Photoluminescence of silicon-vacancy defects in nanodiamonds of

different chondrites

A. A. SHIRYAEV1, 2, #

, A. V. FISENKO3, L. F. SEMJONOVA

3, A. A. KHOMICH

4,

and I. I. VLASOV4,5

1 Institute of Physical Chemistry and Electrochemistry RAS, Leninsky pr. 31, korp. 4,

119071, Moscow, Russia

2 Institute of Ore Deposits, Petrography, Geochemistry and Mineralogy RAS, Staromonetny

per. 35, 119071, Moscow, Russia

3 Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Kosygin Street 19,

Moscow, Russia

4 General Physics Institute RAS, Vavilov Street 38, 119991 Moscow, Russia

5 National Research Nuclear University MEPhI, Kashirskoe Avenue 31, Moscow 115409,

Russia

# Corresponding author email: shiryaev@phyche.ac.ru AND a_shiryaev@mail.ru

Abstract

Photoluminescence spectra show that silicon impurity is present in lattice of some

nanodiamond grains (ND) of various chondrites as a silicon-vacancy (SiV) defect. The

relative intensity of the SiV band in the diamond-rich separates depends on chemical

composition of meteorites and on size of ND grains. The strongest signal is found for the size

separates enriched in small grains; thus confirming our earlier conclusion that the SiV defects

preferentially reside in the smallest (≤ 2 nm) grains. The difference in relative intensities of

the SiV luminescence in the diamond-rich separates of individual meteorites are due to

variable conditions of thermal metamorphism of their parent bodies and/or uneven sampling

of nanodiamonds populations. Annealing of separates in air eliminates surface sp2-carbon,

consequently, the SiV luminescence is enhanced. Strong and well-defined luminescence and

absorption of the SiV defect is a promising feature to locate cold (< 250 °C) nanodiamonds in

space.

INTRODUCTION

Nanodiamonds present in meteorites (meteoritic nanodiamonds – MND) remain an

enigmatic substance. Their matrix normalized abundance may reach 2000 ppm (Huss and

Lewis, 1995). Since their discovery (Lewis et al., 1987) the formation process(es) and

astrophysical source(s) of MND remain highly debatable despite significant efforts (see

extensive review by Daulton (2005)). Whereas isotopic composition of noble gases and, in

particular, of Xe indicates that some of nanodiamonds might be related to supernovae

explosions (e.g., Lewis et al., 1987, Jorgenson 1988; Ott et al. 2012), isotopic compositions of

bulk carbon and of the principal chemical impurity – nitrogen – in the diamond-rich separates

are less conclusive and may support hypothesis of that at least a fraction of MND was formed

in the Solar system (Dai et al., 2002). Processes of MND formation are also debatable, but

combined analysis of information about structure and chemical impurities (Shiryaev et al.,

2011) suggests that the growth process of (at least) N-containing grains should be very fast.

The CVD-like (Chemical Vapour Deposition) process (Daulton et al., 1996), possibly

triggered by a shock wave(s) (Shiryaev et al., 2011), looks plausible, but other processes

cannot be excluded (e.g., Blake et al., 1987; Byakov et al., 1990; Duley and Grishko, 2001;

Kouchi et al., 2005; Stroud et al., 2011).

Analysis of isotopic composition of different elements is indispensable for

identification of nanodiamonds source(s). Eventual detection of nanodiamonds in

astrophysical spectra would provide additional information. Detailed knowledge of

spectroscopic properties of meteoritic nanodiamonds is thus of considerable importance.

Attempts to observe nanodiamond features in astrophysical spectra are rather numerous, but

very few of them can be (relatively) unambiguously assigned to diamonds. The most reliable

observations are those by Guillois et al. (1999) and van Kerkhoven et al. (2002) who reported

observation of infra-red features at 3.43 and 3.53 microns in spectra of several Herbig Ae/Be

stars. Perfect match of these bands to peculiar configuration of C-H bonds on surfaces of

“large” nanodiamonds (about 50 nm) makes the assignment of the observed bands to heated

nanodiamonds plausible. Subsequent spatially resolved studies (Habart et al., 2004; Goto et

al., 2009) showed that the diamond-related emission originates from the inner region (<15

AU) of the circumstellar dust disk, whereas PAH emission extends towards the outer region.

The observed spatial heterogeneity may partly reflect temperature and UV flux distribution in

the dust disk. However, the “diamond” bands are observed in less than 4% of the studied

Herbing stars (Acke and van den Ancker, 2006). It is interesting to note a discrepancy

between the sizes of tentatively observed nanodiamonds derived from radiative energy budget

(1-10 nm, van Kerkhoven et al. (2002)) and the fact that the required well-resolved IR bands

are observed only when the nanodiamond grains become sufficiently large to possess crystal

faces resembling those of macroscopic diamond. Investigation of diamond grains smaller than

30 nm shows that the corresponding IR features are blurred and shifted (Sheu et al., 2002;

Maturilli et al., 2014). The discrepancy might be resolved if the hydrogen surface coverage is

incomplete in contrast to the assumption in van Kerkhoven et al. (2002). Chang et al. (2006)

ascribed so-called Extended Red Emission – a broad luminescence-related emission from

some astrophysical objects (see Witt, 2013 for review) - to the photoluminescence of

nitrogen-vacancy (NV) complexes in nanodiamond particles with sizes approx. 100 nm or

larger. Note that the NV defects are extremely difficult to detect in diamond grains smaller

than 30-50 nm (e.g., Bradac et al., 2009; Vlasov et al., 2010) and they are not observed in the

nanodiamonds extracted from meteorites (Shiryaev et al., 2011).

If correct, these assignments imply existence of large (tens-hundreds of nanometers)

nanodiamonds in space. In the same time, the meteoritic nanodiamonds are characterized by

considerably smaller sizes (median size ~2.6 nm) as shown independently by TEM (Fraundorf

et al., 1989; Lewis et al., 1989; Daulton et al., 1996) and MALDI (Lyon et al. 2005, Maul et

al., 2005). Recently published work with atom-probe tomography also showed presence of

nanodiamonds in the small size range 2-3 nm (Heck et al. 2014). Spectroscopic properties of

nanodiamonds are strongly size-dependent and up to now no reliable astrophysical

observations of features resembling spectra of nanodiamonds similar to those from meteorites

are known.

Recently we have reported observation of an important point defect – the silicon-

vacancy complex (SiV) – in nanodiamond-rich separates from Efremovka (CV3) and Orgueil

(CI) chondrites (Shiryaev et al., 2011). Subsequent studies demonstrated that the SiV

luminescence appears to be confined to the smallest diamond grains with sizes below 2 nm

(Vlasov et al., 2014). We report here on examination of the SiV defects in diamond-rich

separates extracted from meteorites of various chemical classes and groups. Implications of

these observations for astrospectroscopy are discussed.

SAMPLES AND METHODS

The diamond-rich separates were extracted from Orgueil (CI), Boriskino (CM2),

Efremovka (CV3), Kainsaz (CO3), and Krymka (LL3) chondrites. The extraction was

performed according to the standard protocol involving dissolution of the meteorite piece by

HCl, HCl+HF, KOH, H2O2, K2Cr2O7, HClO4 at temperatures up to 220 °С (Tang et al., 1988).

The separates possess a translucent pale yellow color, typical for meteoritic colloidal

diamond. Colloidal ammonia solutions of the Orgueil, Boriskino and Krymka separates were

further separated into grain size fractions by centrifugation at various accelerations and

duration. Efficiency of the employed separation method is confirmed by the differences in

isotopic composition of C, N and noble gases between the different size fractions (e.g.,

Verchovsky et al., 1998, 2006; Fisenko et al., 2004; Fisenko and Semjonova, 2006).

Photoluminescence (PL) spectra were measured at room temperature for the following

samples of nanodiamond-rich separates: bulk separate (OD7) and fine-grain (OD13) fraction

(supernatant after 13500 g (50 h) centrifugation of the bulk separate) of Orgueil; BD5 and

BD9 - fine- and coarse-grain fractions (supernatant and sediment, respectively) after

centrifugation (105 g, 4h) of Boriskino separate; bulk separate of Kainsaz; DE1 and DE2 –

bulk separates of Efremovka, but the sample DE1 was additionally subjected to heavy liquid

sedimentation (ρ=2 g/cm3), which depleted the specimen in the grains with density below

2 g/cm3; bulk separate (DKr) and coarse grain (DKr4) fraction (sediments after 10

5 g (4h)

centrifugation of the bulk separate) of Krymka.

The PL measurements were performed using a LABRAM HR spectrometer with an

Ar+ laser (488 nm). To avoid eventual heating of the samples by probing laser beam a minute

amount of the sample was mechanically pressed into pure oxygen-free copper foil. This

method allows production of very thin nanodiamond sample. Since its “fluffiness” is greatly

reduced, good thermal contact with thermal sink is achieved. The laser power was limited to 1

mW and even prolonged laser irradiation had virtually no influence on recorded spectra,

justifying the applied procedure. The accuracy of the determination of the positions of the

peaks in the PL spectra was ±0.1 nm. The spectra were corrected for wavelength-dependent

sensitivity of CCD detector. For the bulk and coarse-size (DKr and DKr4) fractions of the

Krymka separates the measurements were also performed in temperature range from 25 to

450 °C in water-cooled TS 1500 Linkam stage in air. The duration of our heating experiment

(30-45 min for the total cycle; the exposure to high T’s was much shorter) was clearly

insufficient for noticeable modification of defects structure of the nanodiamonds.

RESULTS AND DISCUSSION

Room temperature photoluminescence spectra of the separates are shown in Fig. 1.

Note that due to the confinement effect the PL spectra of nanoparticles remain fairly broad

even at low temperatures. The spectra are normalised to the maximum of the broad band and

are displaced vertically for clarity. The maximum of the broad structureless band lies between

590 and 610 nm. This broad band represents overlapping signals from non-diamond sp2-

carbon in the separates and from defects on the surfaces of diamond grains (Iakoubovskii et

al., 2000). Variations in its maximum position are due to differences in surface structure of

the nanodiamond grains.

A band around 737 nm is observed in all the samples, albeit with widely different

relative intensities (see below). This feature is due to the so-called SiV (silicon-vacancy)

defect – a silicon ion in a divacancy (can be represented as a rarefied diamond lattice) (for

general review see Zaitsev (2001); Shiryaev et al. (2011), Vlasov et al. (2014) provide

information about SiV in nanodiamonds). At temperatures exceeding 250°C the SiV band is

not observable in the DKr and DKr4 samples with any confidence, which is explained by

strong temperature dependence of this PL feature (e.g., Zaitsev, 2001).

After the heating of the DKr and DKr4 samples in air up to 450 °C and subsequent

cooling to room temperature the relative intensity of the SiV luminescence increases

considerably in comparison with initial spectra. Such behavior is explained by partial

elimination of superficial sp2-carbon on surfaces of nanodiamond grains by oxidation during

annealing. This hypothesis is supported by Raman spectroscopy – whereas it is notoriously

difficult to obtain a decent diamond Raman peak of meteoritic NDs using excitation in visible

range due to strong sp2-carbon scattering, after the annealing the diamond Raman peak at

1332 cm-1

is easily observed even upon excitation at 473 nm (Fig. 2). As expected for

nanodiamonds (e.g., Vul’, 2006) a broad shoulder towards smaller wavenumbers is clearly

pronounced.

The relative area of the SiV band (calculated as SiV peak area divided by area of the

total PL between 490-800 nm) in as-received samples depends on chemical class and group of

meteorite and on the nanodiamond grain size (Fig. 3). As shown by us earlier (Vlasov et al.,

2014) the SiV luminescence is observed in the grains with sizes ≤2 nm, which is smaller, than

the median ND size of 2.6-2.8 nm determined by TEM (Daulton et al., 1996) and MALDI

(Lyon, 2005) for nanodiamonds from Murchison (CM2) and Allende (CV3) chondrites.

Presumably, procedures applied to Krymka and Efremovka depleted the “bulk” separates in

smaller grains, therefore the SiV intensity for the fractions DKr4 and DE1 decreases (Fig. 4).

In the same time, for the Orgueil (CI) and Boriskino (CM2) samples the size effect is small

and probably not significant (Fig. 3).

The luminescent SiV defect is characterised by certain atomic configuration. For

example, a substitutional Si ion in diamond lattice will possess no PL. Therefore at present we

cannot estimate the total silicon content in nanodiamond grains from different meteorites. It is

shown, that the SiV defect may be formed both by direct incorporation into a growing

diamond and by reaction between substitutional Si with vacancies generated, e.g., by

irradiation or Si implantation (Iakoubovskii et al, 2001; D’Haenens-Johansson et al., 2011).

The presence of the SiV defects in the smallest diamond grains might seem to be

counterintuitive, since effect of NDs self-purification from vacancies and impurities is widely

discussed (e.g., Barnard and Sternberg, 2007). However, the first principles Density

Functional Theory calculations verified by experiments indicate absence of the self-

purification in case of SiV defect (Vlasov et al., 2014). It is shown that the SiV formation

energies are virtually identical for nanodiamond grains between 1.1 and 1.8 nm in size when

the defects are placed in the centre of the particle. When this defect is placed near the surface

its formation energy is only marginally (~0.2 eV) lower than the corresponding value in the

centre of the grain. Therefore, the driving force for out-diffusion of the Si ion is small

resulting in stable SiVs even in very small nanodiamonds.

The reason why the separates enriched by smallest nanodiamonds possess higher

relative intensity of the SiV defects is likely due to existence of several populations of

nanodiamond grains, differing in origin and thermal stability (e.g., Huss and Lewis, 1994a).

These populations may reflect formation is different astrophysical sources (e.g., supernovae

and Solar system). In addition, thermal stability of the populations may play an important

role. It should be mentioned that so-called stochastic heating of nanograins by individual UV

photons may drastically increase temperature of the smallest (<2 nm) grains (see Van

Kerckhoven et al., 2002 for ND-related calculations) and their formation and evolution may

differ considerably from that of larger grains (Kochanek, 2014).

The sample-dependent variations of the SiV relative intensities presented at Fig. 3

could be explained by (1) differences in amorphous carbon content in the separates, (2)

variations in the SiV defects concentration in nanodiamond grains of different meteorites, or

by combination of these factors. These possibilities are discussed below.

1) Differences in amorphous carbon content in the separates

Transmission electron microscopy (e.g., Bernatowicz et al., 1990, Garvie 2006, Stroud

et al., 2011) and NEXAFS and Raman measurements (Shiryaev et al., 2011) reveal that the

diamond-rich separates principally consists of nanodiamond grains covered (partly) by sp2-

carbon layer and of subordinate amount of other carbonaceous phases (non-graphitising

carbons such as glassy carbon, amorphous C, etc). Some of these compounds may result from

severe chemical treatment required for MNDs extraction, but at least a part of it is inherited

from the MNDs formation process as suggested by electron microscopy (e.g., Garvie and

Buseck, 2006) and by processes of entrapment of P3 noble gases in MND (Fisenko et al.,

2014 and refs. therein). Potentially these sp2-phases could be responsible for the broad-band

PL dominating spectra of the separates. If the PL is indeed caused mostly by the secondary

(independent from the nanodiamonds) phases, the trend shown on Fig. 3 would reflect

variations in content of non-diamond carbon in the separates due to differences in thermal

metamorphism of meteorites parent bodies.

However, studies of behaviour of the broad PL band from various nanodiamonds

during oxidation, thermal treatment etc. showed that this band is largely due to sp2-carbon

layer on surfaces of nanodiamond grains (e.g, Smith et al., 2010). The present work shows

also that annealing of the Krymka separates in air decreases the PL intensity, but subsequent

storage in air gradually recovers it, thus supporting its genetic link to sp2-carbon directly

connected with nanodiamond grains. Moreover, only one mode of carbon release is observed

during step-oxidation of the separates of different meteorites (e.g., Russell et al., 1996),

indicating that the fraction of the sp2-carbon in the studied separates is either not abundant or

its resistance to thermal oxidation is similar to nanodiamond. The plausibility of the latter

assumption remains an open question. Therefore, we prefer another explanation of the

observed increase of the SiV relative intensity.

2) Variations in concentration of the SiV defects in nanodiamond grains of different

meteorites. These variations could be explained by existence of several nanodiamonds

populations with strongly variable concentration of the SiV defects. The SiV concentration as

well as ratio of the populations in a meteorite depends on conditions of thermal

metamorphism of meteorites parent bodies. Recall that the SiV PL in Krymka samples is

enhanced by oxidative annealing which partly removes and reconstructs the sp2-carbon

superficial layer.

The variations between thermal history of parent meteorites bodies (both temperature

and time) may explain the observed spread. Indeed, the lowest intensity of the SiV defects

(Fig. 3) are observed for nanodiamonds of Orgueil (CI) and Boriskino (CM2) meteorites

which underwent low temperature (~100 °C) metamorphism only (Huss and Lewis, 1994b).

The temperature of ~100 °C is too low to induce atomic diffusion in diamond. The SiV is

stronger in MND from Efremovka (CV3) and Krymka (LL3.1) meteorites, with temperature

of metamorphism of at least 300-400 °C (Huss et al., 2006). In addition, Krymka underwent

at least two strong shocks which led to residual meteorite temperature up to 500 °C

(Semenenko et al., 1987).

Remarkably, the tendency of changes of the SiV relative intensity shown on Fig. 3 for

carbonaceous meteorites correlates with concentration of the P3 component of noble gases in

MND, which might be related to disordered carbonaceous phase on surfaces of nanodiamond

grains (Fisenko et al., 2014 and refs. therein). In the studied meteorite set the concentration of

the P3 noble gases in the NDs of Orgueil and Boriskino is the highest, whereas for the

Efremovka NDs it is the lowest (Huss and Lewis, 1994a; Verchovsky et al., 1998; Fisenko et

al., 2004). Note also that the maximum of the broad PL band of the Orgueil and Boriskino is

somewhat shifted to smaller wavelengths in comparison with other samples. Most likely this

shift indicate some differences in the surface sp2-carbon.

Therefore, the enhancement of the SiV luminescence in the diamond-rich separates is

largely due to thermal metamorphism (annealing) of meteorite parent bodies, which has

promoted defects diffusion, and modification of the surface layer of the nanodiamonds.

Implications for astrophysical search of nanodiamonds

The silicon-vacancy defect in meteoritic nanodiamonds is potentially important for

understanding origin of nanodiamonds because of several reasons. As shown by Vlasov et al.

(2014) up to three emitting centers per particle containing ~400 atoms were observed, though

on limited number of grains. If these numbers are statistically valid, this implies that the

structural silicon impurity in meteoritic nanodiamonds may represent a new isotopic system

for identification of their cosmochemical sources. However, our preliminary Accelerator

Mass Spectrometry (Martschini et al., unpublished) and SIMS measurements revealed a

problem of contamination of nanodiamonds by silicon: dangling bonds on nanodiamond

surfaces may serve as very efficient sorption sites for various elements (e.g., Dolenko et al.,

2014). Silicon is fairly ubiquitous element, and appears to be efficiently sorbed by

nanodiamonds especially during acid dissolution of silicate matrix of a parent meteorite.

Atom Probe Tomography (see Heck et al., 2014) might be the only technique that could

discriminate contributions of surface contamination and of nanodiamonds’ bulk in Si isotopic

analyses.

The luminescence of the SiV defect may also assist in search of astrophysical sources

of nanodiamonds with grain sizes comparable with those observed in meteorites. The

prominent broad band luminescence of nanodiamonds (see e.g., Fig. 1) is not very useful for

such purpose due to several reasons. First of all, the band shape is similar to emission curve of

stars belonging to G0-K9 spectral classes and thus unique identification is barely possible.

The Extended Red Emission (ERE) is almost never peaked at such wavelengths, being shifted

to larger wavenumbers. Only few ERE sources such as galactic cirruses are close in spectral

position, but their emission is much narrower (Darbon et al., 1999 and refs. therein). In

addition, the broad PL band is related to non-diamond superficial carbon and thus a PL

spectrum of a bare nanodiamond in space may differ from that observed in the laboratory. If

NDs in stellar environment are less prone to sp2-carbon surface coverage, the relative

intensity of the SiV luminescence will be stronger than in the laboratory.

As mentioned in Introduction, Chang et al., (2006) showed a nearly-perfect match of

the ERE band from some of the sources with that of the NV defect in large nanodiamonds.

However, this resemblance is achieved only in case of very selective narrow band excitation

of the NV luminescence. A real stellar source emits quasi-continuum spectrum and in this

case several charge states of the nitrogen-vacancy defect will be observed. The overlap of

these contributions will make the band too broad to account for the astronomical observations

(see Fig. 2 of Chang et al., 2006). In the same time, the SiV defect is characterized by very

strong ZPL and the corresponding line at 738 nm remains rather narrow even in

nanodiamonds. Strong temperature dependence of the SiV luminescence (e.g., Fig. 2a)

permits its observation only from cold particles. However, this defect is also visible in

absorption, thus complementing IR observations of C-H bands pronounced in IR emission

spectra of hot particles (>400-500 °C).

The search for the SiV luminescence from astrophysical sources is not trivial due to

expected weakness of the feature and necessary corrections for sky brightness. One may note

a perfect correspondence of the SiV band position with some of Diffuse Interstellar bands

(DIBs, Galazutdinov et al., 2000). Unfortunately the DIBs are far too narrow to be positively

identified as the SiV luminescence. Bands at similar wavelengths are not uncommon in

spectra of supernovae (e.g. Filippenko, 1997), they are mostly due to Doppler-shifted ions

emission (such as O[I], Ca[I]) and reliable identification of the SiV requires careful analysis

of extended spectral region. A dedicated search for the SiV luminescence and absorption from

astrophysical sources is currently underway.

CONCLUSIONS

A band of the silicon-vacancy (SiV) defect in diamond lattice is observed in

photoluminescence spectra of different grain-size fractions of nanodiamonds (ND) extracted

from chondrites of various groups. At present our statistics includes the following classes and

groups: CI, CM2, CO3, CV3, and LL3. The concentration of silicon in NDs lattice may reach

hundreds of atomic ppm, which makes this element important for identification of

astrophysical sources and formation processes of meteoritic nanodiamonds.

The variations in relative intensities of the SiV luminescence between the

nanodiamond-rich separates extracted from the meteorites of different classes are due to

variations of temperature of thermal metamorphism of their parent bodies and/or uneven

sampling of nanodiamonds populations. The silicon impurity is preferentially incorporated

into the smallest grains (less than 2 nm). The thermal history of parent meteorite bodies is

important for enhancement of the luminescence of trapped Si atoms promoting formation of

specific lattice defect and by modification of nanodiamonds surfaces. The strong and well-

defined luminescence and absorption of the SiV defect is a promising feature to locate cold

nanodiamonds in space.

Acknowledgments. This work was partly supported by RFBR grants 12-05-00208

and 15-05-03351. We are grateful to Dr. K. Iakoubovskii and Prof. A. Witt for informative

discussions. Detailed reviews of Prof. T. Daulton, P. Heck and I. Franchi were extremely

useful.

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FIGURES

Figure 1. Photoluminescence spectra of studied nanodiamond-rich separates (only some size

fractions are shown). The curves are normalized to maximum and displaced vertically for

clarity. Note that all shown spectra are related to measurements of the separates in as-received

state (without annealing).

Figure 2. Temperature-induced changes in Raman spectra of the Krymka nanodiamond

recorded in as-received state, in situ at 400 °C and after the annealing. A linear background

partly compensating contribution of temperature-dependent broad-band photoluminescence

was subtracted.

Figure 3. Relative area of the SiV band in dependence of chemical composition of parent

meteorite. The total area was calculated between 490 and 800 nm; the SiV band area was

calculated after linear background subtraction between 720 and 760 nm. For all samples

except Kainsaz points corresponding to size fractions are shown.

Figure 4. Normalised and vertically displaced spectra of two density fractions of MND from

Krymka LL (measured without annealing) and Efremovka CV3 chondrites.