CIM PACA Characterisation Lab Your partner of choice for the chemical characterisation of your materials Partners:
Who are we? The CIM PACA Characterisation Lab was registered in 2005 as a not-for-profit association under French Law. The lab is in the ROUSSET industrial park in the South of France. Members of the association include: major industrial companies (world-leading semiconductor manufacturers) small businesses (specialising in surface analysis, ion implantation, photovoltaic systems and testing & failure analysis for integrated circuits) Université Paul Cézanne, in its own capacity and as a representative of public research bodies in the Provence-Alpes-Côte d'azur region The activities of the lab are managed by an Operations Committee comprising the founding members of the association.
Why work with us? The CIM PACA Characterisation Lab is unique in Europe in offering a range of complementary expertise: in physico-chemical materials analysis and in failure analysis for issues relevant to a wide range of business fields (semiconductors, photovoltaic technologies, aerospace industry, etc.) The lab provides analytic support to help characterise and model processes and solve problems relating to faults and failures. State-of-the-art equipment is used and operated by experts. Our holistic approach looks at an issue in its full context, in order to provide a comprehensive solution The lab has been approved for French Research Tax Credits: which means that any R&D work is eligible for tax credits in France under this scheme
What we offer principally The CIM PACA Characterisation Lab offers comprehensive chemical characterisation service packages (with a detailed materials analysis report provided) It can meet most needs in this area using four complementary microanalysis techniques (see next page): D-SIMS ToF-SIMS Micro-XPS (ESCA) Nano-AES Contacts Vincent GOUBIER Operations Director Office line: +33 (0)4 42 68 51 60 Mobile: +33 (0)6 47 23 84 75 E-mail: vincent.goubier@caracterisation.org Catherine GROSJEAN Micro-analysis Expert Office line: +33 (0)4 42 68 86 08 E-mail: catherine.grosjean@caracterisation.org
Complementary nature of D-SIMS, ToF-SIMS, Micro-XPS and Nano-AES Analysis type Type of information provided Depth of analysis Possibility of using ion etching for profile? Type of output Detection limits D-SIMS ToF-SIMS Micro-XPS Nano-AES Elemental analysis Quantitative (using calibration sample) Depth distribution profile of a dopant From a few nm to several µm Yes (caesium, oxygen) Depth distribution profile From 1 ppm to 1 ppb (depending on the element) Molecular and elemental analysis Semi-quantitative (using reference) Molecular and elemental identification + Semi-quantification of ions whose mass is up to 15,000 amu 0.2 to 0.5nm A few hundred nm in profile mode Yes (caesium, oxygen) Microanalysis, chemical imaging, depth distribution profiles From 1 ppm to 1 ppb (depending on the element) Spatial resolution 10µm * 10µm 0.1µm Elemental analysis (all elements except H) Semi-quantitative Atomic composition of the surface + Relative proportion of the various chemical states of each element (degree of oxidation, etc.) 2 to 8nm A few hundred nm in profile mode Yes (argon) Microanalysis, chemical imaging, depth distribution profiles, angle-resolved analysis (non-destructive profile) over a few nm depth 1% atomic weight 3µm for imaging 10µm for microanalysis Elemental analysis Semi-quantitative Atomic composition of the surface + Identification of the chemical state of some elements (oxidised, metallic, etc.) 0.5 to 5nm A few hundred nm in profile mode Yes (argon) Microanalysis, line scan, chemical imaging, depth distribution profiles 0.5% to 1% atomic weight A few tens of nm (probe size 8nm) Chemical resolution High mass resolution (separates SiH from P) High mass resolution >10,000 Energy resolution 0.48 ev (FWHM Ag3d5/2) Energy resolution 2 ev (peak to peak) Charge neutralisation (for insulating materials) Possible Yes Yes Yes Sample size A few mm2 A few cm2 A few cm2 A few cm2 Destructive test? Yes No (if no profile done) No (if no profile done) No (if no profile done)
Possible applications With D-SIMS technique Semiconductor analysis (distribution of dopants, contaminants or majority elements in materials such as Si, poly-si, SiO2, SiON, ONO, FSG, BPSG, SOI, SiGeC, NiSi, SiC, MnGe, metal multilayers, etc.) Calibration of process simulators Characterisation of ultra-shallow junctions With ToF-SIMS technique Molecular and elemental surface analysis Parallel identification of all ions present (highly sensitive identification of unknown element) Determining the molecular structure of polymers Analysis of insulators and fragile materials (soft ionisation technique) Multilayer analysis (photovoltaic cells, telescope mirrors, etc.) Identification of interface contaminants in the event of delamination With Micro-XPS technique Analysis of surface chemicals and their states (passivation, cleaning residues, etc.) Analysis of insulators (no charging effects) Analysis of fragile materials (powders, etc.) Non-destructive test for thin films of less than 10nm thick With Nano-AES technique Pad analysis (analysis of surface and deep contamination) Characterisation of submicronic defects (particles, filaments, staining, etc.) Analysis of micro-sections prepared using FIB (no shadow effect through use of a coaxial analyser; FIB preparation available at the lab)
[atm/cm3] [atom/cm3] Examples of deliverables with D-SIMS [atom/cm3] 1.E+22 1.E+21 Cameca IMS 7F multi delta de bore dans Si 02+ energie d'impact 500eV, fuite à oxygène Illustration of the depth resolution quality of our equipment with boron multi-deltas (see opposite) 1.E+20 1.E+19 1.E+18 0 20 40 60 80 100 [nm] Calibration of process simulators: arsenic profiles superimposed with simulated profiles 1.E+22 1.E+21 1.E+20 1.E+19 1.E+18 As 3keV 1.4e15 atm/cm² in Si As profiles acquired with 2 different angles and Sentorus Process simulations As 68.5 As 45.6 TAURUS CTRIM ANALYTIC Ultra-shallow junctions: overlay of boron profiles, with and without annealing 1.E+23 1.E+22 1.E+21 1.E+20 1.E+19 1.E+18 1.E+17 Cameca IMS 7f, Overlay des profils Bore [B], Slot 1 [B], Slot 2 [B], Slot 3 [B], Slot 4 [B], Slot 5 [B], Slot 6 [B], Slot 7 [B], Slot 8 1.E+17 1.E+16 1.E+16 1.E+15 0 10 20 30 40 50 60 [nm] 1.E+15 0 100 200 300 400 500 [nm]
Examples of deliverables with ToF-SIMS Intensity [counts] Pad alu n ayant pas été en contact avec une bande adhésive Pad alu n ayant pas été en contact avec une bande adhésive Pad alu ayant été en contact avec l adhésif n R1 Pad alu ayant été en contact avec l adhésif n C1 Al Si C2H3 C3H5 C3H7O C2H5 C3H7 C4H9 CH3O C2H5O C4H7 C8H12N Comparative surface analysis of aluminium pads, some of which had been in contact with an adhesive tape the elemental and molecular analysis for masses between 10 and 100 highlights major differences (see opposite) Parallel depth profiles of various chemical species Pad alu ayant été en contact avec l adhésif n C2 Delamination of a ball bond Na, Cl, K and F found at the interface 5 10 4 10 Substance Mass Color Al 26.98 30Si 29.97 Ti 47.93 Cr 51.94 Fe 55.93 58Ni 57.93 SiO2 59.97 63Cu 62.93 Si2N 69.96 3 10 2 10 1 10 200 400 600 800 1000 1200 1400 1600 1800 2000 Depth / nm
CPS Examples of deliverables with Micro-XPS CPS Relative compositions Depth distribution profile of silicon in its various chemical states within a sample (profiles generated by angle-resolved analysis - AR-XPS) 09-342-70726_slot24.vms : Ti 2p/8 Exp Variable 0 d Pass Energy: 20 W.F.: -4.8 Total Acquisition Time 10.025 (mins) (298.5 (ms) x 5 x 403) Acquired On: 2009/12/ 9 19:30:0 Source: Mono(Al (Mono)) (225 W) x 10 2 Characterisation of titanium in its various chemical states on the surface of 2 samples that had undergone different cleaning processes the relative proportions vary significantly between the 2 samples 09-342-70726_slot25.vms : Ti 2p/7 Exp Variable 0 d Pass Energy: 20 W.F.: -4.8 Total Acquisition Time 10.025 (mins) (298.5 (ms) x 5 x 403) Acquired On: 2009/12/ 9 20:47:29 Source: Mono(Al (Mono)) (225 W) x 10 2 120.0 100.0 0.0 TiOxFy % TiO2 % TiN % 90 80 70 60 Name Ti 2p 3/2 TiN Ti 2p 3/2 TiO2 Pos. 455.4515 458.5446 At% 48.21 51.79 T i 2p 3/2 TiO2 T i 2p 3/2 TiN 70 60 50 Name Ti 2p 3/2 TiOxFy Ti 2p 3/2 TiN Ti 2p 3/2 TiO2 Pos. 459.2226 455.4600 458.5500 At% 49.93 35.16 14.91 T i 2p 3/2 TiOxFy 80.0 60.0 51.8 49.9 50 40 T i 2p 3/2 TiN 40 T i 2p 1/2 TiN 30 40.0 14.9 30 20 10 T i 2p 1/2 TiO2 20 10 T i 2p 1/2 TiOxFy T i 2p 1/2 TiO2 T i 2p 1/2 TiN T i 2p 3/2 TiO2 20.0 48.2 35.2 0 468 464 460 456 452 Binding Energy (ev) CIMPACA - Characterization Platform 0 468 464 460 456 452 Binding Energy (ev) CIMPACA - Characterization Platform 0.0 slot 24 slot 25 slot 24 slot 25
Examples of deliverables with Nano-AES Intensity Intensity Intensity SEM image and corresponding chemical imaging output for a Al stringer Characterisation of a pit (copper compound) SEM Image Copper Aluminium Silicon Depth distribution profile of elements within a pad (showing fluorine contamination on the pad surface) Analysis of a defect (Ti compound) at the bottom 28oct.124_1.lin: Sample 4.1 PHI USA 28oct.124_2.lin: Sample 4.1 of a via, characterised using line scans 2005 Oct 28 20.0 kv 0 FRR 1.7746e+005 max 2005 Oct 28 20.0 kv 0 FRR 1.9091e+005 max O1 (NormLine Binom3) O1 (NormLine Binom3) (below) or chemical imaging (opposite) x 10 5 28oct.124_1.lin x 10 5 28oct.124_2.lin 2 Line 1 W2 Line 2 W2 Ti 2 Ti Al O Al2 Al2 1.8 W Ti1 Al O Ti1 O1 1.8 O1 W 1.6 1.6 PHI 28oct.124_3.lin: USA Sample 4.1 2005 Oct 28 20.0 kv 0 FRR 1.7984e+005 max O1 (NormLine Binom3) x 10 5 28oct.124_3.lin Line 3 2 Ti Al 1.8 O W 1.6 W2 Al2 Ti1 O1 PHI USA 1.4 1.4 1.4 1.2 1.2 1.2 Al 1 1 1 0.8 0.8 0.8 Ti 0.6 Ti 0.6 0.6 0.4 0.4 Ti 0.4 Ti 0.2 0.2 0.2 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Distance (µm) 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Distance (µm) 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Distance (µm) Retrospective data processing identified aluminium in its various chemical states FOV: 1.0 µm 20.000 kev 0.2 µm FOV: 1.0 µm 20.000 kev 0.2 µm FOV: 1.0 µm 20.000 kev 0.2 µm F Sample 4.1 - Via 10 10/28/2005 F Sample 4.1 - Via 10 10/28/2005 F Sample 4.1 - Via 10 10/28/2005
Equipment Description D-SIMS, ToF-SIMS, Micro-XPS and Nano-AES systems
CAMECA IMS7f (D-SIMS) Secondary Ion Mass Spectrometry (SIMS) is a highly sensitive physico-chemical surface analysis technique. The sample surface is sputtered with a primary ion beam, eroding the surface and generating secondary ions, which are detected by the system. SIMS can be used for elemental depth profile analysis (from the nm to µm scale) on solids, with an extremely high sensitivity (in the parts per billion range for some elements). Analysis can be carried out on dopant distribution within silicon, for instance. The minimum analysis size in terms of lateral resolution is of the order of 10*10 µm depending on the target concentration. Key features: Small sample size (approximately 7mm*7mm) High mass resolution (separates 30SiH from P) Can be used on areas < 50µm 2 (with reduced sensitivity) Good ultimate vacuum (Spec 7e-10mbar) Up to 500eV impact energy with O2 + (Shallow B) Up to 3keV impact energy with Cs- (As,P) Up to 500eV impact energy with Cs + Oxygen flooding can be used to reduce surface transient» An AlphaStep profilometer (KLA-Tencor) is used to measure the depth of SIMS craters, which allows for depth calibration of the profiles
ION-TOF 5 (ToF-SIMS) Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) is based on static secondary ion emission. Unlike Dynamic SIMS (D-SIMS), which by nature erodes and deteriorates the sputtered surface, ToF-SIMS uses a total dose of primary ions of less than 10 12 ions per cm² (just one primary ion for every 1000 surface atoms). ToF-SIMS is thus a soft ionisation technique and can therefore be used for molecular surface analysis. The main application is highly sensitive elemental and molecular analysis of trace substances on a surface. A scanning beam of primary ions is used to map the various elements and molecular species present on the surface with a submicronic level of resolution. If the data acquisition process is coupled with an abrasion sequence, a composition profile can be plotted with a very high depth resolution.
KRATOS Axis Nova (Micro-XPS) X-ray Photoelectron Spectroscopy (XPS) can be used to determine the chemical composition at the surface of any solid, to a depth of less than 10 nm. The material is irradiated with a beam of X-rays. The electrons emitted are counted (quantitative analysis) and their energy levels are measured to identify elements and chemical species. This information can be used to: identify all elements present (except H) and determine their atomic concentration (detection limit 1%) determine that nature of bonds, the local environment and/or the degree of oxidation of most of the elements highlight any superficial segregation (angle-resolved analysis and/or ion beam etching) The spatial resolution is 3µm in imaging mode and 10µm in microanalysis mode Depth profiles can also be carried out using a gradual etching process using an argon ion beam
PHI 700 (Nano-AES) Nano Auger Electron Spectroscopy (Nano-AES) can be used for elemental surface analysis on solids (to depths of 0.5nm to 5nm) for elements at concentrations greater than 0.5% to 1%. The material is subjected to a beam of electrons and emits Auger electrons. The electrons emitted are counted (quantitative analysis) and their energy levels are measured to identify elements and chemical species. The scanning Auger nanoprobe uses a field effect electron gun and its argon ion source can be used to sputter surfaces for the purpose of depth profiling. The electron beam can be scanned to produce Auger chemical images. In some cases, the nanoprobe can give information about the bonding state of atoms (oxidised, metallic etc.) Lateral resolution is of the same order of magnitude as an SEM (particles 50nm)