Chapter 6  : Nitrogen addition to a DC-arcjet reactor


This chapter serves to present and analyse the results of both spatially resolved optical emission and film deposition studies, carried out in the DC-arcjet reactor, with particular reference to the addition of trace quantities of nitrogen.


The addition of trace quantities of nitrogen into the feed gas of hot filament[1], microwave[2] and oxy-acetylene torch[3] CVD systems during diamond deposition has been shown to enhance both the growth rate and deposition quality.  In all systems a peak in both the film quality and growth rate is obtained with the introduction of controlled quantities of nitrogen.  The work carried out, and documented, in this chapter aims to study the effect of additional nitrogen on both the gas-phase environment, via Optical emission spectroscopy (OES), and the characteristics of the grown films.  The experimental specifics have been described previously in chapter 5.



6.1             OES Measurements


The use of OES in the characterisation of a gas-phase environment is commonplace in the field of plasma diagnostics due to the ease of data collection and non-invasive nature of the technique.  However, interpretation of the emission data is complicated by a number of factors.  OES only gives information about excited state species which, due to their low relative abundance in the diamond-depositing gas-phase environment, are generally considered to be unimportant in the diamond deposition process.  Relating the excited state information to that of the more abundant and functional ground state species requires detailed knowledge of the production and collisional quenching mechanisms.


While the interpretation of OES suffers from a number of complications, its use as a plasma diagnostic is justified in the study of species as a function of spatial variation and changes in process conditions.


OES measurements taken in this study all used a fixed Ar/H2/CH4 feed gas ratio and flow rate (Ar 87.83%, H2 11.59%, CH4 0.58%, total flow rate

13.8 slm) with the addition of known quantities of N2 in the range 0-100 sccm.


Figure 6.1 shows typical wavelength-dispersed optical emission spectra of both an Ar/H2/CH4 (upper trace) and Ar/H2/CH4/N2 (lower trace) plasmas in the DC-arcjet environment.  Clearly the emission spectra of both plasmas are dominated by the C2 (d3Pg®a3Pu) Swan band system but, as figure 6.1 shows, emission from atomic hydrogen (Balmer-a transition, henceforth Ha) at 656.3 nm is also visible.


The CH4/H2/Ar/N2 plasma spectra also includes emission from the CN(B2S+®X2S+) system (hereafter also referred to as CN (B®X)) at ~388 nm.  CH (A2D®X2P) emission at ~431.4 nm is discernible, but so weak in comparison with the Swan band system that it is not considered in this study.  All emission lines from Ar (neutral and ionic) observed from the pure Ar plasma are quenched on addition of H2, thus preventing their use in actinometric measurements.


Figure 6.1  Wavelength-dispersed optical emission spectra of an Ar/H2/CH4 plasma (upper trace) and with the addition of 10 sccm nitrogen (lower trace).  Both spectra were measured at

z = 10 mm and x = 0 mm with a 2 mm diameter viewing column and the Oriel Instaspec IV monochromator.  Chamber pressure was maintained at 50 Torr.


Throughout the OES studies the measurements of the C2 and CN emission intensities, taken as a function of process condition, were obtained at a fixed wavelength and not as the integral of the vibrational band.  This method was chosen as the overlapping of visible emission from a number of species and vibrational systems complicates the spectrum.  For example, within the region enveloped by the C2 (d®a)(Dv=0) band, emission from Hb also appears at ~486.1 nm.  Prior measurements[4] show that the emission intensity obtained from the integral of a vibrational band and from a fixed wavelength both follow the same trend with changes in the process conditions.


For data used in this study the following wavelengths were probed.  For C2 emission, the (0,0) bandhead at 516.5 nm was monitored.  In the case of the CN(B®X) the emission at 388.8 nm was collected, while Ha was monitored at 656.2 nm.  Since the aim of this study was only to show species intensity trends in terms of either spatial distribution or process conditions, no attempts were made to establish absolute emission intensities.


Figure 6.2 shows the measured variation of the CN(B®X), Ha and C2(d®a) emission intensities as a function of added N2.  The growth in CN(B®X) emission clearly implicates nitrogen as a species that participates in the gas-phase chemistry within the plasma plume, while the plots of C2(d®a) and Ha emission intensities serve to illustrate the substantial quenching induced by the addition of just a trace of N2.  Consistent with the previous discussion regarding the inevitable presence of some background N2 in the process gas mixture, very weak CN(B®X) emission is observed with (nominally) 0 sccm added N2; extrapolating the data displayed in fig. 6.2 provides an upper limit estimate of 2.2 sccm (~160 ppm) as the 'flow rate equivalent' N2 content under these conditions.


Figure 6.2  Variation in OES intensity of CN(B®X) (=), Ha (r) and C2(d®a)(0,0) (<) from intensity measurements taken at 388.83, 656.28 and 516.52 nm respectively (frequency calibration determined from mercury transitions in fluorescent lighting).


Previous measurements of the C2(d®a) Dv = 0 progression, recorded at higher resolution, using the Spex 1870 monochromator, showed no obvious variation in band contour either with process conditions or with spatial location, though it is worth noting that this did not include the ~1 mm closest to the substrate surface (i.e. the region containing the boundary layer).  This encourages the assumption that spatial variations in emission intensities, monitored via the intense (0,0) band head at ~515 nm, are representative of the entire distribution of emitting C2 species.



6.1.1   The C2 molecule


The study of the C2 molecule, in particular the Swan band system, is of particular interest in the field of astrophysics where emission spectra from comets and the absorption spectra of stellar atmospheres have been studied.


At this point it seems prudent to mention some details regarding the electronic configuration of the C2 molecule.  If we consider the electronic configuration of the homonuclear diatomic molecule, from the Aufbau principle, ground-state C2 has the electronic configuration,




With multi-electron molecules it is feasible that electron promotion to the lowest energy excited-orbital may result in an unexpected low-lying excited electronic state, due to the presence of electron-electron repulsion.  This is the case with C2, where excitation of an electron to a higher orbital, results in a low-lying excited energy state with the electronic configuration,




This low lying excited state, labelled a3Pu, is only 716 cm-1 above the ground state and is appreciably populated even at modest temperatures.  This study concentrates on the Swan band system, C2(d3Pg®a3Pu), relying on information gained from the emission between two excited states, and thus reveals little information about the potentially more important ground state species.  The emitting d3Pg state is thought to be produced in the DC-arcjet system via electron impact excitation of the abundant lower lying a3Pu state[5].  Boltzmann calculations show that at a typical plume temperature of 3000 K the number of C2 species in the a3Pu state exceeds that of C2 in the  ground state.



6.1.2   Spatially resolved OES measurements


Figures 6.3(a) and (b) show plots of the spatially imaged C2(d®a) and CN(B®X) emission intensities (at ~515 nm and ~388 nm, respectively, using a 2 mm diameter viewing column) as a function of position along z, measured from the substrate surface.

Figure 6.3  Spatially imaged emission intensities as a function of z for (a) C2(d®a) and (b) CN(B®X) measured at x = 0 mm


The local maxima in emission intensity at a distance of ~3 mm from the substrate surface, for both species, mimics previous OES studies carried out on DC-arcjet reactors[6].  Yamaguchi et al. have commented that it is probable that the maxima is not due to increases in species density, but rather to an increase in the local gas temperature, as the high velocity-high enthalpy species strike the substrate, forming a shock wave close to the substrate surface.


As the plume is cylindrical in nature any emission intensity measurements, taken as a function of co-ordinate x, will be viewing a column of emission, the thickness of which will depend on the x position.  In order to ascertain the emission intensity as a function of a radial co-ordinate, an Abel-inversion is performed on x co-ordinate datasets.



6.1.3   The Abel Transform


The Abel transform is a mathematical function that allows the derivation of a radial dependence to be obtained from taking parallel chords through a cylindrical or spherical object.  Its use is prevalent in plasma diagnostics in such systems that allow a number of assumptions to be made.  These assumptions relate to the axial symmetry of the plasma and the degree of optical transparency.  Both are essential to the analysis, which requires information on the emission throughout the extent of the line-of-sight.  Figure 6.4 outlines the variables associated with the interpretation of an Abel transform.



Figure 6.4  Outline of variables required for Abel transform of cylindrical plasma.


Application of an Abel transform to the line-of-sight data set, enables derivation of the radial dependence of emitting species within the plasma[7], if we assume that the plasma is optically thin at the emission wavelengths of interest.  However, such remains to be proven for the measurements reported here, particularly in the case of CN where the measured emissions terminate on the ground state, but the trends deduced in what follows remain valid even if the measurements are affected by preferential self-absorption at x ~ 0 mm.


All measured species specific lateral emission intensity distributions, I(x), appear symmetric about x = 0 mm (as in figure 6.5), thus satisfying the requirement of cylindrical symmetry for Abel inversion.  Knowing I(x) throughout the range x = 0 to x = R (here chosen as 20 mm), Abel inversion yields the radial distribution of emitting species, i(r), via the integral:


                             Equation 6.1 


The i(r) profile so deduced for the case of C2(d®a) emission measured at

z = 6 mm is shown in fig. 6.5. 



Figure 6.5  Abel-inverted C2(d®a) emission intensity as a function of radial co-ordinate, r (n), together with a data-smoothing function.  The raw C2(d®a) emission data are also shown as a function of x ().


As the raw data in figure 6.5 show, the emission intensity points are collected at 2 mm intervals.  An Abel inversion function is applied to the raw data thus yielding the Abel-inverted emission intensities, which then have a data-smoothing function applied.


Given numerous such profiles, taken at many z values for the CN(B®X), C2(d®a) and Ha emissions, it is possible to generate spatially resolved emission intensity maps for each of these species.  Emission was collected at 1 mm intervals along the z-axis in the region 0 < z < 26 mm (defined in figure 5.10) and at 2 mm intervals in the range -4 < x < 16 mm (i.e. out of plane depicted in figure 5.10) for several different fixed z values, each separated by 5 mm, in front of the substrate surface and perpendicular to the plasma flow.


Figure 6.6  Spatially resolved emission intensity maps for (a) C2(d®a), (b) CN(B®X) and (c) Ha.  Note that each figure has an independent logarithmic 10-point scale where high species intensity corresponds to a darker grey.


Figs. 6.6 (a)-(c) show such plots, as a function of z (horizontal axis, with the front face of the substrate at z = 0 indicated) and radial co-ordinate, r.  All show some spatial inhomogeneity, with maximum emission intensities at the plume centre (x ~ 0).  The CN and C2 emission profiles show similar full width half maxima (FWHM) values in r, indicating efficient mixing within the plume, but the radial emission profile for Ha is narrower and more localised in the upstream, hotter, region of the plasma jet.


Such trends have been reported previously, and discussed, following analysis of plume emissions from a lower power (2.3 kW) DC-arc plasma jet operating on an Ar/H2/CH4 gas mixture6.


All are consistent with formation of C, N and H atoms by thermal decomposition of H2, CH4 and N2 in the hottest regions of the plasma, and the increasing importance of subsequent recombination reactions to form species such as C2, CN, CH and H2 further downstream, at cooler plasma temperatures.  Where the plasma impinges on the substrate surface the large kinetic energy associated with the gas flow is converted into thermal energy, resulting in local gas heating.


Interpretation of the results of OES studies requires some caution, given the nature of the high velocity flux of species in the DC-arcjet environment.  Estimates of the average number of collisions that a species may undergo between exiting the arcjet nozzle and striking the substrate based on Maxwell-Boltzmann statistics, have shown that (assuming a pressure of 50 Torr and an approximate gas temperature of 3500 K) the average number of collisions is of the order of 25.


As the radiative lifetime of the d3P state of C2 is approximately 170 ns, many of the species will have insufficient time to reach thermal equilibrium before emitting.  The interpretation of OES data, in terms of relating excited-state emission intensity to ground-state species number densities, requires the assumption of thermal equilibrium.  While actinometry is commonly used to tackle this problem all argon emission lines are quenched on the addition of hydrogen.


This study confirms the production of CN, which in the high enthalpy plume may be produced via a number of energetically favourable routes.  Rudimentary studies of the gas-phase reaction scheme GRIMECH 3.1[8] (see Appendix 6) identify nitrogen and nitrogen containing species as reactive at temperatures reached within the plasma jet system.  However, the H/C/N gas-phase chemistry scheme is highly complex and strongly dependent on the gas temperature.  For this reason the gas-phase chemistry within the DC-arcjet reactor needs to be studied in more detail, and while previous studies of H/C and H/C/N chemistries at high temperatures have focused on computer simulation of the reactor, further experimental studies are also required to support simulation findings.


Finally, it is worth noting that the present work supports previous suggestions6 that the observation of high C2 emission intensities in a DC plasma jet correlates with higher quality diamond growth.  This finding is in contrast to some of the earlier studies of microwave plasma enhanced CVD which found strong C2 emission to be an indicator of degraded diamond film quality[9].



6.2       Film Deposition


The influence of nitrogen addition was also studied in terms of the films deposited.  While the growth rate and film quality are of obvious importance, this deposition study was also interested in the formation of diamond films with the incorporation of nitrogen.  While natural diamond contains nitrogen as a trace impurity, attempts to synthesize electronically useful nitrogen-doped diamond by CVD techniques have, so far, proven disappointing.


For the purposes of comparison a series of films were deposited with identical Ar/H2/CH4 feed gas ratio and flow rate (Ar 87.83%, H2 11.59%, CH4 0.58%, total flow rate 13.8 slm), with the addition of known quantities of N2 in the range 0-20 sccm.  Each film was deposited for one hour with a chamber pressure of 50 Torr and total input power of 5.9 kW (78 V, 76 A).  All films delaminated on completion of the growth run and were analysed as free-standing samples by a number of techniques.  Each surface diagnostic was undertaken on the centre of the circular samples.



6.2.1       SEM analysis


The use of Scanning Electron Microscopy (SEM) reveals the growth rate, via cross-sectional analysis, and also the surface topology.  Analysis was carried out on an Oxford Instruments SEM system with prior gold coating of the sample surface.  In order to obtain both growth rate and an indication of the surface topology the films were cleaved into sections and mounted at an approximately 45° angle to the mount surface.  This allows visualisation of the cross section and the top surface while allowing a sufficient working distance.


Figure 6.7 shows cross-sectional SEM images obtained as a function of additional nitrogen.  Note the scales are not common between each image.



Figure 6.7  Cross-sectional SEM images of films grown with nitrogen addition of (a) 0, (b) 1, (c) 3, (d) 5, (e) 10 and (f) 20 sccm respectively.


From analysing the SEM images it is clear that films grown without additional N2 are predominantly (111) faceted, and exhibit twinning and secondary nucleation while, with the addition of 1 sccm N2, a central region of largely (100) growth is formed, in which some of the crystallites exhibit facets approaching ~60 mm in size.   Further addition of N2 promotes the growth of ballas-type features.


Clearly N2 addition to the process gas mixture affects the film growth rate and morphology.  Figure 6.8 graphically summarises the influence of nitrogen addition on the growth rate.

Figure 6.8  Plot showing the influence on growth rate from cross-sectional SEM analysis as a function of nitrogen added during deposition.


Figure 6.8 shows the measured growth rate (mm hr-1) generally decreasing with increasing N2; since the films grown at higher N2 partial pressures are increasingly graphitic, and thus have lower density, the growth rate defined as deposited mass per hour would fall off even more steeply with increasing N2.



6.2.2   Laser Raman analysis


Laser Raman spectroscopy was used to assess the quality of the as-grown films using a Renishaw system with excitation from a He-Cd laser operating at 325 nm.  Representative background-corrected Raman spectra of films grown with the addition of, respectively, 0 and 10 sccm of N2 to the process gas mixture are shown in figure 6.9.



Figure 6.9  Representative Raman spectra of films deposited with the addition of 0 (upper trace) and 10 (lower trace) sccm nitrogen.  Note that the spectra have been vertically shifted for clarity.  Both spectra have been background corrected to allow for the underlying one-phonon transition.


Figure 6.9 clearly shows the Stokes shifts associated with sp3 carbon at ~1332 cm-1 and the broad sp2 carbon feature centred at ~1550 cm-1.  While Raman cannot be used to reveal the quality of growth on an absolute scale, it may be used to provide an indication of the film quality by comparing the intensities of the sp3 and sp2 features.  Figure 6.10 summarises the findings of this study, where film quality here is represented by the quotient, QD, for which:


                        QD = ID/(ID+IG),                                    Equation 6.2


where ID and IG are, respectively, the relative intensities of the sp3 C peak (at a Stokes shift of ~1332 cm-1) and the sp2 C feature (centred at ~1550 cm-1). 


Figure 6.10  Plot showing the influence on film quality, QD, as a function of additional nitrogen.


This figure illustrates the general reduction in film quality that accompanies increased N2 flow rates.


Studies in other CVD environments have generally shown some improvement in diamond film quality upon small (ppm) N2 additions, followed by a decline at higher levels of added nitrogen.  Such an effect is consistent with the model of Moustakas et al.1, which predicts that both n- and p- doping of diamond reverses the thermodynamic stability between diamond and graphite favouring the growth of diamond over graphite.


However, we see only a reduction in QD with increasing N2 additions, hinting at an obstructive role for nitrogen in the diamond step growth mechanism.  This may reflect the poorer base vacuum of the large DC-arc plasma jet reactor, such that it is always operating at a background partial pressure of air and thus at nitrogen concentrations above those for optimal diamond film quality.  Consistent with this, we observe a weak Raman feature at

~2328 cm-1 which, it has been suggested[10], should be associated with a carbon-nitrogen stretching mode.  This feature is present in all Raman spectra measured in this study, including those of films grown in a standard CH4/H2/Ar gas mixture with no intentionally added N2.  Unfortunately, it is not sufficiently intense for reliable inter-film comparisons.



6.2.3   Photoluminescence (PL) spectroscopy


Following on from the Raman study, PL spectra were obtained from a Renishaw system operating at 325 nm, with all measurements taken at room temperature.  The use of PL is of particular interest in the analysis of nitrogen doped diamond films, as vacancies in the lattice formed by the inclusion of nitrogen are detectable.  Figure 6.11 shows two representative PL spectra for films deposited with the addition of 0 (upper trace) and 20 sccm (lower trace) nitrogen.


Figure 6.11  Representative PL spectra of films grown with the addition of 0 (upper trace) and 20 sccm (lower trace) nitrogen.


From the PL spectra the following assignments may be made.  The 575 nm (2.154 eV) peak corresponds to a nitrogen neutral [N-V]0 centre and is evident on all spectra.  Neutral [N-V] vibronic modes are all visible in the region 580-640 nm.  The feature at 638 nm is commonly associated with the negative

[N-V]- centre and does not appear on the film deposited in the absence of nitrogen.


The fact that nitrogen vacancies are detected in the film deposited without the deliberate addition of nitrogen again suggests that nitrogen exists in sufficient quantities as a gas-phase impurity to influence the deposition process.



6.2.4       Secondary-Ion Mass Spectroscopy (SIMS)


The use of SIMS was deemed necessary in the study of nitrogen incorporation into the films as prior Auger Electron spectroscopic studies proved too insensitive.  Using a SIMS system, with operation in negative collection mode, mass spectra were collected for each sample.  Figure 6.12 shows a typical mass spectrum of a film deposited with the inclusion of

1 sccm of nitrogen. 


Figure 6.12  Negative Ion mass spectrum of film deposited with 1 sccm additional nitrogen


The spectrum clearly indicates a number of carbon clusters, also detectable are CN- ions with a mass/charge of 26 Daltons.  In order to assess the quantity of nitrogen incorporated into the films the ratio of CN- (26 Daltons) to C2- (24 Daltons) and C- (12 Daltons) was determined.  Figures 6.13 and 6.14 show how the relation of these ratios is dependent on the nitrogen added into the process gas.


Figure 6.13  Ratio of CN- to C2- from negative ion secondary ion mass spectra as a function of additional nitrogen.

Figure 6.14  Equivalent plot to figure 6.14 showing the ratio of CN- to C-.


Both trends clearly show nitrogen incorporation in the films increasing as a function of additional gas-phase nitrogen.  Depth profiling of each sample showed no apparent change in nitrogen incorporation.


The centre of each film is considered to be of higher quality than the outer edges; a consequence of the radial difference in the gas-phase composition and the substrate temperature.  The nitrogen incorporation in the more graphitic outer areas of a film deposited with 1 sccm added nitrogen were also investigated.  The result of this investigation reveals increased nitrogen incorporation as shown in figures 6.13 and 6.14 (´).  The increase in nitrogen incorporation may well derive from the fact that inclusion into a less packed density graphitic lattice carries a smaller energetic penalty than the equivalent addition to a diamond lattice.



6.3       Nitrogen-enhanced Growth Scheme


Growth schemes for the enhanced deposition of diamond, with the addition of gas-phase nitrogen have been proposed.  Butler et al.[11] have suggested a scheme for the enhancement of the nucleation rate on the hydrogen terminated (111) diamond surface by addition of CN.



Figure 6.15  Growth scheme for the CN enhancement addition to (111) surface


Following this, nucleation of the next layer is thought to occur via the scheme shown in figure 6.16.


Figure 6.16  Growth scheme showing the next layer nucleation on a (111) surface following that shown in figure 6.15.


These schemes demonstrate that addition of nitrogen to the growing surface facilitates nucleation of the next atomic layer, by providing a nucleation site, and thus enhancing the growth rate of the diamond surface.  While nitrogen incorporation at the growing surface encourages the growth of both (100) and (111) facets, the (100) surface will be “grown out” by the preferential and therefore more rapid growth of the (100) surface.



6.4       Conclusions


This chapter has reported studies of diamond CVD at growth rates surpassing 100 mm hr-1 in a 10 kW DC-arc jet system, operating with CH4/H2/Ar feedstock gas mixtures.  Controlled addition of N2 to the feedstock gas results in intense CN(B®X) emission and quenches C2(d®a) and Ha emissions from the plasma.  Abel transformation of species selective, spatially resolved OES measurements has allowed derivation of the longitudinal and lateral variation of emitting C2, CN and Ha species within the plasma jet.  SEM and laser Raman analyses indicate that N2 additions also lead to a reduction both in growth rate and quality of the resulting diamond film.  The laser Raman, SIMS and PL measurements also provide conclusive evidence of nitrogen incorporation (as chemically bonded CN) in the films.




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[11]             J.E. Butler, Private Communication.