yelisseyev, H. Kanda, Optical centers related to 3d transition metals in diamond, New Diamond and Frontier Carbon Technology 17 (2007) 127. [26] I. Aharonovich, S. Castelletto, D.A. Simpson, A. Stacey, J. McCallum, A.D. Greentree, S. Prawer, Two-level ultrabright single photon emission from diamond nanocrystals, Nano Letters 9 (2009) 3191. [27] H. Conzelmann, K. Graff, E.R. Weber, Chromium and chromiumboron pairs in silicon, Applied Physics AMaterials Science & Processing 30 (1983) 169. [28] T.M. Hensen, M.J.A. de Dood, A. Polman, Luminescence quantum efciency and local optical density of states in thin lm ruby made by ion implantation, Journal of Applied Physics 88 (2000) 5142.