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Ground state atomic oxygen in high-power impulse magnetron sputtering: a quantitative study

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Journal of Physics D: Applied Physics

Journal of Physics D: Applied Physics

J. Phys. D: Appl. Phys. 50 (2017) 075204 (13pp)

Ground state atomic oxygen in high- power impulse magnetron sputtering:

a quantitative study

Nikolay Britun 1 , Alexandr Belosludtsev 2 , Tiago Silva 3 and Rony Snyders 1,4

1 Chimie des Interactions Plasma­Surface (ChIPS), CIRMAP, Université de Mons, 23 Place du Parc, B­7000 Mons, Belgium

2 Department of Physics and NTIS, University of West Bohemia, Univerzitní 8, 306 14 Plzeň, Czechia

3 Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Universidade de Lisboa, 1049­001 Lisboa, Portugal

4 Materia Nova Research Center, Parc Initialis, B­7000 Mons, Belgium

Received 29 October 2016, revised 8 December 2016 Accepted for publication 29 December 2016 Published 25 January 2017

for publication 29 December 2016 Published 25 January 2017 Abstract The ground state density of oxygen

Abstract

The ground state density of oxygen atoms in reactive high­power impulse magnetron sputtering discharges has been studied quantitatively. Both time­resolved and space­resolved measurements were conducted. The measurements were performed using two­photon absorption laser­induced fluorescence (TALIF), and calibrated by optical emission actinometry with multiple Ar emission lines. The results clarify the dynamics of the O ground state atoms in the discharge afterglow significantly, including their propagation and fast decay after the plasma pulse, as well as the influence of gas pressure, O 2 admixture, etc.

Keywords: HiPIMS, reactive sputtering, atomic oxygen, number density, density calibration, TALIF, optical emission spectroscopy

(Some figures may appear in colour only in the online journal)

1. Introduction

As a result of the evolution of sputtering discharges, magne­ tron sputtering (MS) brought essential advantages to thin film science and technology during the 1960s [1, 2]. In MS dis­ charges, sputtering from a solid cathode is greatly enhanced (compared to cathode sputtering) by placing constant magnets under the cathode, which allows electrons to be trapped, thus improving the sputtering rate significantly. Reactive magne­ tron sputtering (RMS) represents a further step in the evo­ lution of magnetron discharges. It involves sputtering with a reactive gas (such as O 2 , N 2 , etc) as an admixture to the main working gas (typically Ar), and thus covers a wide number of applications related to composite thin films [3, 4]. The numerous benefits of pulsed magnetron sputtering (often referred to as pulsed direct current magnetron sput­ tering, or pulsed DCMS) [5] led to the appearance of so­called high­power impulse magnetron sputtering (HiPIMS)

1361-6463/17/075204+13$33.00

1

discharges in the early 1990s [6, 7]. These belong to the so­ called ionized physical vapor deposition (IEPVD) discharges [8, 9] and represent a further step [6] of DCMS evolution as

a result of the time redistribution of the applied power by

squeezing the plasma pulse and significantly elevating the pulse power while maintaining the time­averaged applied power at a level that is comparable to that in the DCMS case [7]. The pulse repetition frequency in HiPIMS ranges roughly from 0.05 to several kHz, whereas the pulse duration stays within the few µ s to few hundred µ s range. At the same time,

the duty ratio does not exceed a few per cent. As a result, the ionization degree in HiPIMS is significantly elevated during the plasma on­time, compared to DCMS [9]. The HiPIMS pro­ cess is now widely recognized for industrial applications due

to the unique coating properties that can be obtained, such as

high film density, controllable phase constitution, etc [10, 11]. Reactive HiPIMS (R­HiPIMS) discharges, like reactive DCMS

ones, use O 2 , N 2 , etc admixtures to the working gas for the

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J. Phys. D: Appl. Phys. 50 (2017 ) 075204

N Britun et al

Phys. D: Appl. Phys. 50 ( 2017 ) 075204 N Britun et al Figure 1. Top

Figure 1. Top (a) and side (b) views of the HiPIMS reactor with the optical diagnostic alignment used in this work.

synthesis of oxide, nitride, etc coatings, which are currently being investigated intensively [10, 1214]. The problem of quantification of the atomic density of reactive gas, as well as its flux, in sputtering plasmas is important. Knowing the number density of the O, N, etc atoms produced in the plasma bulk and trapped by a growing film surface would clarify our understanding of the film structure significantly, in respect of its surface chemistry, surface morphology and other properties [11]. It might also be helpful for modeling plasma and film growth. Detailed knowledge of the flux of O (N, etc) atoms to the surface would also be extremely useful for controlling film stoi­ chiometry, since the methods for determining the particle velocity in magnetron discharges are rather well­developed in both the DCMS [15, 16] and HiPIMS [17] cases. In addi­ tion, providing the fluxes of the reactive atomic species to the film surface are known, the mentioned atomic reac­ tive species can be delivered artificially to the film surface, with them being produced in a separate plasma source [18]. This type of atom delivery should enhance film stoichiom­ etry control significantly, while at the same time potentially decreasing target poisoning. To date, apart from experimental and modeling studies on the O metastable atoms in R­HiPIMS [19], there has been a significant lack of experimental data for the ground state O density. The main reason for this is the difficulty of meas­ uring the O ground state density directly by optical absorption spectroscopy, which is a straightforward non­intrusive tech­ nique used for this purpose [20]. In the case of ground state O, this technique requires a deep ultraviolet (UV) region, which involves expensive vacuum UV (VUV) spectrometers [21]. The calibration of the O density using Xe gas in combination with the two­photon absorption laser­induced fluorescence (TALIF) technique [22] represents another expensive alterna­ tive, with its own disadvantages related to the gas rarefaction in HiPIMS discharges [9, 17, 23]. Indeed, using Xe gas alone (i.e. without plasma), the local character of the calibration will be lost due to the gas rarefication in the presence of HiPIMS discharges, which should be taken into account separately in this case.

Thus, an easy­to­implement calibration method would be beneficial for reactive gas atom number density determina­ tion in magnetron discharges. Regarding this, the aim of this work was to quantify the density of the ground state O in the HiPIMS case in both time and space using the methods of visible­infrared spectroscopy. In order to keep the discharge unperturbed, non­intrusive spectral diagnostic techniques, combining laser­based spectroscopy and optical emission spectroscopy, were chosen. This paper is organized as fol­ lows. After a short description of the experimental setup, the theoretical background of the proposed calibration methods is given, followed by the results obtained under various HiPIMS discharge conditions. Finally, brief conclusions summarize the work.

2

2. Experimental part

2.1. The HiPIMS reactor

The measurement and calibration of the O atom density in HiPIMS plasma were both performed in a stainless steel vacuum chamber with a magnetron source with a circular planar cathode (target), 10 cm in diameter and 5 mm thick, as described elsewhere [17]. The HiPIMS discharge operated in an ArO 2 gas mixture in a pressure range of 320 mTorr at a total gas flow ranging between 10 and 80 (typically 44) standard cubic centimeters per minute (sccm) with a repeti­ tion frequency of 100 Hz and a pulse duration of 50 µs. Side and top views of the described vacuum reactor with the pur­ pose of O atom detection and calibration are given in figure 1. The relevant discharge parameters are summarized in table 1. The typical current (I) and voltage (V) waveforms for metallic and poisoned discharge modes for the studied metallic targets (Ti, W, Cu, Ag) are given in figure 2. The observed differences in the current and voltage waveforms are the result of changes related to metal ion (in the metallic mode) versus Ar ion (in the poisoned mode) dominated sputtering, as well as changes in the ion­induced secondary electron emission (ISEE) coef­ ficients in these modes, as analyzed in [24]. The discharge

E

where V ( t )

pulse energy E P (defined as

τ

P

=

0

V t I t dt

( )

( )

,

J. Phys. D: Appl. Phys. 50 (2017 ) 075204

N Britun et al

Table 1. Main parameters for the HiPIMS discharge used in this work.

Parameter

Value

HiPIMS pulse repetition rate HiPIMS pulse duration Working pressure O 2 flow fraction range HiPIMS pulse energy (E P ) Distance to target (OES) OES measurement time delay

100 Hz 50 µ s 320 mTorr

540%

0.5 J (typically) 5 cm (typically) 50 µ s

and I ( t ) are the voltage and current profiles respectively, τ is the pulse duration, and t is time) was real­time monitored by

a Tektronics DPO3054 digital oscilloscope and ranged from

0.2 to 1.2 J per pulse. The typically used value of E P = 0.5

J corresponds to a pulse­averaged power of 10 kW and a

pulse­averaged current density of 0.25 A · cm 2 .

2.2. The O atom detection

The detection of O( 3 P 2 ) ground state atoms during the HiPIMS afterglow (plasma­off time) was organized using the TALIF technique, in accordance with the standard exci­ tation scheme with the laser radiation at about 225.6 nm and the fluorescence at 844.6 nm. The detailed parameters for this technique can be found in table 2, or elsewhere [22, 25]. The measurements were performed using a pulsed Sirah dye laser with a pulse duration of 5 ns and a repetition frequency of 10 Hz at the second harmonics (attained with Coumarin 450 dye solution). The fundamental harmonic of the dye laser was real­time monitored and locked using a HighFinesse WS6­200 wavemeter that produced a relative wavelength drift of about 4 · 10 7 during the measurements (see table 2). The measurement and calibration points were located ~5 cm above the target surface, as shown in figure 1(b). An Andor iStar DH740­18F intensified charge coupled device (ICCD) camera in the image accumulation mode was used as a detector for both the OES and TALIF cases. About 300 laser pulses were averaged for each TALIF data point. A Nikkor 50 mm f/1.4 D lens with an optical bandpass filter (840 nm central wavelength and 10 nm bandwidth) repre­ sented the imaging lens. In order to acquire the O TALIF signal, the imaging data were averaged in the region of interest (ROI), followed by background fitting and subtrac­ tion, as shown schematically in figure 3. The laser beam was focalized above the target by an f/50 mm fused silica lens in order to increase the photon density in the ROI. The laser pulse energy inside the vacuum chamber varied from

0.2 to 0.5 mJ, corresponding to the average photon density

in the beam waist of ~3 · 10 15 cm 3 . The variations of the laser energy during the measurements were compensated using the real­time monitored laser energy data, similarly to [17]. The optical emission spectroscopy (OES) measurements were performed at the end of the plasma pulse (i.e. at 50 µs of time delay) using a visible­infrared optical fiber connected

3

delay) using a visible­infrared optical fiber connected 3 Figure 2. The HiPIMS current – voltage waveforms

Figure 2. The HiPIMS currentvoltage waveforms acquired by a digital oscilloscope in metallic and poisoned HiPIMS modes using various sputtering targets at 20 mTorr of Ar pressure and E P = 0.5 J.

Table 2. Parameters for the TALIF experimental setup used for O atom detection.

TALIF parameter

Value

Excitation wavelength (theory) Measured wavelength (first harmonic) Laser pulse energy inside reactor Laser beam waist section Volume of measurements Averaged laser photon density (waist) TALIF measurement delay time Distance to target (z) range

225.58 nm 441.1815 nm ± 160 fm 0.10.3 mJ 0.4 mm × 0.4 mm 0.1 cm 3 3 · 10 15 cm 3 509000 µ s 2565 mm

to an Andor SR750 spectrometer with the above­mentioned ICCD and were averaged along the line­of­sight about 5 cm above the target (see figure 1). The line­of­sight in this case was represented by a slowly divergent cone with a diameter of ~1.5 cm above the target. A corresponding spectral cor­ rection that took the spectral response of the fiber + mono ­ chromator + ICCD system into account was applied to all the OES measurements. The spectral resolution used was about 0.02 nm in the case of the electron temperature measurements and about 0.05 nm otherwise.

J. Phys. D: Appl. Phys. 50 (2017 ) 075204

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Phys. D: Appl. Phys. 50 ( 2017 ) 075204 N Britun et al Figure 3. (a)

Figure 3. (a) The appearance of the O TALIF signal on the ICCD sensor, along with the dedicated ROI. (b) The background fitting and subtraction procedure used in this work.

3. O density calibration methods

In this work two spectroscopic techniques, one based on optical emission and one based on optical absorption spectr­ oscopy, are proposed for quantification of the O atom density in HiPIMS discharges. Both of them are based on the optical actinometry principle.

3.1. Optical emission actinometry

Optical actinometry is a well­known non­intrusive technique that allows us to determine the absolute density of species by the ratio of spectral emission lines [26]. In this case, a certain amount of a foreign gas (called the actinometer) with a known concentration is added to the gas mixture. This technique has numerous applications, e.g. determining the CO density in microwave plasma [27], etc. Its principle is based on the fact that the emission intensity I ij corresponding to a particular spectral transition between the upper (i) and lower ( j ) atomic or molecular states is proportional to the population of the upper state (see e.g. [28, 29]). Assuming that electron impact is the dominant excitation mechanism, for the transition light intensity we can write:

I

ij

=

Ch A n

ν

ij ij

i

=

Ch A

ν

i j i j

k

n n k

e

k

<

i

ki

/

k

<

i

A

ik

+

Q ,

i

(1)

4

where C is a constant related to the detection system, hν ij is the quantum of light corresponding to the ij radiative transition,

A ij is the coefficient of spontaneous emission,

describes the electron excitation of the level i coming from

all the lower levels with densities n k , n e is the electron den­ sity, k ki is the electron impact excitation coefficient for k­i

excitation,

upper level i, and Q i is the collisional quenching of the level i,

defined as Q

evant quenchers of the level i with densities n j and quenching rates k Q i ). The electron impact excitation coefficient can be expressed in the form [29]:

A ik represents the radiative losses from the

k

<

i

n n k

k e ki

k

<

i

i

= ∑ n k

j

i

Q

i (the summation goes over all the rel­

j j

j

k

ki

=

ε

0

f

(

ε σ ε

)

(

)

d ,

ε

(2)

where f ( ε ) is the electron energy distribution function (EEDF), σ ( ε ) is the electron impact excitation cross­section and ε 0 is the electron excitation threshold for this transition. In low­pressure discharges (mTorr range) for radiative trans­ itions the collisional quenching can be neglected compared to

the radiative de­excitation. In addition, the first sum in expres­ sion (1) is normally reduced to the n n k 0i term representing the electron excitation from the ground state level (the so­ called corona approximation). While this approximation works

in most low­pressure discharge cases [27], in some cases the

contribution of the intermediate metastable levels should also

be taken into account. In particular, in the case of Ar­containing

discharges, which are relevant to this work, the contribution

of the Ar 4s 1s x ( x = 5,4,3,2) states can be essential, starting

from several mTorr, as studied by Boffard et al [30]. Taking into

account these considerations, the expression (1) yields:

0

e

(3)

where n 0 denotes the ground state density and

α

metastable states to the population of the i excited state. In this case the summation covers the relevant metastable levels k < i . Based on equation (3), the expression giving the ground state number density of the species of interest (n ) through the ground state number density of the actinometer (n act ) can be obtained by making a ratio of the corresponding emission lines:

is the relative contribution of the

k

I

ij

= Chν A n n k 1 + α

ij ij

0 e 0i

(

ki

)

/ ( n k )

0

0i

)/

m et

A ,

i k

met

≡ ∑ n k

k

(

x

0

0

n

x

0

n

act

0

=

I

x

x

λ A

ij

ij

act

act

 

act

A

x

ij

 

k

0

i

( 1

+ α

met

)

ik

I

act

ij

λ

act

ij

A

x

k

x

0

 

( 1

+ α

x

)

.

ij

i

met

A

act

ik

(4)

Since in our case n = [ O] and n = [ Ar ] , neglecting the

), for the ground state

x

0

act

0

contribution of O metastables (α

x = 0

met

O atom density we obtain:

[ O] = [ Ar ] R ( 1 + α

act

Ar

met

) β ,

ij

(5)

where some terms are redefined as R

sion peaks ratio), and

act

I / I act (i.e. the emis­

x

ij

ij

J. Phys. D: Appl. Phys. 50 (2017 ) 075204

N Britun et al

Table 3. Spectral transitions used for calibration of the O ground state density by emission actinometry.

Ar upper

Wavelength

Ar

state

(nm)

β

ij

(at T e = 2 eV)

α

met

(from [30] a )

2p

1

750.39

0.42

 

0.06

 

2p

2

826.45

0.05

0.21

 

727.29

0.007

 

696.54

0.02

 

2p

3

840.82

0.1

 

0.23

 
 

738.40

0.04

 

706.72

0.02

2p

5

751.47

0.11

 

0.13

 

a The estimations are performed at 15 mTorr, taking into account both Ar metastable and resonant states and assuming that the Ar 1s 5 density is equal to 5 · 10 10 cm 3 (top estimation).

β

ij

x

λ A

ij

act

ij

k

act

0

i

A

x

ik

λ

act

ij

A

x

ij

k

x

0

i

A

act

ik

.

(6)

Following the work of Boffard et al [30], where the rela­ tive contributions from the Ar 4s group to the Ar excited states are analyzed, only the Ar spectral transitions with a minimal contribution from Ar metastables were chosen for this study,

as summarized in table 3. The top estimated values of the α met (at 15 mTorr) are also shown in table 3. The typical density of the Ar metastables for this estimation was determined based on separate measurements. We have to note that the accuracy of optical actinometry depends strongly on the electron temperature T e . This is related to the fact that the electron impact excitation coeffi­ cient k 0i is sensitive to this parameter when T e < 3 eV, which falls in the typical T e range for magnetron plasmas. This effect is illustrated in figure 4(a), where the ratios of the electron

for several Ar excited states are

presented. The electron cross­section data in this case are taken from [31, 32]. In our case, T e was determined exper­ imentally using the Ar spectral peak ratio method proposed by Silva et al [33]. In our case, the calculations of the electron impact excitation coefficients were performed at T e = 2 eV (see section 4.1) assuming a Maxwellian EEDF, which is a good approximation for HiPIMS plasmas [9, 34]. Indeed, the non­thermal (hot) electrons that may be present in the HiPIMS plasma pulse likely play a minor role in our case, since our measurement point is chosen at the end of the plasma pulse, whereas the hot electrons mainly exist at the beginning of the pulse. The EEDF changes to a single­slope Maxwellian dis­ tribution at the end of the HiPIMS pulse, where T e is typically about 2 eV, as studied by Poolcharuansin et al [35]. The quick disappearance of the hot electrons during the HiPIMS pulse is also confirmed by our recent LIF observations [17]. In addition to the electron temperature, the gas temper­ ature is also important, as estimates of the Ar ground state density are involved in the described calibration procedure. This temperature was taken to be equal to 550 K at the end of the plasma pulse, based on [36]. The Ar, etc ground state densities were estimated using the ideal gas laws assuming uniform pressure in the discharge volume.

excitation coefficients k / k

Ar

Ar

0i

O

0 i

5

volume. excitation coefficients k / k Ar Ar 0 i O 0 i 5 Figure 4.

Figure 4. (a) The ratio of the electron excitation coefficients for O(3p 3 P J ) and Ar(4p 2p x ) excited states as a function of electron temperature, calculated using the available cross­section data [31]. (b) The electron impact excitation cross­sections for the Ar (1s 5 ) [31] and O (3 s S 2 0 ) [54] metastable states, along with a Maxwellian EEDF (at T e = 2 eV). The ratio of Ar and O excitation coefficients (shown by dashed areas, representing the corresponding integrals) in this case is equal to 0.93.

5

3.2. Optical absorption actinometry

During the discharge afterglow the actinometry principle can still be applied to the non­radiative (metastable) upper states. Since in pulsed magnetron discharges the population of metastable states can be significant for both O [19] and Ar [17, 37] atoms, the principles of emission actinometry can be transferred to the metastable levels. Since the number den­ sities of the corresponding metastable states are normally determined by atomic absorption spectroscopy [37, 38], the proposed method can be called absorption actinometry. This method is supposed to be particularly useful in the HiPIMS afterglow, when plasma emission is vanishingly small, the electron excitation is negligible and the metastable state popu­ lations can be reliably determined by absorption techniques in the UVinfrared spectral range [19, 3740]. Let us consider two metastable states of the atom of interest and the actinometer (O and Ar in our case). During the plasma pulse they are both populated by electron excitation and, by the definition of metastable states, they are only depopu­ lated by collisional quenching (in the first approximation). Assuming there are no intermediate metastable levels between the ground state level and the considered metastable levels, the ratio of their populations during the plasma on­time can be written as:

J. Phys. D: Appl. Phys. 50 (2017 ) 075204

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Phys. D: Appl. Phys. 50 ( 2017 ) 075204 N Britun et al Figure 5. The

Figure 5. The evolution of the Ar (1s 5 ) and O (3 s S 2 0 ) metastable state densities measured in the ArTi40% O 2 HiPIMS discharge by optical absorption spectroscopy. Repetition frequency = 1 kHz, pulse duration = 20 µ s, gas pressure = 20 mTorr and E P = 0.3 J. The density fits in the afterglow are shown by the dashed lines. The vertical dashed line corresponds to the end of the plasma pulse. Adapted from [55].

5

 

O

[ O ] k

O

Q

Ar

n

0met

=

ex.met

met

 

Ar

[

Ar

]

k

Ar

Q

O

,

n

0met

ex.met

met

(7)

are the populations of the corresponding

metastable states at the end of the plasma pulse or right at the

where n 0met

O

Ar

and n 0met

beginning of the afterglow, k ex.met are their electron excitation

coefficients and Q met

states. The electrons cool down rather quickly in the HiPIMS afterglow and electron excitation can normally be neglected about a hundred µ s after the plasma pulse [41]. Due to this fact, the metastable states should be depopulated exponen­ tially at a rate mainly defined by their quenching coefficients:

O,Ar are the quenching coefficients of these

O,Ar

(8)

where t is the time from the beginning of the afterglow.

and

n

Combining (7) and (8) and redefining n

n

met

met

( t ) = n

0met

Exp( t Q

m et

O

) ,

met

( t ) = [ O

met

]

Ar

met

( t ) = [ Ar

]

, for the O ground state density we obtain:

[

O

]

=

[

Ar

]

[ O

met

]

k

Ar

ex.met

Q

O

met

[

Ar

met

]

k

O

ex.met

Q

Ar

met

Exp

( (

t Q

Ar

met

Q

O

met

) ) .

(9)

It can be shown that for the two considered Ar and O meta­

1 at T 2 e V , as illustrated in

Ar

stable states, k / k

ex.met

O

ex.met

e

figure 4(b). Taking into account the fact that molecular oxygen can be considered as the main quencher at high O 2 admix­ tures, whereas quenching by Ar can be neglected [42, 43],

we can write Q = [ O ] k

(where k q.met = 1.4 · 10 10

cm 3 s 1 [44] and k

quenching rates of the considered O and Ar states by O 2 , and [O 2 ] is the O 2 ground state density). In this case, the final expression for the O atom ground state density through the population of the metastable states in the afterglow can be written in the form:

= 2.1 · 10 10 cm 3 s 1 [45] are the

O,Ar

met

O,Ar

q.met

O

2

Ar

q.met

[

O

]

=

[

Ar

]

[ O

met

]

k

O

q.met

[

Ar

met

]

k

Ar

q.met

Exp

( [

t

O

2

] (

k

Ar

q.met

k

O

q.met

)) .

(10)

Table 4. Comparison of the O atom ground state density determined by the optical absorption actinometry and emission actinometry methods, as proposed in this work (in the ArTi40%O 2 HiPIMS discharge working at 1 kHz, 20 mTorr, E P = 0.3 J and pulse duration = 20 µ s).

Time

 

[O]

emiss.

delay

[

O

met

] / [

Ar

m et

]

[O 2 ]

[O] abs.actinom.

actinom. a

50 µ s

0.1

 

3 · 10 14 cm 3

2.4 · 10 13 cm 3

1.4 ·

 

10

13 cm 3

100

µ s 0.2

 

3 · 10 14 cm 3

1.7 · 10 13 cm 3

1.4 ·

 

10

13 cm 3

200

µ s 0.8

 

3 · 10 14 cm 3

9 · 10 12 cm 3

1 · 10 13

cm 3

a The emission actinometry is applied at the end of a 20 µ s plasma pulse (in the 1 kHz, 20 mTorr and E P = 0.3 J ArTi HiPIMS discharge). Afterwards the results are extrapolated to the afterglow using the O density trends shown in figure 15.

The O density estimates through absorption actinometry

are made based on the number densities of Ar (3p 5 4s 1 1s 5

referred to as the Ar 1s 5 state below) and O (3s S 2 ) metastable states measured by absorption spectroscopy in an R­HiPIMS discharge operating at 1 kHz at 20 mTorr in a TiAr40% O 2 gas mixture at E P = 0.3 J. The obtained density evolutions for these conditions are given in figure 5. The results for O density estimation using the absorption actinometry method at different time delays in the 1 kHz discharge are given in table 4, where they are compared (approximately) to the emission actinom­ etry results obtained for the same discharge conditions. The obtained discrepancies between the two methods are within a factor of two, which may be due to (i) the low stability of the absorption measurements applied for O and Ar metastable state density determination, (ii) the strong role of the electron excitation at short time delays after the plasma pulse, (iii) the

influence of the Ar 1s 5 state on the population of O metastable states during the afterglow (Ar + OAr + O m et ) and (iv) the uncertainties of the emission actinometry method. In our

opinion, more careful absorption measurements of the Ar and

O metastable state density performed during the afterglow

time could increase the precision of the absorption actinometry technique, making it comparable to that of TALIF. This might

virtually eliminate the necessity of having a bulky laser setup

for the determination of O ground state density.

5

2

met

4. Results and discussion

4.1. Electron temperature

The electron temperature in this work is determined at the end

of the HiPIMS pulse using the following expression (see [33]):

6

T

e

=

(

7.04

N ( 1 s

5

)

Log

0.19

R

0.10

)

1

/(

6.03

17.86

N ( s

1

5

)

0.17

)

,

(11)

where R is the intensity ratio of the Ar 425.9 nm and

750.4 nm emission lines (corresponding to the Ar 3p 1 1 s 2

and 2p 1 1 s 3 transitions, respectively) and N( 1s )

is the

5

J. Phys. D: Appl. Phys. 50 (2017 ) 075204

N Britun et al

Phys. D: Appl. Phys. 50 ( 2017 ) 075204 N Britun et al Figure 6. The

Figure 6. The appearance of the Ar 425.94 nm emission peak acquired for the case of (a) Ag, (b) Ti, (c) Cu and (d) W targets with a spectral resolution of about 0.02 nm showing the peak distortion by the surrounding spectral lines [46].

population of the Ar 1s 5 state normalized to the Ar ground state density. The relative error of T e calculated by expression (11) is supposed to be about 10%, as estimated in [33]. The visibility of the Ar 425.9 nm emission peak plays an important role in T e determination in our case, whereas the 750.4 nm Ar peak always has a high intensity. The high­res­ olution spectra of the 425.9 nm peak are given in figure 6. As we can see, in spite of the presence of the metallic emission peaks in the vicinity of Ar peak, the overlap is rather small [46]. In the case of the Ag target, the side Ag I emission lines result in the broadening of the resulting spectral line, and at the same time do not influence its amplitude significantly. Another important parameter for T e determination, namely the Ar 1s 5 state density, is taken to be equal to ~10 10 cm 3 at 20 mTorr of working pressure, based on the separate optical absorption measurements performed in the ArTi HiPIMS discharge under our discharge conditions (at the end of the plasma pulse, 5 cm above the target). Since expression (11) is weakly sensitive to

7

target). Since expression ( 11 ) is weakly sensitive to 7 Figure 7. The electron temperature

Figure 7. The electron temperature determined at the end of the HiPIMS discharge pulse (50 µ s) using the Ar line ratio method [33] as a function of (a) O 2 flow fraction (at 15 mTorr) and (b) Ar pressure (at 40% O 2 ). E P = 0.5 J.

the pressure­induced changes of the Ar 1s 5 state population in the studied pressure range, this dependence is neglected. The T e values determined in our case are given in figure 7. As we can see, T e does not change much as a result of O 2 addi­ tion, decreasing slightly as the working pressure increases. The last observation correlates well with the general elec­ tron temperature behavior in a glow discharge obtained by Sato [47]. Since all the estimated T e values are grouped around 2 eV, this value is taken for calculation of the elec­ tron excitation coefficients. If necessary, for a broader range of plasma conditions, when T e changes considerably, further corrections can be made, based on figure 4(a). The obtained T e values correlate with those measured in a HiPIMS dis­ charge during the plasma pulse [34], as well as right after the plasma pulse [41].

4.2. Time-resolved discharge evolution

Figure 8 represents the time evolution of the 2D distributions corresponding to the excited species at the beginning of the plasma afterglow for three target materials. In this case, the emission signal is mainly represented by the excited Ar (2p 3 and 2p 8 states), with a small ( < 10%) contribution from the excited O. As we can see, at the beginning of the afterglow the excited species are concentrated in the racetrack vicinity, and they then propagate upwards in the form of a merged wave. These results correlate very well with the time­resolved behavior of Ti ground state ions in the HiPIMS afterglow [17], as well as the OES imaging results obtained by Hala et al [13]. The TALIF signal from the atomic ground state oxygen (rep­ resented by a bright horizontal line) only becomes visible at

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Phys. D: Appl. Phys. 50 ( 2017 ) 075204 N Britun et al Figure 8. The

Figure 8. The OES mapping corresponding to the Ar 2p 3 and 2p 8 excited states (O emission contribution is < 10%) measured through an optical 840 nm (10 nm wide) bandpass filter after the HiPIMS pulse. The time delays are indicated in the corners. The bright horizontal line corresponds to the O TALIF signal. Pressure = 15 mTorr, O 2 flow fraction = 40% and E P = 0.5 J.

about 6570 µ s, i.e. 20 µ s after the plasma pulse. It is much weaker in the Ti case. The TALIF signal increases gradually during the off­time, being horizontally uniform, which is dif­ ferent from the spatial distributions obtained for Ar metasta­ bles and Ti ground state ions in HiPIMS [17]. At the same time, the appearance of an O TALIF signal corroborates the spatial distribution of the sputtered neutrals arriving during this time to the volume of interest [17], implying that some part of the O atoms is obtained from dissociation of the sput­ tered compounds, as suggested in [38]. In addition, direct sputtering of the O atoms from the poisoned target surface might also lead to the measured increase in O atom density, as suggested in [19, 48]. A detailed time evolution of the O density in the plasma off­time measured for different target materials is given in figure 9. In spite of the fact that the plasma afterglow emission affects the TALIF signal detection strongly at the beginning of the off­time, the general increase in O ground state density after the HiPIMS pulse is clearly visible (it is less pronounced

8

the HiPIMS pulse is clearly visible (it is less pronounced 8 Figure 9. The evolution of

Figure 9. The evolution of the O TALIF signal after the HiPIMS pulse for different target materials. Ar pressure = 15 mTorr, O 2 flow fraction = 40% and E P = 0.5 J.

for Ag, though), confirming the presence of the O atom wave after the plasma pulse, similarly to the Ti neutrals [17, 37]. In addition, the data presented in figure 9 allow us to displace the OES and TALIF measurement points for the sake of O atom density calibration (shown by arrows) in order to avoid strong afterglow emission preventing reliable TALIF signal detection at low laser power.

4.3. O atom number density

4.3.1. O 2 admixture effect. The O atom number densities measured by emission actinometry as a function of O 2 flow

fraction in the gas mixture are shown in figure 10. In this case, the Ar emission lines listed in table 3 were used (except for the 750.4 nm peak, which was excluded from the consideration to reduce data dispersion). The measurements were performed at 15 mTorr of working pressure at the end of the plasma pulse

50 µ s). The influence of Ar metastables is neglected in this case, since it might only increase the obtained densities by a factor of about 1.2 (see table 3). The errors bars shown cor­ respond to the standard deviation of the values obtained by different Ar spectral peaks. As one can see from figure 10, the measured O atom den­ sity increases proportionally to the O 2 flow fraction, showing comparable values for Ag, Cu and W targets. In the case of the Ti target, however, the O number density values are sev­ eral times smaller. The relative O density values measured by TALIF are also given (see figure 10(e)), showing rather good correlation with the OES data. The TALIF data points are nor­ malized to the 50 µ s time delay in this case, using the trends shown in figure 9. The total change of the O TALIF signal in the W case is much smaller than that measured by OES, which remains unclear and requires additional experimental verifica­ tion. The values obtained at an O 2 flow fraction of 40% were taken as the reference values for TALIF signal calibration for the further results. Assuming that electron impact is the main mechanism for O 2 dissociation, the production of O atoms as a result of this process (O + e O + O ) should be comparable for the con­ sidered targets, as the ISEE coefficients in the poisoned mode are roughly comparable for these materials [49, 50]. At the

(

2

J. Phys. D: Appl. Phys. 50 (2017 ) 075204

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Phys. D: Appl. Phys. 50 ( 2017 ) 075204 N Britun et al Figure 10. O

Figure 10. O ground state density determined using the OES (a)(d) and TALIF (e) techniques as a function of the O 2 flow fraction in the ArO 2 mixture. The TALIF data are renormalized to a 50 µ s delay time, according to figure 9 . Ar pressure = 15 mTorr and E P = 0.5 J.

same time, the fact that the O TALIF signal obtained with a Ti target is comparable to that of the other targets (figure 10(e)), whereas the O number density found by OES is several times lower in the Ti case, deserves special attention. This effect might be related to Tis significantly higher getter rate, which is known from the literature [51]. Sputtered Ti (or Ti­based com­ pounds) may also chemisorb reactive gases (O in our case) in the discharge volume [52], even though this process seems to be less probable, taking into account the low Ti densities in the poisoned mode ([Ti] < 10 11 cm 3 versus [O] > 10 12 cm 3 ). While the gettering of O 2 by the Ti target should reduce O pro­ duction in the discharge volume, the O­containing compounds

9

sputtered and dissociated by electron impact should be the

main source of O (Ti O + e Ti + O) in this case. As a result of gettering, the OES measurements show a reduced value of O oxygen in the discharge volume. On the other hand, in the presence of a laser, photodissociation may be a decisive factor for detaching O from Ti compounds (clusters, etc). This may elevate the O atom quantity in the laser­probed volume and increase the resulting TALIF signal (according to XO + hν X + O , where XO detones the sputtered

compounds, accompanied by

O

The photodissociation of the O 2 molecules that dominate in the discharge ([O 2 ] ~ 10 14 cm 3 ), at the same time, should be comparable for all targets, and negligible, according to the estimates of Li et al [53]. The lack of photodissociation cross­ section data for Ti­based (as well as other compounds) does not allow us to verify this hypothesis, however. Joint exper­ imental and modeling studies that take into account the effects of gettering and compound sputtering, their photoionization, and other relevant mechanisms, should clarify this issue. The dissociation degree of the molecular oxygen in the

discharge volume is defined as

, where [] denotes

the ground state number density. According to our measure­ ments, at the point of interest ( z 5 cm) the dissociation degree does not depend much on the O 2 flow fraction and is estimated to be ~2030% for Ag, Cu and W, and only about 6% for Ti. This should be related to the general stability of the electron temperature for these conditions, as shown in figure 7(a). It should be noted, however, that O 2 density in our case is determined based on the global pressure, neglecting the gettering effect, which may introduce a systematic error into the determined dissociation degree. The precise dissocia­ tion degree of O 2 can only be obtained by applying local O 2 density measurements.

las

+

2h

ν

las

O

O

h

+ ν

f luor

).

1

2

[ O] / [ O ]

2

4.3.2. Pressure effect. The O number density as a func­ tion of the gas pressure (for the Ar40% O 2 gas mixture) is given in figure 11. A rather good correlation between the OES (figures 11(a)(c)) and TALIF (figure 11(d)) data is obtained.

The O density increases proportionally to the gas pressure, dem­ onstrating a total jump of about 1.5 orders of magnitude. The

O density values for Ti target are lower, as in the previous case. The degree of O 2 dissociation in this case changes by a

factor of nearly two with the increase of the gas pressure from 3 to 20 mTorr, as shown in figure 12. The obtained dissocia­ tion degrees for Ar and Cu are very close, ranging between 20 and 40%. In the case of Ti, this parameter, as expected, is about threefour times lower, correlating with the data shown previously.

Another effect is observed

under the change of the total gas flow, while the gas pressure

is kept constant (15 mTorr in this case). As shown in figure 13,

the O atom density increases by a factor of about four (for Ag) and about two (for Ti) as a result of the gas flow increase from 10 to 80 sccm. These effects also correlate well with the TALIF measurements of the O atom density (data not shown here).

4.3.3. Gas flow and power effects.

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Phys. D: Appl. Phys. 50 ( 2017 ) 075204 N Britun et al Figure 11. O

Figure 11. O ground state density determined using the OES (a)(c) and TALIF (d) techniques as a function of the total gas pressure. The TALIF data are renormalized to a 50 µ s delay time according to figure 9. O 2 flow fraction = 40% and E P = 0.5 J.

Interestingly, the measured O ground state density remains weakly sensitive to the discharge power (or pulse energy E P ). As shown in figure 14, where the O atom density is given as a function of E P , the production of ground state atomic oxygen increases by a factor of ~1.5 during a nearly fivefold increase of the pulse energy. This effect is rather surprising, taking into account the direct proportionality of the sputtered material to the pulse energy in HiPIMS [17]. This phenomenon might be explained by the competition of the sputtering and the recombination of O atoms with the growing amount of sputtering material (atoms, molecules and clusters) at the elevated pulse energies. This effect can be clarified in the future, based on modeling studies that take O production and O recombination rates carefully into account.

The main advantage

of the laser­based detection of O atoms in the discharge is the ability to measure this quantity during the plasma afterglow, which is especially important in the HiPIMS case. In our case,

4.3.4. Time-resolved and spatial effects.

10

In our case, 4.3.4. Time-resolved and spatial effects. 10 Figure 12. The O 2 dissociation degree

Figure 12. The O 2 dissociation degree 5 cm above the target calculated at the end of the plasma pulse (50 µ s) based on the data from figure 11. O 2 flow fraction = 40% and E P = 0.5 J.

11 . O 2 flow fraction = 40% and E P = 0.5 J. Figure 13.

Figure 13. O ground state density determined by OES for (a) Ag and (b) Ti targets as a function of total gas flow. O 2 flow fraction = 40%, pressure = 15 mTorr and E P = 0.5 J.

the OES­based calibration of the number density is realized at the end of the plasma pulse, as mentioned earlier. The results of the time­ and space­resolved measurements of the O ground state density in the HiPIMS afterglow are presented in figure 15. The measurements are performed for four target materials at an O 2 flow fraction of 40%. The measurement errors of in this case are determined by density

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Phys. D: Appl. Phys. 50 ( 2017 ) 075204 N Britun et al Figure 14. The

Figure 14. The variations of the O TALIF signal as a function of the pulse energy E P for two target materials. Pressure = 20 mTorr and O 2 flow fraction = 40%. The delay times are 100 µ s (W) and 300 µ s (Cu).

calibration and are similar to those shown in figures 10 and 11.

In figure 15 the total range of the O number density covers

nearlythreeordersofmagnitude,startingatabout5·10 14 cm 3 at the very beginning of the plasma off­time before it decays rapidly down to the detection limit at the end of the off­time, when the TALIF signal is comparable to the

detector noise (~10 12 cm 3 ). As in the previous cases, the dynamics of the O density is comparable for all the target materials, with somewhat lower densities corresponding

to the Ti case, as observed previously. It should be noted

that the O atom density values we obtained from the target surface for Ti at z = 25 mm (see figure 15 ), when recal ­ culated to an O 2 flow fraction of 5% (~10 13 cm 3 ), are in good agreement with the modeling results obtained in the HiPIMS ionization region at the end of the pulse at a com­ parable pulse energy [48]. For each target material, the O density distributions are already merged (or equilibrated) after about 200 µ s, showing rather close density values and nearly the same behavior, nearly independent of the distance. At short time delays, how­ ever, the O density depends strongly on the distance from the target, changing by a factor of about ten (for Ti and Cu) when the values found at z = 65 mm and at z = 25 mm are com ­ pared. The propagation of the wave of neutral O atoms is also visible in the case of Cu and W (shown by arrows). A rough estimate of the velocity of this wave gives a value of ~1 km

s 1 , which is comparable to the typical velocity of sputtered atoms found for similar conditions in HiPIMS by LIF [17] and OES [13], and also to the values found in DCMS [15]. Interestingly, in all cases, the temporal evolution of the

O atom density reveals a weakly pronounced peak at a time

delay of about 500 µ s. Its appearance correlates very well with the refill of Ar metastables in the discharge volume detected in [17]. Due to this observation, we may suggest

the presence of a small (but decent) contribution of Ar meta­ stables to the O dissociation process in the bulk of HiPIMS

), together with Ar met ­assisted

creation of the O metastable states (Ar

afterglow (O

),

as suggested elsewhere [19, 40]. The contribution of Ar met to

O 2 dissociation during the plasma on­time should be much more essential, causing the large difference in the Ar met den­ sity measured during the plasma on­time and off­time [37].

2

+ Ar

met

O + O

met

+

O O

m et

+ Ar

11

2 + Ar m e t → O + O met + O → O m

Figure 15. (a)(d) The time­ and space­resolved O ground state density determined for different target materials in the HiPIMS afterglow. The distance z from the target surface is indicated on the legend. (e) The magnified view of the W case. The arrows indicate the O density peaks observed at selected distances. Pressure = 15 mTorr, O 2 flow fraction = 40% and E P = 0.5 J. the vertical dashed lines mark the end of the plasma pulse.

5. Conclusions

In this work, the O ground state atom density is determined in a short­pulse (50 µ s) reactive HiPIMS discharge using a combination of optical emission spectroscopy and laser­

induced fluorescence techniques. In addition to the calibration of O atom density by emission actinometry, a method (called absorption actinometry) based on the ratio of O and Ar meta­ stable state populations is proposed. These two calibration methods give comparable results.

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The effects of O 2 admixture, gas pressure and applied

power on O atom number density are studied, and generally show good agreement between the OES and TALIF data. The

O number density in the discharge afterglow ranges between

~10 12 cm 3 and ~5 · 10 14 cm 3 , depending on the time delay

in the afterglow and the distance to the target. The O atom

density is found to be weakly sensitive to the applied power. In addition, the O atom density in the case of the Ti target appears to be several times lower than in the other examined cases (Ag, Cu and W). Further experiments involving the veri­

fication of the role of photoionization, as well as different O density calibration methods, may clarify this point. Time­ and space­resolved measurements show that the O atom density equilibrates at the time delays above 150 µ s after the plasma pulse. At the beginning of the off­time (1050 µ s after the plasma pulse) the wave of neutral O atoms

is detected. Its propagation velocity (~1 km s 1 ) is compa­

rable to the typical velocity of sputtered atoms in DCMS and

HiPIMS discharges. In addition to this, a faint but clearly vis­ ible secondary O density maximum appearing at about 500 µ s

in the off­time correlates clearly with the refill of the Ar meta­

stable atoms in this discharge region (measured previously), indicating the role of O 2 dissociation by metastable species. It should be also noted that the performed measurements

may contain errors. Some of these relate to the assumptions of the corona + metastable excitation in the actinometry method

or come from the electron temperature estimates, but the main

source is probably the gas rarefaction above the target. Indeed,

it is suggested that the proposed density calibration comes at

the end of the plasma on­time above the target surface, where Ar gas can be rarefied. The global Ar pressure measurements used in this work for Ar density estimation do not take this effectwhich can only be measured locallyinto account. However, we think that at the moderate applied power levels used in this study the effect of Ar rarefaction at 5 cm is rather small. The precision of the proposed quantification techniques

can be further enhanced by e.g. (i) quantification of the gas rarefaction above the target by laser­based measurements (with and without discharge) in the calibration point, (ii) pre­ cise calculation of the excitation coefficients, (iii) improved T e determination, including direct probe measurements, (iv) precise calculation of the role of metastable states in Ar exci­ tation, (v) more reliable metastable density detection for absorption actinometry and (vi) improved signal­background separation during and after the plasma pulse, etc. In general, the results of this work establish new ways to quantify the O ground state density in HiPIMS discharges, which are in great demand for future research work related to reactive

sputtering. The obtained results can also be used to calculate the

O atom flux on film surfaces, estimate the dissociation degrees of

molecular oxygen in the plasma bulk and model reactive HiPIMS discharges.

Acknowledgments

This work is supported by the Belgian government through the Pôle dAttraction Interuniversitaire(PAI, P7/34, PlasmaSurface Interaction, Ψ ). NB acknowledges the support of the

12

REFORGAS GreenWinproject (grant no. 7267). AB thanks the University of West Bohemia in Plzeň for support under the projects SGS­2016­056 and INTER­16. TS was partially supported by the Portuguese FCT, under the projects UID/ FIS/50010/2013 and PTDC/FIS­PLA/1420/2014.

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