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Copyright D. Depla 1
Reactive magnetron
sputter deposition:
a journey from target to substrate
D. Depla
Dedicated Research on Advanced Films and Targets
Ghent University
D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Setting the scene
Who ?Some keywordsMain features of the model
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Copyright D. Depla 2
D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Who ?
Further development of the RSD modelSimulations
Koen Strijckmans
Oxide formation on the target
Roeland Schelfhout
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
RSD2018
December 6th and 7th.
Short course : December 5th www.rsd2018.be
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
A few keywords
The RSD model aims to get a betterinsight in the reactive sputtering processKey features are
• Analytical approach• Click on/off approach• GUI to assist the user• Main focus on the “hysteresis”
D. Depla, S. Heirwegh, S. Mahieu, and R. De Gryse, J. Phys. D-Appl. Phys. 40404040 (7), 1957 (2007).D. Depla, X. Y. Li, S. Mahieu, K. Van Aeken, W. P. Leroy, J. Haemers, R. De Gryse, and A. Bogaerts, J. Appl. Phys. 107107107107 (11) (2010).K. Strijckmans, W. P. Leroy, R. De Gryse, and D. Depla, Surf. Coat. Technol. 206206206206 (17), 3666 (2012)K Strijckmans and D Depla, Journal of Physics D: Applied Physics 47474747 (23), 235302 (2014)K. Strijckmans and D. Depla, Appl. Surf. Sci. 331331331331 (0), 185 (2015)K. Strijckmans, Ghent University, 2015
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Target processes
As we know ions getimplanted, we describe theion implantation in the bulk
Initially the implantedatoms are not chemicallybonded. We describeexplicitly the chemicalreaction
knrnmSurface processes are described as abalance between removal and addition
The transport is defined bysputtering and redeposition
K. Strijckmans and D. DeplaJournal of Physics D: Applied Physics 47 (2014) 235302
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
An example
Target poisoning occurs not onlyat the surface, but also in thesubmonolayers.The major contribution is reactiveion implantation.The RSD model accounts for thechemical reaction between theimplanted species and the targetmaterial.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Question 1 : Can we predict the first critical point ?
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
An experiment
Target material : aluminiumCircular planar target (2 inch diameter)Pumping speed : 35 l/s
The first critical point linearlydepends on the discharge current
Before the first critical point hardly anincrease of the oxygen pressure
Origin : the target and thedeposited material react with theintroduced oxygen.Getter pump action.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
A few experiments more …
Different conditions show a similar behaviour
Can we describe this more quantitative ?
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Copyright D. Depla 6
D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Some equations, sorry !We assume the target is much smaller than the deposition area, orstated differently before the first critical point the gas is onlyconsumed by the deposited material
The condition of the deposited material is given by the following balance equation
chemisorption compound deposition metal deposition
But the target is hardly poisoned :
Metal deposition
The maximum getter is just given by the product of the discharge current, andthe metal sputter yield. Or the first critical point scales linearly with thecurrent. And what about your experiments ?
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Database
Your data is stored in a database(currently 120 entries, 32 differenttarget-gas combinations)
Slope between experimental flow at the1st critical point, and maximum getter rateis 0.541.
Engineering approach
���� sccm ��� 3.75 sccm/A ���
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
How good is our model ?
Perform simulations (53248 in total)
Most common value for �̅�̅� : 0.575
Simulations for different substrateareas, sticking coefficients, sputteryields, pumping speed (colour coderefers to combinations) But we also deviations from the fit …
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
DeviationsLet us return to assumptions …
Low reactive gas pressure before critical point
Not true for low reactivity materials
Only consumption by the deposited material
Not true at high pumping speeds
Only consumption by the deposited material
Not true at low discharge currents
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Copyright D. Depla 8
D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Question 1 : Can we predict the first critical point ?
Answer 1 : Yes, reasonable well…
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Question 2 : Can we predict the discharge voltage behaviour ?
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Experimental observation
M = metalX = nitrogen/oxygen
M = metalX = nitrogen/oxygen in the bulk
at the surface
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Why do we have this relation ?For high values of R (>1), we have a reduced oxide (nitride) target surface.Reduced oxides (and most nitrides) are (semi)-conductors with a low electronyield or high discharge voltage during poisoning. The opposite holds for lowvalues of R (<1).
Another interpretation of R : it is a measure for the difficulty to form a fullystoichiometric compound during ion bombardment.
But, despite the impressive amount of experimental data supporting this idea,we need first to proof that during reactive sputtering, we indeed have areduced oxide surface.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
XPS to confirm …reactive sputtering of Ta
target
1” magnetron
A new design of a 1’’magnetron always toremove the target invacuo and transfer itto the XPS analysischamber.
For Ta…
For Ta, suboxides are formed, but athigh fractions, the stoichiometricoxide is observed.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
XPS to confirm it … reactive sputtering of Al
For Aluminium only theoxide and the metal aredetected. No suboxides areobserved.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Relation discharge voltage-oxide fraction
Al
Ta
The discharge voltage can be correlated with the presence of thestoichiometric oxide.
The oxygen fraction during reactive sputtering, even in poisoned mode, isseldom larger than 0.2
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Answer 2 : Yes, and we understand the mechanism.
Question 2 : can we predict the discharge voltage behaviour ?
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Question 3 : Do we have data on the oxide sputter yield ?
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Is data on the sputter yield important … ?
The ratio between the metal sputteryield Ym and the compound sputter yieldYtot defines to a large extend thehysteresis phenomenon.
So, a simple conclusion is that hysteresisis caused by the lower sputter yield ofcompounds.
“…the authors come to the conclusion that the sputtering yield of oxides are in most cases similar to oreven higher than those of the corresponding metals.", and further in the same overview “For comparison,measured data for Si and Ta are included. For SiO2, the sputter yields are about the same magnitude orslightly lower than Si, but for Ta2O5, generally higher yields than for Ta are observed."
G. Betz and G. K. Wehner, \Sputtering of multicomponent materials," in Sputtering by Particle Bombardment II: Sputtering of Alloys and Compounds, Electron andNeutron Sputtering, Surface Topography, edited by R. Behrish (Springer Berlin Heidelberg, Berlin, Heidelberg, 1983) pp. 11-90.
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Copyright D. Depla 13
D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
This is the data we have …
Tantalum oxide
In agreement with theexpectation, no hysteresisobserved.
J. M. Ngaruiya, S. Venkataraj, R. Drese, O. Kappertz, T. P. L. Pedersen, and M. Wuttig, Physica Status Solidi a-Applications and Materials Science 198198198198 (1), 99 (2003).K. Juškevičius, M. Audronis, A.s Subačius, S.. Kičas, T. Tolenis, R. Buzelis, R. Drazdys, M. Gaspariūnas, V. Kovalevskij, A. Matthews, and A. Leyland, Thin Solid Films 589589589589, 95 (2015).
Niobium oxide
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
But there is a problem …
Tantalum oxide12 times lower
Niobium oxide5 times lower
Why is there a huge drop in deposition rate ? Most points are addressed.
Bombardment by O2+ instead of Ar+ ?
Not always a valid argument
Ta Nb
Yield (Ar) 0.876 0.688
Yield (O2+) 0.384 0.502
��
��
� � ���� !!
��!!
��
��
"��#$%�
�$�
"�#$%
Deposition profileswill be similar.
Voltage are different.�$�
�
�#$%�
��, '(
�#$% ��, '(
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Copyright D. Depla 14
D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Can we trust the sputter yields ?Measuring the mass difference and discharge current at constant discharge voltage
Difficulties1. Electron yield2. Neutrals3. Ion energy
NeutralsCharge exchange mechanismWindow based on literature
I.Y. Burmakinskii et al.Tech. Phys., 49 (1) (2004), pp. 119–122
E. Bultinck, et al., New J. Phys., 11 (2009)
Consistent with advancedsimulations
E. Bultinck, et al., New J. Phys., 11 (2009)
M.J. Goeckner, J.A. Goree, T.E. SheridanIEEE Trans. Plasma Sci. 19 (1991), 301–308
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
But for oxides …
The weight loss, and so thesputter yield, as a function ofthe discharge current duringreactive sputtering (poisonedmode) of an aluminiumtarget.
Re-deposition on the target was excluded by shielding the re-deposition areas.
Can we proof it in another way ?
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Copyright D. Depla 15
D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
An alternative way to measure the sputter yield
)#% � )� � )� � )�
Balance equation
) $%� � )� � )� ��
2�#$%
In poisoned mode, theconsumption rate isdirectly related with thecompound sputter yield.
Measure with a mass spectrometer the oxygenpressure (simple explanation)
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Comparison
This new method confirmsthe current dependency ofthe sputter yield
Reason : we now work onthe hypothesis that thetarget contains non-reactedimplanted oxygen atoms. Atlow discharge current theseatoms can diffuse from thetarget. At high dischargecurrent their presencereduces the sputter yield.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Overview sputter yields
Several observations
• Not related to the targetcondition (see sputter cleaningexperiments)
• Large difference between ratiobased on ion beam experimentsand deposition rate experiments
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Correlation between compound sputter yieldsA remarkable plot because R ensuresthat the flux from the target equalsthe compound composition.There is a big difference betweenion beam (or sputter cleaning)experiments, and sputtering inpoisoned mode
Ar+ Ar+ O2+
O2
The removal of an oxygen atom increases the probability to sputter a metal.
A removed oxygen atom, can be replaced by another (implanted) oxygen atom.
Outliners are probably related to texturing.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Answer 3 : No, we have not. Moreover the mechanisms are not fully clear.
Question 3 : Do we have data on the oxide sputter yield ?
“…the authors come to the conclusion that the sputtering yield of oxides are in most cases similar to oreven higher than those of the corresponding metals.", and further in the same overview “For comparison,measured data for Si and Ta are included. For SiO2, the sputter yields are about the same magnitude orslightly lower than Si, but for Ta2O5, generally higher yields than for Ta are observed."
G. Betz and G. K. Wehner, \Sputtering of multicomponent materials," in Sputtering by Particle Bombardment II: Sputtering of Alloys and Compounds, Electron andNeutron Sputtering, Surface Topography, edited by R. Behrish (Springer Berlin Heidelberg, Berlin, Heidelberg, 1983) pp. 11-90.
This is 35 years ago !
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Question 4 : And what about the time dependency of the process ?
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Consumption/sputter yield as a function of time (x2)
Just wait …
Again … can we trust this sputter yield behaviour ?
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Sputter cleaning to proof
Sputter cleaning experiments give information about initial target behavior
Measure cleaning time
Calculate Y:
(With fixed thickness d = 2 nm)
+ (,'%#%- ∝/
Confirmation of our experiments.Origin is probably due todiffusion of the non-reactedoxygen from the target.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Desorption
An abrupt change as a function of the reactive gas fraction is noticed.Slow outdiffusion of nitrogen is detected.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
The reaction rate constant
So, the reaction rate constant is an effective reaction rate constant
The grey regions are based on adedicated fitting of hysteresisexperiments for Y and Al,published before this work andusing other data.
knrnm
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Answer 4 : Diffusion (radiation enhanced, thermal, pressure driven) is the processwe need to describe to quantify in detail our experiments. Moreover, for pulsedexperiments, it will become a necessity.
Question 4 : And what about the time dependency of the process ?
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Question 5: Does our traditional view show all details ?
P (or V)
Q
P
Q
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Our “traditional” view on reactive sputtering
In literature different ways are used to study the hysteresis phenomenonFlow control (Q)Stepwise change of the reactive gas flowWorking at constant current (I), voltage (V) or power
Measuring the change in voltage, current and pressure (P)
P (or V)
QPressure control (P)Stepwise change of the reactive gas pressureWorking at constant current (I), voltage (V) or power
Measuring the change in voltage, current and pressure (P)
P
Q
Of course, voltage control is also possible. It has several advantages.It is fast, easy and permits to work in a “random” way to exclude any long termeffects such as target erosion.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
PVIQ plot : metallic to poisoned mode
high pressure, low voltagePoisoned mode
low pressure, high voltagemetallic mode
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Comparison with common plots (projections from (P,V,I,Q)
voltage (V)Pressure(Pa)
I-V characteristic for the metallic mode
I-V characteristic for the poisoned mode
flow (sccm)
Current(A)
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
PVIQ plot : metallic to poisoned mode
high pressure, low voltagePoisoned mode
low pressure, high voltagemetallic mode
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
PVIQ plot : from poisoned to metallic mode
When don’t get the same result when the (P,Q,I,V) space isaccessed in a different direction.
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
So forward and back is different
From metallic to poisoning
From poisoning to metallic
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Double hysteresis
Origin :
1. An avalanche due the getteringcapacity of the deposited material which cause a single S (see first critical point)2. An avalanche due to the reaction kinetics of the implanted reactive ions which causes the double S .
The existence of a double S-shaped process curve during reactive magnetron sputteringR. Schelfhout, K. Strijckmans, D. DeplaApplied Physics Letters 109 (2016) 111605
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Origin of the double hysteresis : a possible answerSetting the scene Question 1 Question 2 Question 3 Question 4 Question 5 Final question
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D. Depla Plasma diagnostics and modelling, Mons, 2018 www.DRAFT.ugent.be
Question 5 : Does our traditional view show all details ?
Answer 5 : No. The new approach confirms the model, but adds new challenges.
We observe a double hysteresis in the simulations,but the fit with the experiment is not completely successful.
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