titan themis - cea/leti (english)son...zineb saghi, adeline grenier, daniel lichau 3d chemical...
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Zineb Saghi, Adeline Grenier, Daniel Lichau
3D CHEMICAL ANALYSIS OF COMPLEX NANO-DEVICES BY ANALYTICAL ELECTRON AND
ATOM PROBE TOMOGRAPHY
Titan Ultimate
Titan Themis
| 2
Electron tomography:
Julien Sorel
Martin Jacob
Nicolas Bernier
Vincent Delaye
CEA-Leti, GrenobleMachine learning:
Francisco de la Pena
University of Lille
Compressed sensing:
Toby Sanders
Arizona State University
Philippe Ciuciu
NeuroSpin, CEA Saclay
Samples:
Rafael Bortolin Pinheiro
Frédéric Mazen
Marie-Claire Cyrille
Gabriele Navarro
Véronique Sousa
CEA-Leti, Grenoble
3DAM partners
Atom probe tomography:
Adeline Grenier
CEA-Leti, Grenoble
Isabelle Mouton
CEA Saclay
Daniel Lichau, Sebastien Millot
Thermo Fisher Scientific
Isabelle Martin
Cameca
Sample preparation:
Audrey Jannaud
Guillaume Audoit
CEA-Leti, Grenoble
CONTRIBUTIONS
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WHY 3D IN SEMICONDUCTOR INDUSTRY?
Composition / Doping
3D TOF-SIMS, APT, STEM-EDX/STEM-EELS
tomography
Dimensions / Morphology
X-ray tomography, serial sectioning by FIB-
SEM, HAADF-STEM tomography
From IMEC
3D architecture
Decreasing size
Increasing complexity
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BASICS OF ELECTRON TOMOGRAPHY
?
1. Acquisition 2. Alignment 3. Reconstruction
A standard electron tomography
experiment:
1. Imaging mode: HAADF-STEM
Incoherent (no diffraction contrast)
Z contrast (I ~ Z2)
2. Automated acquisition: -90°:1°:90°, ~3h,
~500Mb.
3. Automated alignment and reconstruction (~1
day).4mm
1 0 0 0 n m1 0 0 0 n m
Commercial software:•Inspect 3D (FEI)
•TEMography (JEOL)
•3D tomography (Gatan)
•DigiECT (Digisens)
Freeware:
•IMOD
•TomoJ
•TOM software toolbox
•Protomo
•UCSF tomography
•Tomo3D
•ASTRA
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STANDARD ALIGNMENT AND RECONSTRUCTION ALGORITHMS
መ𝑓 = 𝑎𝑟𝑔min𝑓
ℝ𝑓 − 𝑝 22
E. Hanssen, Cellular Imaging: Electron Tomography and Related
Techniques, 2018.
Tilt series alignment
by cross-correlation or with fiducial markers
Reconstruction by SIRT
(simultaneous iterative reconstruction technique)
G. Haberfehlner, 3D nanoimaging of semiconductor devices and materials by electron
tomography, 2013.
Work well if a large number of projections are acquired (tilt increment: ~1-2°)
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EXAMPLE: HAADF-STEM TOMOGRAPHY OF A FLASH-MEMORY CELL
(C. KUBEL ET AL., MICROSC. MICROANAL. 11, 378–400, 2005)
0° HAADF-STEM projection
(contrast inverted)Segmented volume Slice through the reconstruction
Need for spectroscopic modes!
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As Ga
Fe3+
Fe2+
EDX: Energy-dispersive X-ray spectroscopy
EELS: Electron energy loss spectroscopy
SrHAADF-STEM
O
Ti
Atomic chemical mapping of SrTiO3.
Oxidation states in iron oxide nanoparticles.
Atomic chemical mapping of GaAs.Super-X EDX system with 4
detectors
(Fast STEM-EELS: 1000sp/sec)
Spectrum image
Spectrum image
SPECTROSCOPIC MODES
Simultaneous EELS / EDS map of a FinFET (P.
Longo et al., Materials Science in Semiconductor
Processing 65 (2017))
FEI application note
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Titan Ultimate
80-300kV
Image- and probe-corrected
Dual-EELS capabilities
Monochromated source
Titan THEMIS
80-200kV
Probe-corrected
Dual-EELS capabilities
Super-X system with 4
EDX detectors
Simultaneous EELS/EDX
E1 E2 E3 E4 E5
E1 E2 E3 E4 E5
Hyperspectral analysis
Tilt angle (e.g. -90°:10°:90°)
Tilt angle
Reconstruction
(2)
(3)
(1)
(1): stack of hyperspectral datacubes
(2): stacks of elemental maps or chemical phases
(3): 3D reconstruction for each stack.
Tilt angle
ANALYTICAL ELECTRON TOMOGRAPHY
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Issues!
• Electron tomography requires a large number of projections
• Spectroscopic modes require long exposure times and high electron doses (+manual acquisition)
200kV, GL 1.5, Spot size 3, C2 aperture: 30um,
cam. Length: 32mm, probe current: 120pA.
HAADF-STEM: 1024x1024 pixels, pixel size:
0.53nm, frame time: 16.7sec.
STEM-EELS: 100x75 pixels, pixel size: 2.04nm,
dispersion 1eV/ch, SI acquisition time: 18min.
Compromise
• Reduction of the number of projections + advanced alignment and reconstruction algorithms
• Reduction of acquisition time for spectrum images + Multivariate statistical analysis methods
• (Subsampled scanning acquisition + recovery using inpainting techniques)
Projection-Slice Theorem Example of acquisition parameters
CHALLENGES RELATED TO ANALYTICAL ET
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Issues!
• Electron tomography requires a large number of projections
• Spectroscopic modes require long exposure times and high electron doses (+manual acquisition)
200kV, GL 1.5, Spot size 3, C2 aperture: 30um,
cam. Length: 32mm, probe current: 120pA.
HAADF-STEM: 1024x1024 pixels, pixel size:
0.53nm, frame time: 16.7sec.
STEM-EELS: 100x75 pixels, pixel size: 2.04nm,
dispersion 1eV/ch, SI acquisition time: 18min.
Compromise
• Reduction of the number of projections + advanced alignment and reconstruction algorithms
• Reduction of acquisition time for spectrum images + Multivariate statistical analysis methods
• (Subsampled scanning acquisition + recovery using inpainting techniques)
Projection-Slice Theorem Example of acquisition parameters
CHALLENGES RELATED TO ANALYTICAL ET
| 11T. Printemps et al., Ultramicroscopy 160 (2016) 23–34
3-step alignment:
• Cross-correlation between neighboring
projections
• Common line algorithm to get a precise
shift correction in the direction of the tilt
axis.
• Intermediate reconstructions to
precisely determine the tilt axis and
shift correction in the direction
perpendicular to that axis
GUIDAR (GRAPHICAL USER INTERFACE FOR DENOISING ALIGNMENT AND
RECONSTRUCTION)
| 12T. Printemps et al., Ultramicroscopy 160 (2016) 23–34
GUIDAR (GRAPHICAL USER INTERFACE FOR DENOISING ALIGNMENT AND
RECONSTRUCTION)
| 13T. Printemps et al., Ultramicroscopy 160 (2016) 23–34
GUIDAR (GRAPHICAL USER INTERFACE FOR DENOISING ALIGNMENT AND
RECONSTRUCTION)
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Astra toolbox (J. Batenburg)
Compared to commercial packages:- Fast and fully automated
- Optimized for needle-shaped samples
- Works well on datasets with large tilt
increments (5-10°)
T. Printemps et al., Ultramicroscopy 160 (2016) 23–34
GUIDAR (GRAPHICAL USER INTERFACE FOR DENOISING ALIGNMENT AND
RECONSTRUCTION)
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HAADF-STEM ELECTRON TOMOGRAPHY - APPLICATION TO AN EMBEDDED MULTILAYER FIN
30 at. % of Ge in thecenter of the SiGelayers, 50 at. % on thesides
Ge composition map (EDS-STEM)
SiO2
Si
SiGe
• Reference measurements on blanket multilayer :
• RAMAN : ~ 31 at.%
• EDS, Si-K and Ge-L lines, Ge of ~ 28 % at. • EDS, Si-K and Ge-K lines, Ge of ~ 30 % at.
Embedded Multilayer Fins
FIB needle shaped specimen
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Tilt series Aligned tilt series 3D reconstruction (SIRT)
SiGe
Si
SiO2
Acquisition parameters:
• 30 projections from -90° to +90°
• Frame size: 2048x2048 pixels
• Frame time: 20sec
• Pixel size: 133pm
HAADF-STEM ELECTRON TOMOGRAPHY - APPLICATION TO AN EMBEDDED MULTILAYER FIN
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TV
SIRT
Δθ = 5°(27 projections)
Δθ = 10°(13 projections)
Δθ = 15°(9 projections)
TV
SIRT
segmentation
Quantification
Z. Saghi et al., Nano Letters 2011, 11(11), 4666.
R. Leary et al., Ultramicroscopy 2013,131, 70.
TV
SIRT
SIRT: መ𝑓 = 𝑎𝑟𝑔min𝑓
ℝ𝑓 − 𝑝 22
TV: መ𝑓 = 𝑎𝑟𝑔min𝑓
λ 𝑓 𝑇𝑉 + ℝ𝑓− 𝑝 22
with: 𝑓 𝑇𝑉 = 𝛻𝑓 𝑑𝑥
COMPRESSED SENSING RECONSTRUCTION ALGORITHM
Michael Lustig,
http://www.eecs.berkeley.edu/~mlustig/
CS.html
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Issues!
• Electron tomography requires a large number of projections
• Spectroscopic modes require long exposure times and high electron doses (+manual
acquisition)
200kV, GL 1.5, Spot size 3, C2 aperture: 30um,
cam. Length: 32mm, probe current: 120pA.
HAADF-STEM: 1024x1024 pixels, pixel size:
0.53nm, frame time: 16.7sec.
STEM-EELS: 100x75 pixels, pixel size: 2.04nm,
dispersion 1eV/ch, SI acquisition time: 18min.
Compromise
• Reduction of the number of projections + advanced alignment and reconstruction algorithms
• Reduction of acquisition time for spectrum images + Multivariate statistical analysis methods
• (Subsampled scanning acquisition + recovery using inpainting techniques)
Projection-Slice Theorem Example of acquisition parameters
CHALLENGES RELATED TO ANALYTICAL ET
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MULTIVARIATE STATISTICAL ANALYSIS FOR EELS AND EDX
• Number of components estimation :
• Prior knowledge on the observed sample.
• Principal Components Analysis scree-plot.
• Endmembers estimation/extraction :
• Principal Components Analysis
• Independant Components AnalysisDe la Peña et al., Ultramicroscopy, 2011
• Hierarchical clusteringTorruela et al., Ultramicroscopy, 2018
• Bayesian Linear UnmixingDobigeon et Brun, Ultramicroscopy, 2012
• Non-negative Matrix FactorizationShiga et al., Ultramicroscopy, 2016
• Vertex Component AnalysisDobigeon et Brun, Ultramicroscopy, 2012
E1 E2 E3 E4 E5Tilt angle
N TiSpectral
unmixing
Energy axis (eV)
Inte
nsity
Energy axis (eV)
Identification of 3
chemical phases
Inte
nsity
TiAl3GaN TiNStudy of Ti- and Al-Rich
Contact Metallization for
AlGaN/GaN high electron
mobility transistors, T.
Printemps et al. (2017)
Ag nanocube localised
surface plasmon resonances
by STEM-EELS tomography.
Nicoletti et al. Nature 502
(2013) 80-84
NMF is an approach to decomposition
that assumes that the data and the
components are non-negative.
| 20
HAADF-STEM acquisition:
Tilt series: -90°:5°:+90°
Frame size: 2048x2048 pixels
Pixel size : 0.26nm
15sec frame time
EDS-STEM acquisition (using the Super-X system):
Tilt series: -90°:10°:+90°
Datacube size: 193x163x2048
Pixel size : 1nm
10min frame time
Titan THEMIS
80-200kV, probe-corrected
Dual-EELS capabilities
Super-X system with 4 EDX detectors.
Aim of the study
• Conformality of As implantation.
• Dopant depth profiling in 3D.
• Roughness of the sidewalls of
the structure.
Ionized
gaz
Pulsed DC Supply
+
-
-
-
-
-
-
-
- -
+
+
+
Plasma implantation
Collaboration with F. Mazen
HAADF-STEM AND EDX-STEM TOMOGRAPHY OF AS-DOPED SI FIN-SHAPED STRUCTURE
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HAADF-STEM AND EDX-STEM TOMOGRAPHY OF AS-DOPED SI FIN-SHAPED STRUCTURE
50 nm
3D surface roughness of
the left sidewall of the
structure
Mean cluster size: ~15nm3
RMS roughness: ~3nm
xy
HAADF-STEM tomography
(-90°:5°:+90°)
Collaboration with F. Mazen
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SiO2Si AsChemical phase
analysis by NMF
(3 components)
As
SiO2
Si
Si
SiO2
As
As
xy
Chemical phases present: Si, SiO2, As.
As implantation depth: ~20nm
Mean cluster size: ~20 nm3
xyDepth distance (nm)
Inte
ns
ity
(a.u
.)
Collaboration with F. Mazen
As
SIRT
TV
HAADF-STEM AND EDX-STEM TOMOGRAPHY OF AS-DOPED SI FIN-SHAPED STRUCTURE
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GE-RICH GE2SB2TE5 (GST) FOR PHASE CHANGE MEMORY (PCM) APPLICATIONS
TOP ELECTRODE
PCM
HEATERACTIVE
VOLUME
X
Y
Example of an industrial PCM device
From: Phase change materials: science and
applications, S. Raoux and M. Wuttig, Springer
Verlag, New York, 2009.
Current challenge: PCM memory
devices stability is challenged at high
temperature (automotive applications).
SET RESET
0 100 200 300 40010
-3
10-1
101
103
105
GST
GST+Ge30%
GST+Ge35%
GST+Ge40%
GST+Ge45%
GST+Ge Opt.
RE
SIS
TIV
ITY
[c
m]
TEMPERATURE [°C]
Ge-rich GSTTc~380°C
Ge2Sb2Te5
Tc~170°C
Increase of Ge at. %
Increase of crystallization temperature (Tc)Collaboration with V. Sousa, G. Navarro and M-C. Cyrille
| 24
Different grain size after annealing
can impact the programming
reliability of the PCM device
Large grains Finer crystalline
structure
SET operation (i.e. crystallization)
becomes more reliable thanks to a
finer crystalline structure:
→ A lower resistance is achieved
Ge-rich GST crystallisation Phase separation GST & Ge
GE-RICH GE2SB2TE5 (GST) FOR PHASE CHANGE MEMORY (PCM) APPLICATIONS
| 25
Capping
SiO2
SiN
GST /
Ge
HAADF-STEM AND STEM-EELS TOMOGRAPHY OF GE-RICH GST MATERIALS ANNEALED AT
450°C
Titan THEMIS
80-200kV, probe-corrected
Dual-EELS capabilities
Super-X system with 4 EDX detectors.
Acquisition parameters:
200kV, GL 1.5, Spot size 3, C2 aperture: 30um,
cam. Length: 32mm, probe current: 120pA, mag
160kx.
HAADF-STEM (-90°:5°:+90°): 1024x1024 pixels,
pixel size: 0.53nm, frame time: 16.7sec.
STEM-EELS (-90°:10°:+90°): 100x75 pixels, pixel
size: 2.04nm, exposure time: 0.1sec (450eV,
1eV/ch), SI acquisition time: 18min.Collaboration with V. Sousa, G. Navarro and M-C. Cyrille
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1
2
3
4
0 . 0 5 µ m50 nm
<
1
2
3
4
N K-edge: 401eV
Sb M4,5-edge: 528 eV
O K-edge: 532 eV
Te M4,5-edge: 572 eV
Ge L2,3-edge: 1217 eV
Si K-edge: 1839 eV
600 800 1000 1200 1400 1600
2000
4000
6000
8000
10000
12000
14000
16000
18000
Inte
nsity
(a.u
.)
eV
GST
Ge
0
Chemical phase
analysis by VCA
(6 components)
Collaboration with V. Sousa, G. Navarro and M-C. Cyrille
HAADF-STEM AND STEM-EELS TOMOGRAPHY OF GE-RICH GST MATERIALS ANNEALED AT
450°C
| 27
GSTGe
xyxz xzxy
Cross-correlation alignment
SIRT reconstruction
Collaboration with V. Sousa, G. Navarro and M-C. Cyrille
HAADF-STEM AND STEM-EELS TOMOGRAPHY OF GE-RICH GST MATERIALS ANNEALED AT
450°C
| 28
WAVELET-BASED COMPRESSED SENSING ALGORITHM
SIRT: መ𝑓 = 𝑎𝑟𝑔min𝑓
ℝ𝑓 − 𝑝 22
TV minimization: መ𝑓 = 𝑎𝑟𝑔min𝑓
λ 𝑓 𝑇𝑉 + ℝ𝑓− 𝑝 22 , with: 𝑓 𝑇𝑉 = 𝛻𝑓 𝑑𝑥
Wavelet-based CS: መ𝑓 = 𝑎𝑟𝑔min𝑓
λ Ψ𝑓 1 + ℝ𝑓− 𝑝 22
Collaboration with Neurospin, CEA Saclay.
HAADF-STEM tilt series Ge (blue) and GST (red) tilt series
isotropic anisotropic
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• HAADF-STEM electron tomography: ok for 3D morphological analysis but we want more.
• “Dopant” diffusion & activation studied by analytical ET.
• Analytical ET now possible with recent developments in spectral analysis and reconstruction algorithms.
• Even if EDS & EELS are now sensitive enough to detect “dopant” in 3D structures, quantification with
standard methods & low SNR remains challenging.
Perspectives
• MSA techniques for low dose EDX and EELS
• EDX & EELS quantification in 2D & 3D
• Correlation with other techniques (APT, SIMS…)
SUMMARY ON ANALYTICAL ET
| 30
APT holderET holder
2 mm
Sup
po
rt t
ipA
nal
ysis
vo
lum
e
CORRELATIVE ET/APT
Same sample is prepared by FIB and mounted onto ET and APT holders
2 µm 2 µm
2
µm
Devices to be
analysed2 µm 200 nm 200 nm
| 31
ATOM PROBE TOMOGRAPHY BASICS
P O
R
Xtip, Ytip Xdet, Ydet
L (L≫R)(m+1) R
Magnification (lateral scaling): M= 𝐿
𝑚+1 𝑅
depends on – unknown - radius evolution during analysis.
Depth is calculated from sequence: zi = zi-1+dzi with dzi = 𝑉i.𝑀
2
𝑄𝑑𝑒𝑡.𝑆D
(𝑄𝑑𝑒𝑡 : detector efficiency, 𝑆D : detected surface, 𝑉i: applied voltage)
Radius parameter is estimated typically either from:
o Applied voltage 𝑅 𝑧 =𝑉 𝑧
𝐸.β
(E: evaporation electric field, β: instrument’ field factor)
o Tip cone shank angle α
o Tip profile, e.g. measured from TEM image
APT reconstruction basics
R
α
Time Of Flight measure Continuous voltage +
electric or laser impulsion
(V ≈ 3-15 kV, T ≈ 20-80 K, E> 10 V/nm)
APT acquisition
3D spatial
atom locationsTOF mass spectrometer Detector impacts
APT
reconstruction
| 32
APT RECONSTRUCTION ARTEFACTS
Local magnification effects
Presence of two phases
Local radius variation
with different fields of evaporation
Inhomogeneous distribution of the electrostatics field Preferential evaporation phenomena
L
(m+1).R M =
V
β.E R =
Ion trajectory aberrations
Si
STEM HAADF
SiO2
50 nmESiO2 = 1,25 ESi
Si
ETiN = 1,15 ESi
EHfO2 = 1,45 ESi
Si
TiN
HfO2
B. Gault et al.
Si
TiN
HfO2
20 nm
Density
correction
Reconstructions is less distorted -> is the quantification reliable?
Heterogenous structures with non-uniform
evaporation lead to:
- variable local magnification
- distortions of reconstructed volume
- abnormal atom density variations
- species crossovers.
D. J. Larson et al.
| 33
10 nm 50 nm
Si
SiO2
3D electron tomography
reconstruction of the 45 nm
device after segmentation.
3D APT reconstruction of the
45 nm device
Density corrected algorithm
+
3D boron distribution
inside the gate with
minimal distortions.
Si
SiO2
B
O
Si
B
CORRELATIVE ET/APT RESULTS
Improvement of APT reconstruction using the combination of electron tomography results with
density corrected APT algorithm.
A.Grenier, S. Duguay, F. Vurpillot et al, APL, 106, 213202 (2015)
| 34
Comparison between the reconstructions of GaN/InGaN/AlGaN multilayers obtained
from (a) the standard method and (b) the two-step, interface-flatness driven, process.
ATOM PROBE TOMOGRAPHY – ARTEFACT CORRECTION BY AN INTERFACE-FLATNESS
PROCESS
F. Vurpillot et al., Ultramicroscopy 132 (2013), 19.
| 35
ATOM PROBE TOMOGRAPHY – CORRELATION BY RIGID BODY TRANSFORMATION
The reconstruction algorithm uses the initial tip
radius (R0) and shank angle (α), which is the angle
between a tip axis and a tip surface. Image
compression factor and detection efficiency are
considered to have a constant value of 1.6 and 62%
respectively
I. Mouton et al., Ultramicroscopy 182 (2017), 112.
| 36
Indium
concentration
Low Indium
3D iso
STEM HAADF
Low Indium reference 3D volume
(reconstructed from 2D TEM image)
Affine registration
ATOM PROBE TOMOGRAPHY – CORRELATION BY NON-RIGID BODY TRANSFORMATION (AVIZO)
Non-rigid registration
EDX/EELS-STEM
tomography?
| 37
Phase Separation in an Alnico 8 Alloy.
Guo et al., Microsc. Microanal. 22, 1251 (2016)
EDX-STEM
tomographyAPT EDX-STEM
tomographyAPT
Nanomagnetic properties of the meteorite cloudy zone.
J.F. Einsle et al., PNAS 49, 115 (2018)
Ni
Fe
ATOM PROBE TOMOGRAPHY AND EDX-STEM TOMOGRAPHY
| 38
ATOM PROBE TOMOGRAPHY AND EDX/EELS-STEM TOMOGRAPHY
Future trends:
- Correction of distortions in the APT volumes, by using the AET
volumes as prior knowledge.
- Combination of large field-of-view AET volumes with APT sub-
volumes (small precipitates resolved, and low concentration
dopants detected).
- Use of APT reconstruction to validate the quantification
methods developed by the AET community.
EELS/EDX-STEM tomography:
Non-destructive, large fields of view, high spatial fidelity,
limited spatial resolution (few nms), LLD ~1×1020 at.cm-3,
quantification methods not fully developped.
APT:
Destructive, small fields of view, limited spatial fidelity, high
spatial resolution, LLD ~5×1018 at.cm-3, quantitative method.
| 39
Thank you for your attent ion!