Analytical Capabilities of a Pulsed RF Glow Discharge Plasma Source with GD-OES

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Versão do seminário apresentado por Celia Olivero (Horiba) na seção UCS do Instituto Nacional de Engenharia de Superfícies no dia 28 de junho para um público de 18 estudantes, professores e …

Versão do seminário apresentado por Celia Olivero (Horiba) na seção UCS do Instituto Nacional de Engenharia de Superfícies no dia 28 de junho para um público de 18 estudantes, professores e profissionais de empresas.

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  • (終了画面)
  • We will today mainly present some results in different fields
  • Brief principle of the technique (identical to a Ne light tube)
  • View of the HJY lamp and of a crater. The 2 electrodes are totally disymetric. This is responsible of the creation on the sample surface (conductive or non) of a constant negative voltage, the DC bias (Vdc). This DC bias voltage accelerates the Ar ions which sputters the sample surface. The sputtering is very fast and the unique double pumping system permits to get flat and deep craters. The depth resolution is sample dependant but has been shown to be as good as 1-2 nm and the maximum depth attainable in one shot can be more than 150 microns.
  • The design principle of GD has also no much changed since its introduction by Dr Grimm in the 70’s. The sample is usually placed on the o’ring sealing the chamber and is one of the electrode. It faces a Cu tube that is the other electrode. The operation is not that different from a lamp used for lightning. A low pressure gas is flushed in the chamber. When the RF power is switched on an electrical plasma is set up. This plasma assures both the sputtering of the sample and the excitation of the sputtered species. In GD we have a spatial separation of the erosion at the sample surface and the excitation in the gas phase and so (in first approximation) a dissociation of the 2 phenomena that allows multimatrix calibrations and depth profile quantification.
  • Benefits of the RF source. Better for surface (often oxidized so partly non conductive) and allowing simpler calibrations
  • Pulse permits to do fragile samples and to get better depth resolution
  • The instrument is essentially a polychromator for the simultaneous measurement of all elements (in depth profile we need a simultaneous measurement).An additional monochromator can be added for flexibility.
  • Polyscan is limited. Not simultaneous, same resolution as poly, limited spectral range. Mono is better. The addition of a monochromator in the instruments provides a superior flexibility. The mono permits to measure any N+1 element simultaneously in a depth profile The mono has the highest resolution The mono also permits (if the sample is homogeneous) to run a full spectrum measurement (Image)
  • The GD instrument is first an optical spectrometer and that commands for the largest part the obtainable results due to the spectral range covered, the resolution you can achieve and as the GD source is not a very intense source of light, the grating quality that mainly commands light throughput of the instrument. We have 2 types of GD instruments, the GD-Profiler 2 shown here and the GD-Profiler HR. They differentiate by the different focal length of their optics.
  • This is to explain the differences between the bulk analysis and the Depth Profile Analysis (named QDP: Quantitative Depth Profile). Bulk analysis: Analysis of a metal piece…, sputtering to remove contamination, analysis time: several seconds Results: Chemical composition of the sample Depth profiling: Substrate with different layers or surface treatments, Sputtering through the different layers, no pre-integration time, very fast acquisition rate up to 2000 acquisition/second. A lot of points of measurements from the surface until the matrix Results: plot of chemical composition of the sample for all elements simultaneously versus the depth (from the surface to the substrate)
  • Quick summary
  • To summarize, these are the general questions GD can bring a piece of information
  • If we look now to the depth profile of a more industrial multi layers sample, here an alternance of TiN and TiAln deposited on a stainless steel, we can sse the degradation of the depth resolution with the depth due to large change of sputtering rate between the materias and the roughness effect (I will come back on this issue later).
  • Samples here are various steels, Ti, Ni and carbides. Coatings can also be used within multimatrices calibrations.
  • We will today mainly present some results in different fields
  • Help for industry and for research : an example in the paper from Prof. Alvarez
  • An other example showing a benefit of Rf GD-OES, the ability to measure O, N and Cl, H not shown on the slide. This allows to follow all sorts of surface treatments and indicates why the technique is precious for corrosion studies.
  • Classical applications where GD has a lot to bring. Control of treatments. Quick comparisons of samples. Very popular in Iran
  • This is an overlap of both profiles: Good and bad process showing clearly the different behavior of the N and C, and the influence of the process on the treatment.
  • Full range of applications
  • Now some examples coming from EU projects. GD can be used to follow ionic implantation
  • European project about C3N4 coating. Realisation of layers harder than diamond.
  • Let us now focus on thin layers This result has been presented in Spain at AIN by the customer. The sample has 107 layers deposited (CrN, TiN) on steel. The diagram shows the result of 2 quantified measurements performed on the same sample. The depth resolution and the repeatability are clearly revealed by this example. Of course the depth resolution degrades with the depth due to preferential sputtering, induced roughness etc but it remains pretty good.
  • Now back to flat samples and real thin layers Lot of work done on such thin films. Anodised Al Consider next another coated sample. This one is prepared by anodising a polished Al substrate in various solutions. The result is an Al substrate, then a 240 nm thick Al2O3 layer, followed by a 120 nm outer AlOx layer containing about 3% B, and a Cr spike about 2 nm thick at 40 nm from the outer surface. Just in front of the Cr spike is a region with bubbles.
  • Let us see an example illustrating the benefits of RF GD-OES. As we have seen the instrument is capable to sputter microns/minute (hundreds of nm per second) but as optical signals can be recorded fast this speed of analysis is not an handicap for the depth resolution. Here is shown a thin anodised layer. Anodisation was done in acid pH, the anodisation is porous and a delta layer (Cr) a few nm thick was deposited at the bottom of the pores (See the TEM view).
  • This sample has been used to compare RF GD and SIMS. The depth resolution was similar with the 2 techniques and of course the time of analysis is without comparison. Such an approach certainly changes the way people appreciate surface analysis. It is now possible to quickly run multiple samples assuring nearly immediate feedback.
  • Yes we can do surface !! Surface contamination can be important to check and monitor when it can be linked to the process. An example illustrating that point is given here. It comes from the electronic industry and shows the capability of RF GD for ultra thin films analysis. Customer is producing ultra pure Cu, base to electronic circuit boards. The first result shows the top surface (less than 1s of sputtering) of a good sample, the second one is from problematic sample: contamination is obvious and coming from the rinsing water used.
  • This result was presented in 2004 in JAAS. The sample is a monolayer of thiourea deposited on electropolished Cu. The layer is sputtered in 20ms but the distribution of species precisely follow the structure of the molecule.
  • To be sure of the previous result a second molecule parallel to the surface was deposited and immediately measured
  • An other important aspect is the control of the source. Our source can operate in continuous mode or in pulsed mode. Source can be pulsed at ms frequency (from 33Hz up to several kHz). This example is on an other type of coated glass and shows the potential benefits of the pulse mode. Without pulsing (left), even with a low power some crack may happen, with the pulse mode (with high power sent in each pulse – but a resulting power average equivalent to the first case) we obviously have less problems. The synchronised acquisition allows to record signals only during the time the source is on improving signal/background ratio.
  • With pulse glasses can be done easily without damage (here a thick glass and deep crater)
  • Use of pulsed in PV. For Na. Here an other glass with coatings : pulse : no diffusion of Na !!
  • Example of CIGS
  • Other benefit of this pulsed mode is the reduction of the sputtering rate and the minimization of surface damages while keeping interesting information. Reducing the fast SR of GD is often asked: usually the only way to do it is to reduce the applied power (hence limiting the sensitivity). The pulsed operation provides enough power for excitation while reducing the SR. It is also a useful approach to identify details on the surface and it minimizes sample heating and damage.
  • We will today mainly present some results in different fields
  • We have seen that RF GD has a very fast sputtering, it is also a very soft one – when compared to SIMS for instances. This is due to the plasma characteristics. The possibility to obtain a very fast erosion due to the high density of the plasma but a soft one due to the relatively low energy of the incident particles is at the origin of a new application: to use the RF GD as a cleaning system tool and a sample preparation technique for SEM.
  • The example here shows a stainless steel sample, mirror polished and a part of the GD spot inside. The preferential sputtering, usually a drawback, is here turned into an advantage and used to clearly reveal the structure of the sample beneath the surface.
  • Let us see now a couple of slides showing some SEM views after mechanical polishing and RF GD operation.
  • We will today mainly present some results in different fields
  • Now some figures of merits comparing rf GD to classical surface techniques as a possible conclusion.
  • The capability of GD to characterize quickly multilayers at the nm scale make it an interesting tool in many fields.
  • GD operates directly from the sample surface, SEM requires a cross section. Very often in a lab the 2 techniques are used complementarily: can we go further and have the 2 domains more closely together: may be !
  • Finally I would like to mention 2 recent books released on GD where valuable information can be found. Thanks for your attention.
  • (終了画面)

Transcript

  • 1. Analytical Capabilities of a Pulsed RF Glow Discharge Plasma Source with GD-OES Celia OLIVERO Applications GD-OES lab manager Celia.olivero@horiba.com Horiba Jobin Yvon 16-18 rue du canal 91165 Longjumeau Cedex, France© 2012 HORIBA Scientific. All rights reserved.
  • 2. © 2012 HORIBA Jobin Yvon. All rights reserved.© 2012 HORIBA Scientific. All rights reserved.
  • 3. Introduction to the Technique© 2012 HORIBA Scientific. All rights reserved.
  • 4. History and Context  The analytical Glow Discharge Optical Emission Spectrometry was invented in Europe by researchers from the Steel Industry  For many years it has been primarily applied to the metal industry  The developments made in the last 12 years (RF, pulsed RF, pulsed RF with automatic matching) have drastically changed the situation  Pulsed RF GD-OES is now a flexible tool for thin and thick films analysis of conductive/non conductive materials  In parallel the EU project coordinated by HJY (www.emdpa.eu) has led to the development of the Plasma Profiling TOFMS™ that couples the same pulsed RF plasma source to a Time of Flight Mass Spectrometer and offers complementary possibilities  We will present today the analytical capabilities of GD-OES© 2012 HORIBA Scientific. All rights reserved.
  • 5. GD: Principle of Glow Discharge  When the voltage  Low pressure gas increases the cell begins to glow and the  2 electrodes cathode is sputtered.  Power supply  The glow is not uniform.  Physical separation of sputtering (near cathode) and excitation zone (near anode)© 2012 HORIBA Scientific. All rights reserved.
  • 6. View of the HJY GD « source » External sample mounting Sample is the cathode Pulsed RF power: Conductive and non conductive materials Control of crater shape: atomic layer by atomic layer© 2012 HORIBA Scientific. All rights reserved.
  • 7. Source Design principle windo w vacuum Ar λ 4mm crater Anode Vacuum R Sample F Cooling© 2012 HORIBA Scientific. All rights reserved.
  • 8. Pulsed RF source  Both conductive and non conductive samples and layers  Stable signals from the start: Surface! analysis  Simple: one source optimized  One calibration for composites (bulk and layered samples, conductive and non) 0.9 0.8 0.7 0.6 P 0.5 S Si 0.4 Ni Cr 0.3 0.2 0.1 0.0 2 5 2 2 9 1 :25 :01 :28 :54 :0 :2 :0 :3 :4 :5 09 09 11 11 14 08 10 10 11 13© 2012 HORIBA Scientific. All rights reserved.
  • 9. Pulsed RF: details RF Pulsed Source -Short duration (30 μs to 1 ms) - Various repetition rates (duty cycles) - Possibility to use high instantaneous powers (> 60 W) for sensitivity -Possibility to use soft conditions for plasma cleaning - Ph. Belenguer, et al. Spectrochim. Acta B 64, 7 (2009) 623-641.Main Advantages for OES: Example: PVD deposition of- Low average power magnetic layer on PET(analysis of heat-sensitivematerials)- Tunable (Slower) sputteringrate- Control on the crater shape- Improved depth resolution© 2012 HORIBA Scientific. All rights reserved.
  • 10. Light Collection and Simultaneous analysis(polychromator) High Dynamic Detector Rowland circle Secondary slit Sample Lens Grating Primary slit Spectrometer Source © 2012 HORIBA Scientific. All rights reserved.
  • 11. Flexibility of the monochromator  N+1 element in depth profile  Measurement of additional elements for bulk  Spectrum acquisition© 2012 HORIBA Scientific. All rights reserved.
  • 12. Monochromator: spectrum of a sample andcomparison to libraries © 2012 HORIBA Scientific. All rights reserved.
  • 13. HJY GD-OES: GD-Profiler2 Sample position Spectral range from H 121nm to K 766nm All elements of periodic table© 2012 HORIBA Scientific. All rights reserved.
  • 14. Targets of materials characterization Bulk Analysis Depth Profiling Fe Weight % Cr Ni Px5 N Cr Depth (Micrometers)© 2012 HORIBA Scientific. All rights reserved.
  • 15. Main features Characteristics of pulsed RF GD-OES instruments  All elements of periodic table  Fast sputtering (15-150nm/s)  Depth Profile and Bulk  Thin and thick films  Atomic information  No isotopic information except for deuterium  Excellent depth resolution© 2012 HORIBA Scientific. All rights reserved.
  • 16. What materials?  Conductive and non conductive  Solid materials (resistant to few bars locally)  Bulk  Coated: single or multi  Flat on analysis surface (curved surface possible with special accessory use)  Min size: > 3mm  Typical analysis surface: over 4mm diameter© 2012 HORIBA Scientific. All rights reserved.
  • 17. What Questions are answered by rf GDS?  What elements are present in the sample?  At what concentration levels?  Is the sample homogeneous in depth?  Were any coatings or surface treatments applied to the sample?  Where is this surface defect coming from?  How many coatings have been applied?  How thick are the coatings? What is the coating weight?  What are the competitors doing ?  Is there any contamination at the interface?  Any oxidation or corrosion of the sample? How this material reacts to corrosion?  Any diffusion in the coatings?  GD will tell within seconds to minutes !© 2012 HORIBA Scientific. All rights reserved.
  • 18. Typical result:Complex multilayer coating (quali) Distribution of the elements as function of time (depth) => qualitative Multilayer TiN/TiAlN on Stainless steel © 2012 HORIBA Scientific. All rights reserved.
  • 19. Same quantified (in At%) © 2012 HORIBA Scientific. All rights reserved.
  • 20. Quantification basis  GD is a comparative technique.  Calibration needed.  Calibration in GD can be done using a multimatrix approach correcting for Sputtering Rate.  The GD sputtering efficiency is sample dependant.  Depth Profile: Sputtering rate usually changes with the depth.© 2012 HORIBA Scientific. All rights reserved.
  • 21. Quantification: Simple ci q M = k i I i where The measured intensity for a – ci composition given element is – qM sputtering rate proportional to its concentration in – Ii intensity the plasma – ki constant© 2012 HORIBA Scientific. All rights reserved.
  • 22. Sputter Rate Correction Multimatrices Calibration for Cr Aluminum Base SR 0.1 Iron / Steel Bases SR 0.4 Sputter Rate Concentration % Zinc Base SR 1.2 Lead Base SR 2.0 10% Cr IAl IFe IZn IPb Light Intensity© 2012 HORIBA Scientific. All rights reserved.
  • 23. Sputter Rate Correction Multimatrices Calibration for Cr Aluminum Base Which Concentration of Cr should give SR 0.1 Iron / Steel Bases the same light in a material having a SR 0.4 SR = 1? Concentration % Virtual Base SR 1 Apply Sputter Rate Correction to this point Zinc Base SR 1.2 Conc. X SR Lead Base SR 2.0 10% Cr IAl IFe IZn IPb Light Intensity© 2012 HORIBA Scientific. All rights reserved.
  • 24. Sputter Rate Correction Multimatrices Calibration for Cr SR X Only ONEof Unknown Sample Analysis Cr Calibration Curve Concentration % Valid for Multimatrices Virtual Base SR 1Virtual CrConcentration Light Intensity IX © 2012 HORIBA Scientific. All rights reserved.
  • 25. Sputter Rate Correction Analysis of Unknown Sample Fe Cr Ni Mn VirtualVirtual Cr % Virtual Virtual Fe % Ni % Mn % I Fe I Cr I Ni I Mn Virtual Concentration Fe . SR 50 % Fe . SR + Cr . SR + Ni . SR + Mn . SR = 75 % Cr . SR 10 % Ni . SR 10 % All the elements within the unknown Mn . SR 5 % sample have the SAME SR Total (Conc. X SR) = 75 % Real Concentration (Fe + Cr + Ni + Mn) . SR = 75 % Fe = 50 % / 0.75 = 66.67 % SR = 75 % / (Fe + Cr + Ni + Mn) Cr = 10 % / 0.75 = 13.33 % Ni = 10 % / 0.75 = 13.33 % Sum of Concentration = 100 % Mn = 5 % / 0.75 = 6.67 % Sum Normalization Total (True Conc.) = 100 % SR = 75 / 100 = 0.75 © 2012 HORIBA Scientific. All rights reserved.
  • 26. Illustration: Calibration for bulk. Mo in stainless steels with 2mm anode © 2012 HORIBA Scientific. All rights reserved.
  • 27. Calibration for depth profiling.Multimatrix calibration © 2012 HORIBA Scientific. All rights reserved.
  • 28. Applications© 2012 HORIBA Scientific. All rights reserved.
  • 29. Bulk: precious metal samples with GD spots Control of Product quality © 2012 HORIBA Scientific. All rights reserved.
  • 30. Bulk: precious metal LOD© 2012 HORIBA Scientific. All rights reserved.
  • 31. Some applications in automotive Application Description Base metals Chemical composition of all metals and alloys (Fe, Al, Zn, Mg ..) Li batteries Control of electrodes Ceramic coatings Engine antiwear coatings * Zn coatings All Zn coatings can be characterised (ISO norm) Thermal treatments Nitruration, etc Organic coatings (Bonazinc Composition and behaviour of the coatings * etc) Phosphatations Control of phosphatations DLC coatings Hard coatings used for instances in Formula 1 Corrosion studies Identification of defects, studies of new processes * Cataphoresis Control of cataphoresis bathes and coatings * Glasses UV protection coatings on glasses * Benchmarking Comparative study of all parts of competitive cars * Plastics Coatings on plastics * Electronic parts Control of suppliers, defects Painted car bodies In depth analysis of a car body down to 200 microns * * indicates presence of non conductive layers. They count for more than 50% of the work done in an automotive laboratory.© 2012 HORIBA Scientific. All rights reserved.
  • 32. GD : Help for industry and for research  Selection of right material for application  Control of preadjustment of surface before process  Selection and control of right nitriding parameters  GD complementary to other surface techniques  Speed of analysis is crucial for multiparametric research © 2012 HORIBA Scientific. All rights reserved.
  • 33. Thick coatings:Thermal treatment on steel © 2012 HORIBA Scientific. All rights reserved.
  • 34. Depth Profile: Carbonizing and nitriding steel 100 80 Fe Carbonizing Concentration / at% and nitriding 60 40 C(× 3) Ni Steel 20 N(× 2) 0 1 2 3 Depth / um © 2012 HORIBA Scientific. All rights reserved.
  • 35. Nitro-carburizing Overlay Good / Bad Process N Weight % Fe Fe Fe Bad N N C N x 10 Good C x 10 Fe N N C N C C Depth (Micrometers)© 2012 HORIBA Scientific. All rights reserved.
  • 36. Paint on car (1)© 2012 HORIBA Scientific. All rights reserved.
  • 37. Paint (zoom)© 2012 HORIBA Scientific. All rights reserved.
  • 38. Paint quantified© 2012 HORIBA Scientific. All rights reserved.
  • 39. Applications: typical interests in coated material Composition Composition (%) 100 40 60 80 20 0 Protective coating 0.0 Native oxide (few nm) 10-100 nm 0.5 Corrosion protection Tribological improvement 1.0 Depth Depth µm) 1.5 Complex coating ( 2.0 Structure: Multilayer, Gradient,.. 10-1000 nm Elemental Composition 2.5 Interface details 3.0 Layer Intermixing Compound formation 3.5 100 nm Intermediate layer Adhesion improvement Element Inter-diffusion Substrate protection 1 mm Substrate Element Inter-diffusion39 © 2012 HORIBA Scientific. All rights reserved.
  • 40. Ionic implantation Implanted sample Disorganized region Crystaline region “Oxide” Atoms implanted Metallic atoms Courtesy of AIN Spain© 2012 HORIBA Scientific. All rights reserved.
  • 41. Successive implantation of C and N 100 90 80 Fe 70 N 60 % At 50 40 C 30 Cr 20 10 0 0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 Profundidad (µm) Courtesy of AIN Spain © 2012 HORIBA Scientific. All rights reserved.
  • 42. Thin layers. PVD coating. 107 layers 20nm CrN/TiNOverlap of 2 measurements © 2012 HORIBA Scientific. All rights reserved.
  • 43. Multilayers: depth resolution issue  Mirror for X ray Alternance Mo/B4C/Si 60 periods 60 periods Each layer (Mo or Si) is Substrate 6.97nm thick Sample used for a RR experiment prepared by Prof. Tolstoguzov on depth resolution (by SIMS mainly). OES results presented at the SIMS 2011 conference© 2012 HORIBA Scientific. All rights reserved.
  • 44. Qualitative profile© 2012 HORIBA Scientific. All rights reserved.
  • 45. Zoom on qualitative profile© 2012 HORIBA Scientific. All rights reserved.
  • 46. Example on thin Anodised Al (nm) 120 3% B Cr 240 bubbles Al substrate© 2012 HORIBA Scientific. All rights reserved.
  • 47. Speed of analysis 10 Cr 8 Note the Cr peak Al Intensity (V) 6 B 4 O O*7 2 H P Cu 0 0 5 10 15 Time (s) Thin anodised Al analysis© 2012 HORIBA Scientific. All rights reserved.
  • 48. Analysis Time issue (a) SIMS (b) GD-OES Vacuum time : Vacuum time: 1hour No Analysis time: Analysis time: 3 hours 15 seconds Total Time: 4 hours Surface of 150 nm Al2O3 film (with a Cr marker of ~ 2nm) formed on highly flat Al by anodic oxidation Analysis by (a) SIMS and (b) GD-OES. Shimizu et al. Spectrochimica Acta B 58 (2003) 1573-1583 48 /14© 2012 HORIBA Scientific. All rights reserved.
  • 49. Surface issue: Electrolytic Cu plate Surface contamination by rinsing water © 2012 HORIBA Scientific. All rights reserved.
  • 50. Rf GD for surface studies •Sample preparation Mirror-finished, high purity aluminium, electropolished in perchloric acid-ethanol bath, then rinsed. Post-electropolishing immersion treatment in a chromic acid- phosphoric acid solution to remove the thin Cl- doped surface film remaining after electropolishing. Finally, the specimen was rinsed in distilled water and warm air- dried. A new hydrated oxide surface, about 4 nm thick, is developed on the surface after the previous treatments. •Result description The rf GD-OES depth profile shows the oxide was hydrated throughout, in agreement with XPS studies. However, in addition, rf GD-OES shows copper enrichment in the aluminium just below the oxide.© 2012 HORIBA Scientific. All rights reserved.
  • 51. Sub nm resolution. Adsorbed molecule © 2012 HORIBA Scientific. All rights reserved.
  • 52. Sub nm resolution (BTA benzotriazole) © 2012 HORIBA Scientific. All rights reserved.
  • 53. Pulsed operation with synchronized acquisition RF RF 75 µs 40 WNo pulse 5 W Pulse time time 0.6 ms © 2012 HORIBA Scientific. All rights reserved.
  • 54. Cationic exchange Deep Craters in Thick Glass Over 80 µm, Flat Crater© 2012 HORIBA Scientific. All rights reserved.
  • 55. Coatings on Glass Repro: 2 measurements overlaid New pulsed RF source© 2012 HORIBA Scientific. All rights reserved.
  • 56. Importance of Pulsed Operation for Coatings on Glass Precise measurements of major and traces (for instances Na). No diffusion induced during measurement. © 2012 HORIBA Scientific. All rights reserved.
  • 57. CIGS: Quantified Depth Profile© 2012 HORIBA Scientific. All rights reserved.
  • 58. Lower sputtering rate in pulsed mode normal pulsed → Electric coating (CrO) on Steel : 100 nm. In pulse mode, a C peak in the CrO layer is detected. This peak is also seen in XPS.© 2012 HORIBA Scientific. All rights reserved.
  • 59. Double layer of polymers Follow up of C, H, molecular band CH and elements (here Cu)© 2012 HORIBA Scientific. All rights reserved.
  • 60. Thick Organic Layers Access to Embedded Interfaces Patent filed 105 µm organic layer sputtered in 12 min ! Flat crater No chemicals ! Applications: PV (measurement of encapsulated cells), DVD profiles…© 2012 HORIBA Scientific. All rights reserved.
  • 61. Coated polymer films: multilayered InOx/Ag © 2012 HORIBA Scientific. All rights reserved.
  • 62. GD as Cleaning tool© 2012 HORIBA Scientific. All rights reserved.
  • 63. Rf GD as sample preparation technique for microscopy  Plasma sputtering. Plasma density (1014cm-3)  Low energy of the Ar ions in GD : 50eV => nearly no surface damage  No surface charge with RF  No priviledged direction of the incident ions onto the surface  Use for SEM: no chemicals use  Turn preferential sputtering into an advantage© 2012 HORIBA Scientific. All rights reserved.
  • 64. SamplePreparation forSEM/TEM© 2012 HORIBA Scientific. All rights reserved.
  • 65. Stainless steel, mirror polishedSEM view : part of GD spot inside © 2012 HORIBA Scientific. All rights reserved.
  • 66. Zoom on crater bottom: constrasts shows all different phases© 2012 HORIBA Scientific. All rights reserved.
  • 67. GD-OES for EBSD (Electron Backscatter Diffraction) EBSD is an analysis technique that measures crystal information near sample surface (at the order of a few tens of nm). Therefore sample surface condition of the area of interest is a very important factor. A sample surface needs to be clean and flat to do EBSD analysis. Grain A Electron beam × No good EBSD result can be obtained from a insufficiently prepared sample surface Sample surface Grain B EBSP ○ Electron beam Sample surface Grain A Grain B EBSP© 2012 HORIBA Scientific. All rights reserved.
  • 68. Complementary technique© 2012 HORIBA Scientific. All rights reserved.
  • 69. © 2012 HORIBA Scientific. All rights reserved.
  • 70. © 2012 HORIBA Scientific. All rights reserved.
  • 71. GD and SEM 500 400 100% 100% 100% x% y% z% Intensity (V) X Cr Cr Y Ti Ti Z Cr Cr 300 200 0.5 µm 0.5 µm 0.5 µm 100 100% 0 Substrate Si 0 2 4 6 8 10 12 14 Si Sputtering time (s) Concentration (%) Quantification Depth (µm)© 2012 HORIBA Scientific. All rights reserved.
  • 72. Raman microanalysis within a GD crater Laser : λ = 514nm P=0,8mW CrIII peak Laser © 2012 HORIBA Scientific. All rights reserved.
  • 73. High temperature oxidesComparison SNMS/GD Courtesy FZJulich © 2012 HORIBA Scientific. All rights reserved.
  • 74. Recent researches conducted in GD OES  CIGS solar cells characterisation  Interactions plasma/surfaces  RF GD plasma characterisation through modelling and electrical measurements  Use of GD plasma for Scanning Electron Microscope  D analysis and control of H migration through D investigation in various high temperature oxides  Pulsed plasma nitriding control  Instrumentation development: RF coupling improvement on non conductors  Li batteries (special device developed)  Cr speciation with GD OES (ratios Cr/O)  Fuel Cells control  These researches have been done within phD thesis or are part of advanced works in major industries; They are not exhaustive but only here to give an idea of the variety of possible applications of GD.© 2012 HORIBA Scientific. All rights reserved.
  • 75. More info on GD Recent Books Marcus: “Glow Discharge Plasmas in Analytical Spectrometry” Wiley, November 2002 Nelis and Payling: “Practical Guide to Glow Discharge Optical Emission Spectroscopy” Royal Society of Chemistry, Cambridge, 2003 Web www.emdpa.eu www.glow-discharge.com© 2012 HORIBA Scientific. All rights reserved.
  • 76. Conclusions  Pulsed RF GD OES is an analytical technique with many potentials  Fast analysis : We will be pleased to run some samples for you free of charge under non disclosure agreement if required and evaluate the potential of the techique for your research  Large samples needed (about 2*2cm)  Complementarity to other techniques  Feel free to contact us  celia.olivero@horiba.com  patrick.chapon@horiba.com Contact in Brazil: Philippe.ayasse@horiba.com HORIBA Scientific HORIBA BRASIL Av. das Naçoes Unidas 21735 Jarubatuba 04795-100 Sao Paulo SP-Brasil Tel. +55 11 5545-1595 Fax +55 11 5545-1570 Mobile +55 11 9458 3205© 2012 HORIBA Scientific. All rights reserved.
  • 77. Thank you © 2012 HORIBA Jobin Yvon. All rights reserved.© 2012 HORIBA Scientific. All rights reserved.