Facilities, Services and Rates

Transcription

1 Facilities, Services and Rates Our unique facilities are available for public and private research centers as well as for the industry, who will find in the LMA equipment, a unique research capacity and technological development only available in very few research centers worldwide. Below you can find the facilities available in our center as well as what type of information you can obtain with this equipment. In addition, a careful design of combined experiments with the different instruments in the LMA will provide you with a full picture of the morphology, composition, and properties of your sample. Dual Beam, SEM, XPS, and XRD areas Cryogenic Dual Beam Nova 200 Dual Beam Helios Nanolab 600 and 650 Environmental Scanning Electron Microscope SEM-Quanta FEG 250, ESEM Field Emission Scanning Electron Microscope CSEM-FEG INSPECT 50 XRD: Bruker D8 Advance High Resolution Diffractometer XPS-AES: Kratos AXIS Ultra DLD X-Ray Photoelectron Spectrometer Transmission Electron Microscopy (TEM) Area Titan High-Base for High Resolution Imaging: FEI TITAN 3 Analytical Titan Low-Base: FEI TITAN Low-Base Transmission Electron Microscope: Tecnai F30 TEM: Sample Preparation Service Scanning Probe Microscopy (SPM) Area Low Temperature (LT), Ultra High Vacuum (UHV-LT) Scanning Probe Microscopy (SPM) Laboratory SPM with High Magnetic Fields and Low Temperature SPM in Environmental Conditions

2 Cryogenic Dual Beam Nova 200 The cryogenic dual beam instrument is dedicated mainly to analysis of electron sensitive materials (soft materials). The equipment core is based on the Nova Nanolab 200 model, but upgraded with a cryo setup that allows the analysis of materials at low temperatures. This capability consists of a cryotransfer setup and a cryochamber with embedded sputtering system. For example, this system permits to in situ generate controlled fractures on quenched soft materials, avoiding the mechanical damage associated with room temperature fractures. In addition to the study of the material in its original state (porosity, embedded nano objects, internal heterogeneities, etc.), any internal distribution of materials can be determined by using the Focused Ion Beam (FIB) to produce cross sectional surfaces. A combined strategy between this equipment and the Helios Dual Beam Model 650, also available at our Center, is being conducted to produce series of ioncuts of biological materials embedded in epoxy. These images are being used to produce three dimensional (3D) information of material distributions. Appropriate software for compositional analysis based on Energy Dispersive X ray micro analysis (EDX) is also included in this equipment. Additionally, the equipment also holds an Omniprobe nanomanipulator for lamellae preparation as well as 5 gas injectors. The expertise of our scientific and technical staff is also offered to researchers from public and private research centers and also to professionals from industrial sectors that require the use of this instrument. What can be done with this instrument? Image (resolution 1.4 nm)/ Analysis: By using the different detectors available within this instrument, the following information can be obtained: Image with secondary electrons and topography by means of an ETD/TLD (Everhart Thornley/ Thru the Lens Detectors).

3 Image (back scattered electrons) and composition by using a BSED (Back Scattering Electron Detector). Image with secondary ions, sensitive to crystallographic direction. Elementary Chemical Analysis by EDX (Energy Dispersive X ray micro analysis). STEM (scanning transmission) images. Nanofabrication (lateral dimension between 50 nm and tens of microns) FIB: focused ion beam; etching of a predesigned motif over the sample. FEBID/FIBID: focused electron/ion beam induced deposition. PRECURSOR GASES (CH 3 ) 3 (CpCH 3 )Pt, Co 2 (CO) 8, W(CO) 6, TEOS + H 2 O SiO 2, Selective Carbon Mill (MgSO 4 7H 2 0) Micromanipulation Lamellae preparation in conventional mode. Thinning at low temperatures (samples for TEM observation). Nano manipulator (Omniprobe). Low Temperature Fast freezing and cryo fracture of materials. Samples can be fractured in the 180 to 150 ºC range. The observation can be made between 130 and 140 ºC ± 1 ºC. Sample requirements Non conductive samples need metallization, which can also be done in our Centre. Conductive and non conductive samples as bulk, films, powder (compacted), etc. can be studied. Samples should be compatible with high vacuum conditions. Samples in the 1 mm to 100 mm range can be studied. They should be less than 10 mm thick. Use of the cryo option allows the measurement of liquid samples, semi liquids and beam sensitive samples, polymers, resins, MOFs (metal organic frameworks), etc.

4 Technical Specifications Electron beam resolution Ion beam resolution Landing Voltage Range Probe current High Precision 5 axes motorized stage 2.5 nm at 1 kv, 1.4 nm at 15 kv 7 nm at 30 kv E beam: 200 V 30 kv I beam 2kV 30kV E beam 1.4 pa (1kV) up to 37 na (30kV) I beam: 1 pa up to 20 na at 30 kv XY: 50 mm Z: 25 mm T: 10 to +60 R= 360 (continuous) Chamber <2.6 x 10 6 mbar (after 24 h pumping) vacuum Maximum size: 150 mm diameter with full rotation( larger Sample Size samples possible with limited rotation). Weight: max 500 g (including the sample holder). Cryo option Model PPT2000 with Cryo transfer from Quorum Technologies After freezing and vacuum transfer the sample is placed on the preparation chamber cold stage. Stage temperature is normally set Transfer to between 130 o C and 140 o C (precisely controlled to with +or 1C) Sample can be fractured using either the cooled probe or cryo Fracturing knife Tools. SUBLIMATION (ETCHING): COATING Water (ice) can be sublimed (etched) from the sample by raising the stage temperature (typically to between 80 o C and 100 o C. Sample is sputter coated with Pt or C and then transferred in to the SEM cold stage.

5 Images Lamellae preparation and thinning at low temperature. a) Pt deposited by e over multilayer organic magnetic tunnel junctions b) View of milling by i+ beam during the process to make lamella previous to the lift out. a) Electron image of lamella of organic magnetic tunnel junctions on the grid. b) Final view of the lamella, ion image c) details and thickness of lamella by ion image, the final process was made at low temperatures ( 160 ºC)

6 Cryo Fracture in organic materials.

7 Dual Beam Helios Nanolab 600 and 650 In the Clean Room facilities of the INA LMA, several lithography facilities permit to pattern structures at the micro and nano meter scale and to create devices. In particular, the two dual beam instruments (Helios 600 and Helios 650) assigned to the nanolithography and lamellae preparation areas are located on two concrete platforms inside the 125 m 2 10,000 class Clean Room. The Dual Beam Helios 600 model consists of a 30 kv field emission scanning electron column and a 30 kv Ga focused ion beam placed at 52º one from each other. The ion column is able to work properly at low voltage (5 kv and lower), allowing the preparation of lamellae with low ion damage. In this equipment, there are five gas injectors which allow the growth of nano deposits with high resolution, such as W based superconducting nano deposits with lateral size of 40 nm and Co based ferromagnetic nano deposits with a lateral size of 30 nm. These ultranarrow dimensions are at the forefront of research in these topics. In addition, electrical microprobes (Kleindiek ) could be placed inside the chamber for in situ electronic transport measurements; electron beam lithography is also possible thanks to a Raith software/hardware. The Dual Beam Helios 650 model is an improved version of the Helios 600 one. Thus, the SEM column has resolution of 0.9 nm and it bears a monochromator and beam deceleration. The FIB column is differentially vacuum pumped at the lowest part, allowing a well defined beam profile impacting on the sample surface. Results with such a column indicate that ultranarrow nano deposits can be grown. This Focused Ion Beam (FIB) column is nicely suited for lamellae preparation too, in combination with the Omniprobe nanomanipulator. The equipment has got 5 gas injectors and electrical microprobes (Kleindiek ). Both instruments are working properly for the requested main tasks, i.e., lamellae preparation, cross section imaging, nanolithography based on ion patterning, ion/electron nanodeposition, electronic transport measurements and electron beam lithography (Raith software/hardware).

8 The expertise of our scientific and technical staff is also offered to researchers from public and private research centers and also to professionals from industrial sectors that require the use of this instrument. What can be done with these instruments? Image (resolution 1.4 nm)/ Analysis: By using the different detectors available within these instruments, the following information can be obtained: Image with secondary electrons and topography by means of an ETD/TLD (Everhart Thornley Detector / Through Lens Detector). Image (back scattered electrons) and composition by using a BSED (Back Scattering Electron Detector). Images of secondary ions sensitive to crystallographic direction by using CDEM/ICE (Channel Detection Electron Multiplier / Ion Conversion and Electron) detectors. Elementary Chemical Analysis by EDX (Energy Dispersive X ray micro analysis). STEM (scanning transmission) images. Nanofabrication (lateral dimension between 50 nm and tens of microns): Direct FIB: focused ion beam; etching of a predesigned motif over the sample. Direct FEBID/FIBID: focused electron/ion beam induced deposition. PRECURSOR GASES (CH 3 ) 3 (CpCH 3 )Pt, Co 2 (CO) 8, W(CO) 6, TEOS + H 2 O SiO 2, Selective Carbon Mill (MgSO 4 7H 2 0), I 2, XeF 2 Indirect: e beam lithography (Raith ). Micromanipulation Lamellae preparation for TEM observation Omniprobe. Micro tweezers (Kleindiek ). In situ electrical measurements 4 Microprobes Kleindiek.

9 Sample requirements Non conductive samples must be coated with a conductive material (by sputtering or evaporation, which can also be done in our Centre). Conductive and non conductive samples as bulk, films, powder (compacted), etc. can be studied. Samples should be compatible with high vacuum conditions. Dimensions of the samples: less than 1 mm to 100 mm (sample height < 10 mm). Technical Specifications Electron beam resolution Ion beam resolution Landing voltage range Probe current High Precision 5 axes motorized stage Chamber vacuum Sample size 0.9 nm at 5 kv 4.0 nm at 30 kv E beam: 20 V 30 kv I beam: 500 V 30 kv E beam: 0.8 pa up to 26 na I beam: 0.1 pa 65 na (15 position aperture strip) XY: 150 mm, piezo driven Z: 10 mm motorized T: 10 to + 60 R: n x 360 (endless), piezo driven Tilt accuracy (between 50 to 54 ): 0.1 X,Y repeatability: 1.0 µm Compucentric rotation and tilt < 2.6*10 6 mbar (after 24 h pumping) Maximum size: 150 mm diameter with full rotation (larger samples possible with limited rotation) Weight: max. 500 g (including the sample holder)

10 Images Growth of nano deposits with high resolution: EBL: electron beam lithography (Raith software/hardware)

11 Electrical microprobes (Kleindiek ) Lamellae preparation (Omniprobe micromanipulator)

12 Environmental Scanning Electron Microscope SEM Quanta FEG 250, ESEM The Quanta FEG 250 SEM instrument is an environmental Scanning Electron Microscope used for high resolution imaging and composition analysis by energydispersive X ray microanalysis (EDS). The FEG column in Quanta 250 allows beam deceleration, which permits to achieve a resolution of 1.4 nm even at 1 kv electron landing voltage. The Quanta equipment can work under three different pressure ranges, the maximum pressure being 2600 Pa. This permits observation of life sciences samples without previous metallic coating, i.e., studies in environmental conditions (ESEM). This microscope allows the use of a Wet STEM, which permits to analyze samples with controlled humidity and temperature, which is crucial in life science samples. The SEM Quanta can also use a heater to perform observations on samples heated up to 1000 ºC and detect changes in the morphology of the material. In addition, with this microscope de acceleration of the electron beam over non conductive samples can be performed leading to 1.4 nm resolution even at 1 kv. The expertise of our scientific and technical staff is also offered to researchers from public and private research centers and also to professionals from industrial sectors that require the use of this instrument. What kind of information can be obtained with this instrument? Image / Analysis By using the different SEM Detectors with which this instrument is equipped, the following information can be obtained: Image with secondary electrons Topography: using an ETD/FLD (Everhart Thornley Detector/ Large Field) detector for secondary electrons.

13 Image (back scattered electrons) and composition by using GAD/vCD (Gaseous Analytical Detector/Low voltage High Contrast) detector. Images with secondary electrons from the gas phase by using a GSED/GAD (Gaseous Secondary Electron Detector/Gaseous Analytical) detector, for secondary electrons from the gas phase. Elemental chemical analysis by means of Energy dispersive X ray spectroscopy (EDX). STEM (scanning transmission) Images by using a Scanning Transmission Electron Microscopy detector. In situ experiments Heatting stage: annealing of the sample up to 1000 ºC with observation using a secondary electron detector. Peltier stage: changes in pressure, temperature and relative humidity of the chamber observing the sample using secondary electron or back scattered electron detectors. Wet STEM y STEM: Scanning Transmission Electron Microscopy in wet mode and also at high vacuum with dried samples. Sample requirements Liquid and non conductive samples observed at high vacuum mode need to be dried and metallized prior to observation. Samples studied at low vacuum or ESEM modes do not require any previous preparation. Types of samples that can be studied with SEM Quanta FEG 250 include: Bulk materials, films, coatings, and compacted powders either conductive or non conductive can be studied. Samples compatible with high vacuum, low vacuum and ESEM mode conditions. Wet samples. Sample can have a diameter from less than 1 mm up to 5 cm for high and low vacuum. ESEM (environmental SEM) observations require small samples (5 mm).

14 Technical Specifications Quanta FEG 250 specifications SEM 1 kv 3.0 nm without BD 30 kv 1.0 nm 3 kv (low vacuum) 3.0 nm Maximum beam 200 na current Vacuum Modes High Vacuum Low Vacuum (up to 200 Pa) ESEM (2600 Pa) Stage X x Y x Z (mm) 50 x 50 x 50mm Detection Solid state BSE BSED, vcd, DBS STEM Low vacuum ESEM STEM LFD, GAD GSED, GBSD, ESEM GAD Imaging Scan strategies FEI Smartscan, DCFI Cleanliness Navigation & large images CryoCleaner EC, Integrated Plasma Cleaner MAPS, Nav Cam Chamber Large chamber, 10 ports

15 Images

16 Field Emission Scanning Electron Microscope CSEM FEG INSPECT 50 A scanning electron microscope (SEM) is a type of electron microscope that produces images of a sample by scanning it with a focused beam of electrons. The electrons interact with the sample, producing various signals that can be detected in the electron microscope detectors giving information about surface topography and composition of the sample. The Inspect F 50 SEM instrument is a general purpose field emission Scanning Electron Microscope for highresolution imaging and composition analysis by energydispersive X ray microanalysis (EDS). The expertise of our scientific and technical staff is also offered to researchers from public and private research centers and also to professionals from industrial sectors that require the use of this instrument. What kind of information can be obtained with this instrument? Image / Analysis By using the different SEM Detectors with which this instrument is equipped, the following information can be obtained: Images with secondary electrons image and topography by means of an ETD (Everhart Thornley Detector). Image and composition by using a BSED (Back Scattering Electron Detector). Elemental chemical analysis by means of Energy dispersive X ray spectroscopy (EDX).

17 Sample requirements Liquid and non conductive samples observed need to be dried and metallized prior to observation. Samples studied at low vacuum can be used without metallization at low voltage (low contrast and low sharpness images). Types of samples that can be studied with Inspect F 50 SEM include: Conductive and non conductive samples, bulk, films, coatings, powders (compacted), etc. Samples compatible with high vacuum conditions. Sample Diameter from less than 1 mm up to 50 mm. Technical Specifications Inspect F 50 SEM 1 kv resolution 3.0 nm without BD 30kV resolution Maximum beam current 1.0 nm 200 na Vacuum Modes High Vacuum X x Y x Z (mm) 50 x 50 x 50 mm Stage Tilt angles 15º to 75º Rotation 360º Detection Solid state BSE BSED ETD

18 Images

19 Bruker D8 Advance high resolution X ray diffractometer: HR XRD and XRR X ray scattering is routinely used to determine the crystal structure, orientation, lattice parameters and crystal quality in crystalline materials (X ray diffraction) and thickness, density or roughness of thin films and multilayers (X ray reflectivity). The equipment configuration is optimized for high resolution X ray diffraction (HR XRD) and reflectivity (XRR) studies in nanostructured thin films and superlattices. For this purpose it includes incident and diffracted beam monochromators, collimators, attenuators and eulerian sample holder. It also allows the local mapping of flat samples through motorized lateral displacements. XRD at LMA uses a D8 Advance diffractometer provided by Bruker Española S.A. This instrument has several modes, including: High resolution diffraction in epitaxial films and multilayers Reciprocal space maps Wafer mapping X ray reflectivity Structural characterization of single crystal or strongly textured thin films Grazing incidence diffraction (GID) The XRD equipment is mainly used by researchers growing epitaxial thin films in the following applications and research lines: Epitaxially strained thin films Magnetic thin films and nanostructres for applications in Spintronics Multiferroic films and multilayers Thin films showing thermoelectric effects (such as spin Seebeck) The expertise of our scientific and technical staff is also offered to researchers from public and private research centers and also to professionals from industrial sectors that require the use of this instrument.

20 What kind of information can be obtained with XRD? XRD and XRR provide the following information in thin films: Chemical composition Crystal structure Lattice parameters Substrate and film orientation Miscut angle in single crystal substrates Crystalline quality and texture Roughness Density Thickness Defects, dislocations Stress Sample requirements Although this facility is very versatile and the analysis of powder samples is feasible, the current configuration is optimized for the study of thin films. Technical specifications X ray generator with copper anode (022) Ge monochromator (Cu K 1 line) Parallel beam optics (Göbel mirror) Eulerian cradle and XYZ translation stage Zeta and Xi tilt stage for grazing incidence X ray diffraction Suction device for securing flat samples Soller slits X ray beam intensity attenuator Automatic alignment control by microscope and laser beam Scintillation counter Analysis software and databases

21 Images XRRR measurement (black line) l and best fit using the Leptos software from Bruker (pink line) of an epitaxial heterostructu ure MgO//Fe 3 O 4 /MgO/Fe/MgO. The thickness and root-mean square roughness values are shown in the table.

22 Reciprocal space map measured around the pseudocubic 013 reflection of an epitaxial SrRuO 3 /BaTiO 3 heterostructure grownn on a GdScO 3 substrate.

23 XPS AES Kratos AXIS UltraDLD, X Ray photoelectron Spectrometer XPS is a surface sensitive quantitative spectroscopic technique mainly used to analyze the surface chemistry of a material. XPS is capable to measure elemental composition, empirical formula, chemical state and electronic state of the elements that exist within a material. XPS is routinely used in the characterization of polymers, alloys, semiconductors, minerals, inks, adhesives, inorganic materials, glass, thin films, etc. and to study surface effects/process as segregation, diffusion, adsorption and desorption, corrosion, degradation, adhesion, soldering, contamination, cleaning, coating, functionalization, etc. Typical areas of interest are, among others, the following: Thin films and coatings. Surface functionalization. Polymers and adhesives. Mineralogy, geochemistry, and petrochemistry. Metalurgy. Catalysis. Microelectronics and semiconductors. Surface characterization of solids. XPS is a surface sensitive spectroscopy (first 3 to 10 nm). ARXPS (angle Resolved XPS give us also information about depth profile (distribution of elements, thickness of coatings, multilayers and oxide layers ). Combining XPS analysis and Ar + ion sputtering the technique is capable to carry out depth profile studies of several hundred of nanometers. The expertise of our scientific and technical staff is also offered to researchers from public and private research centers and also to professionals from industrial sectors that require the use of this instrument. What kind of information can be obtained with XPS? XPS spectroscopy provides the following information about the sample:

24 Elemental composition Quantitative and qualitative elemental analysis Chemical structure Imaging Quantitative and qualitative analysis of oxidation states of elements Lateral distribution of chemical composition (elements / oxidation states) Depth profiling (Angle Resolved XPS / sputtering) Depth profile of chemical composition Thickness of coatings, functionalized layers and oxide layers Detection limits. Sensitive to elements with Z 2 (all elements except for H and He). Typical minimum detectable concentration: 0.1 1% (atomic). Typical quantification error: ~10%. Resolution limit (imaging mode): 3 μm. Sample requirements Any sample (conductive, non conductive, magnetic, organic, inorganic, powder, bulk, viscous) provided it is compatible with high vacuum. There is no need of any specific sample preparation or coating process. Non destructive analysis. Sampled area from 10 μm (minimum) 500 μm (standard). Analysis depth: 3 10 nm (higher is possible by etching). Technical specifications Analysis chamber with base pressure < 10 9 Torr. Al mono and Al/Mg dual X ray. Multi detector energy analyser and 2D image in parallel. Sample holder for 4 axis high precision displacements. ARXPS Angle Resolved XPS. Electron gun for AES/SEM/SAM.

25 Ar + ion milling for cleaning and etching (depthh profile). Charge neutralizer (flood electron gun and magnetic lenses). Analysis software and databases. Images and examples Fig.1 Martín et al. Chem. Eur. J. 2014, 20, Fig.2 Lucía González et al. Chem. Mater., 2013, 25 (22), pp

26 Fig.3 Mizrahii et al. Langmuir 29 (2013) Fig.4 Ballesteros et al. Langmuir 2011, 27,

27 Titan High base for High Resolution Imaging: FEI TITAN 3 The Titan High Base has a spherical aberration corrector (CEOS Company) at the objective lens, the lens that forms the image. It is therefore the ideal instrument for ultra high resolution imaging (HRTEM). This microscope also has a biprism for Electron Holography analysis and a Lorentz Lens to perform High Resolution Lorentz Microscopy. Working at low voltage (60 kv, 80 kv), and because of the aberration corrector, high resolution images can be obtained even on beam sensitive materials such as graphene, carbon nanotubes, zeolites and mesoporous materials, etc. The working voltages for this instrument are: 60, 80, 120, 200 and 300 kv. The expertise of our scientific and technical staff is also offered to researchers from public and private research centers and also to professionals from industrial sectors that require the use of this instrument. What kind of information can be obtained with this instrument? Image (0.09 nm resolution) Size and morphology information (TEM). Crystalline Structure (Electron Diffraction and High Resolution TEM). Composition: Scanning Transmission imaging with a High Angle Annular Dark Field detector (STEM HAADF). The contrast in the image depends on the atomic number (Z contrast). Energy Filtered TEM (EFTEM) yields information about a specific element. Chemical Analysis Electron Energy Loss Spectroscopies (EELS). Combined with the STEM mode: chemical composition with spatial resolution: composition maps and profiles.

28 Vector Field Analysis Electric and magnetic field studies by Electron Holography. Magnetic domain studies by Lorentz Microscopy. Stress and strain studies by HRTEM imaging. In situ physical properties measurements Changes of crystalline phase (Electron diffraction) Defect structure by bright field/dark field imaging (BF/DF) and Weak Beam imaging (WBDF). Technical specifications This Transmission Electron Microscope works at voltages between 60 and 300 kv. It is located in a box (cube) to avoid mechanical and thermal perturbations. It has a normal FEG (Shottky emitter) and a Gatan 2k x 2k CCD camera for (HR)TEM images acquisition. The main working modes in this microscope are: HREM: since this microscope is devoted for High Resolution Transmission Electron Microscopy (HRTEM) studies, it is equipped with a SuperTwin objective lens and a CETCOR Cs objective corrector from CEOS Company allowing a point to point resolution of 0.09 nm. STEM: In addition this Titan 3 is equipped with the basic STEM facilities (BF, DF detectors) for STEM imaging at medium resolution. EELS: a Gatan Energy Filter Tridiem 863 allows Titan 3 to perform EELS experiments in a standard and routine way (energy resolution of 0.7 ev). Lorentz and holography: as for the dedicated Titan STEM, beside these spectroscopy capabilities, the Titan 3 corrected microscope is fitted with a Lorentz lens and an electrostatic biprism allowing Lorentz and medium resolution electron holography experiments to be carried on. Images

29 In Situ Formation of Carbon Nanotubes Encapsulated within Boron Nitride Nanotubes via Electron Irradiation Ref.: ACS Nano 8, (2014) doi: /nn502912w

30 Aberration corrected HRTEM image of a magnetite nanoparticle epitaxially coated by a 1-nm-thick MgO layer. The insets show the FFT calculated from the areas marked with white squares. Ref.: Chem. Mater., 2012, 24 (3), pp doi: /cm202306z

31 Analytical Titan Low base: FEI TITAN Low base The Titan Low base has a spherical aberration corrector (CEOS Company) at the condenser lens, the lens that forms the probe. Consequently, this microscope is appropriate for ultra high resolution imaging in Scanning Transmission mode (HRSTEM) and chemical composition mapping with atomic resolution by Electron Energy Loss Spectroscopy (STEM EELS). This microscope has a monochromator and a High Brightness source (XFEG), which makes it ideal to determine optical properties by low loss EELS as well as oxidation states studies by core loss EELS and observation of the fine structure of the energy absorption edges by Energy Loss Near Edge Spectroscopy (ELNES). Working at low voltages (60 kv, 80 kv), and because of the aberration corrector, high resolution images can be obtained even on beam sensitive materials such as graphene, carbon nanotubes, zeolites and mesoporous materials, etc. The working voltages for this instrument are: 60, 80, 120, 200 and 300 kv. The expertise of our scientific and technical staff is also offered to researchers from public and private research centers and also to professionals from industrial sectors that require the use of this instrument. What kind of information can be obtained with this instrument? Image (0.09 nm resolution) Size, morphology and crystalline structure information (TEM and STEM modes, electron diffraction). Composition: Scanning Transmission imaging with a High Angle Annular Dark Field detector (STEM HAADF). The contrast in the image depends on the atomic number (Z contrast). Energy Filtered TEM (EFTEM) yields information about a specific element. Three dimensional (3D) reconstruction: electron tomography. Chemical Analysis

32 X Ray (EDS) and Electron Energy Loss Spectroscopies (EELS). Combined with the STEM mode: chemical composition with spatial resolution; composition maps and profiles with atomic resolution. Vector Field Analysis Electric and magnetic field studies by Electron Holography. Magnetic domain studies by Lorentz Microscopy. Stress and strain studies by HRTEM imaging. In Situ physical properties measurements Changes of crystalline phase (Electron diffraction). Defect structure by bright field/dark field imaging (BF/DF) and Weak Beam imaging (WBDF). Technical Specifications This Scanning Transmission Electron Microscope works either in TEM or in STEM modes at voltages between 60 and 300 kv. It can be used at low voltage to analyse electron irradiation sensitive materials. It is fitted with the last generation of a high brightness Schotky emitter developed by FEI (the so called X FEG gun), a monochromator, and a Gatan 2k x 2k CCD camera. STEM: As this microscope is devoted for STEM and EELS experiments, it is equipped with a CESCOR Cs probe corrector from CEOS Company allowing for the formation of an electron probe of 0.09 nm mean size. The TEM is equipped with all the STEM facilities (BF, DF, ADF and HAADF detectors) and 0.09 nm spatial resolution has indeed been achieved in STEM HAADF mode. EELS and EDS: For EELS experiments, the microscope is fitted with a Gatan Energy Filter Tridiem 866 ERS and a monochromator. An energy resolution of 0.14 ev can be achieved with this setup. In addition, an EDS (EDAX) detector allows performing EDX experiments in scanning mode with a spatial resolution of about ~0.2 nm. Lorentz and holography: in addition to the above described analytical capabilities, the Titan STEM corrected microscope is fitted with a Lorentz lens and an electrostatic biprism allowing Lorentz and medium resolution electron holography experiments to be carried out in a field free environment (as needed for magnetic materials studies). Tomography: a tomography set up with a +/ 70 single tilt stage permits to perform 3D reconstructions either in TEM or STEM modes.

33 Images (a) Z-contrast images along a particular planar defect of a YBCO nanocomposite. (b) exx deformation map showing in colors (red and green) different deformation values. Ref.: Appl. Phys. Lett. 102, (2013) doi: / : a) Ball-and-stick model, shown in perspective, of the Cd-loaded zeolite A. Cd in violet, O in red, and Si and Al in blue. b) Cs-corrected STEM image of a CdA. The FFT inset was indexed assuming Pm3m Ref.: J. Phys. Chem. C, 2013, 117 (46), pp

34 Transmission Electron Microscope Tecnai F30 The Tecnai F30 (FEI company) is a versatile high resolution Transmission Electron Microscope. It can work in TEM or STEM (Scanning Transmission) modes. It is equipped with all the analytical techniques to obtain morphology, structure and composition information with atomic resolution. The working voltages in this microscope are 200 and 300 kv. The expertise of our scientific and technical staff is also offered to researchers from public and private research centers and also to professionals from industrial sectors that require the use of this instrument. What kind of information can be obtained with this instrument? Image (Resolution 0.19 nm) Size and morphology information (TEM). Crystalline Structure (Electron Diffraction and High Resolution TEM). Composition: Scanning Transmission imaging with a High Angle Annular Dark Field detector (STEM HAADF). The contrast in the image depends on the atomic number (Z contrast). Energy Filtered TEM (EFTEM) yields information about a specific element. 3D reconstruction: electron tomography. Chemical analysis X Ray (EDS) and Electron Energy Loss Spectroscopies (EELS). Combined with the STEM mode: chemical composition with spatial resolution; composition maps and profiles. Vector Field analysis

35 Magnetic domain studies: Lorentz Microscopy. Stress and strain studies by HRTEM imaging. In situ Physical properties measurements Changes of crystalline phase (Electron diffraction) Defect structure by Bright Field/Dark Field imaging (BF/DF) and Weak Beam imaging (WBDF). Technical Specifications This 300 kv Field Emission Gun (FEG) TEM is fitted with a SuperTwin lens allowing a point resolution of 1.9 Å. This TEM can work in TEM and STEM mode. For Z contrast imaging in STEM mode, it is fitted with a High Angle Annular Dark Field (HAADF) detector. This TEM is equipped for spectroscopy experiments performed either in EDS (X Ray Microanalysis) or in Electron Energy Loss spectroscopy (EELS). For the latter, it is fitted with the Tridiem Gatan Energy Filter (GIF). This EELS set up allows Energy Filtered TEM (EFTEM) images to be recorded as well as line spectra or spectrum imaging experiments to be performed. A 2k x 2k Ultrascan CCD camera (Gatan) is located before the GIF for TEM imaging. In addition to these capabilities the F30 TEM is also fitted with a Lorentz lens which permit the study of magnetic materials in an environment free of magnetic field (for magnetic domain imaging). Furthermore, the F30 allows tomography experiments to be performed both in TEM and STEM mode using a dedicated single tilt holder (+/ 70 ) from Fischione. Images

36 Electron tomography reconstruction from a HGNP, a rough surface caused by fast galvanic replacement is shown. Ref.: Lab On Chip 2014, 14, doi: /c3lc50999k Spatial distribution of the elements of immuno-functionalized core-shell superparamagnetic magnetite nanoparticles.

37 Ref.: ACS Nano May 28;7(5): doi: /nn306028t

38 TEM Sample Preparation Service Transmission Electron Microscopy (TEM) is based on the use of transmitted electrons to form images of the materials. However, the electron is a strongly interacting charged particle and TEM samples are required to be extremely thin (tens of nm) to be electron transparent. Some materials are inherently electron transparent (nanoparticles, nanotubes, etc.). However, many other materials (bulk materials, thin films, devices ) have much larger dimensions and it is frequently required a TEM sample preparation procedure to make them thin. The LMA has set the complete Sample Preparation Laboratory equipped with the necessary instruments to Sample Preparation Laboratory perform this task. Among the many procedures to produce electron transparent specimens, the most important and frequently used is based on mechanical thinning of the materials in a highly controlled way. This produces a flat specimen of a few microns thickness with smooth surfaces that afterwards follows a low angle, low energy ion milling of the surfaces to achieve extremely thin areas ready for TEM observation. When sitespecific (for instance, to analyze the cross section of a small nanodevice) or highly reproducible specimen preparation is required, TEM lamellae can also be prepared by Focused Ion Beam (see Dual Beam Laboratory in the Clean Room of the LMA). Ultramicrotomy is another technique to produce TEM samples of soft materials. The procedure consists in cutting some slices of the sample using the diamond knife of an ultramicrotome. These slices are around 50 nm of thickness of polymers and biological samples. Depending on the specific features of the materials, samples can be cut between 180 ºC and room temperature. In the case of biological samples, a previous treatment is necessary in which the samples (tissues, cells, bacteria...) need to be fixed (using glutaraldehyde and osmium tetroxide), dehydrated and embedded in epoxy resin before cutting with the ultramicrotome. In the LMA it is possible to vitrify samples and analyze them in cryogenic Ion mill equipment to obtain electron transparent areas in the samples for the TEM observation.

39 conditions. In this case, aqueous solutions like macromolecules, proteins, viruses, etc. can be vitrified using liquid ethane. These samples can be observed using cryo TEM technique. Instruments available for TEM sample preparation Ion Mill Fischione Model Plasma Cleaner Fischione Model Low/high speed polishers. Tripods and grinders. Dimpler. Diamond wire saw. Stereographic microscope. Metallographic microscope. Inverted microscope. Ultramicrotome Leica EM UC7. Cryo ultramicrotome Leica EM FC7. FEI Vitrobot (vitrification). Materials that can be prepared for TEM observation Nanoparticles, nanotubes,... Inorganic materials (oxides, metals, ceramics) in cross section and plane view). Polymers Organic molecules (proteins, DNA, gels, virus,...) Cells and biological tissues

40 Low Temperature (LT), Ultra High Vacuum (UHV LT) Scanning Probe Microscopy (SPM) Laboratory The laboratory of Low Temperature, Ultra High Vacuum (UHV LT) is specifically designed for surface science microscopy and spectroscopy methods. The aim is to cover a wide variety of problems in surface science, from molecular chemistry to atomic magnetism. Three systems available in our laboratory are equipped with different preparation techniques under UHV conditions, as well as with a large variety of epitaxial growth facilities. Force and Tunnel based methodologies can be combined, allowing investigating substrates with different electronic properties. The accessible temperature range for experiments is from 0.5 K to 1300 K. The laboratory is composed by three UHV set ups hosting 4 different SPM heads, each with complementary characteristics: 1. Joule Thompson STM with axial magnetic field and variable temperature SPM (called internally Moncayo and Arán instruments). 2. Low Temperature STM in UHV (Ordesa instrument). 3. Low temperature STM/AFM in UHV (Ainsa instrument). 1. Ultra low Temperature STM with axial magnetic field and variable temperature SPM Moncayo and Aran Instruments This equipment is specifically oriented to investigate atomic scale magnetism and to high resolution spectroscopy (0.1 mev) of molecules and atoms, as well as to study the physicalchemical phenomena of surfaces function of temperature and gas dosing.

41 Both aspects are covered by two UHV SPM heads connected under UHV conditions as a part of a multichamber system. One of them Moncayo features a base temperature of 1.1 K (can be extended down to 0.5 K by using He 3 instead of He 4 in the Joule Thompson stage), a 3 Tesla axial field and a hold time of 100 h. Spin Polarized STM measurements can be performed routinely. The other one Arán is a variable temperature STM/nc AFM (from 100 K to 1300 K), with a fast and flexible measurement approach. Two additional chambers with independent vacuum allow the user the preparation of samples in situ and the epitaxial growth of organic and inorganic thin films on surfaces. What kind of information can be obtained with this instrument? Energy spectra of the density of states and quantum energy levels of atomic scale objects. Electronic and structural properties of surfaces with atomic resolution. Spin structure and magnetization curves of magnetic nano objects from the range of 100 nm down to sub atomic and sub molecular resolution. Engineering functional nanostructures by atomic manipulation. Real time monitoring of catalytical activity as a function of temperature and reacting gases. Physical chemical characterization of surface steered self assembly processes. Sample requirements Preferably grown in situ. Metallic, semiconducting or ultra thin (3 monolayer) insulating surfaces. Surface roughness < 1 nm. Substrate or specimen maximum size: 3 mm thick and 10 mm wide.

42 Technical Specifications Low Temperature STM (internally called Moncayo) Joule Thomson cryostat (1 K 10 K) UHV STM; 3 T axial B field. Metal and organic epitaxy in situ. Vendor: SPECS GmbH Variable Temperature STM Variable Temperature AFM Aarhus variable temperature (100 K 1300 K) STM; Non contact AFM. Vendor: SPECS GmbH (internally called Arán) Sample preparation LEED/Auger characterization facilities; 9 Molecular Beam Epitaxy pockets (5 of them with fast reload option), 1 effusion cell, 3 sputter guns, 4 e beam heaters, 2 in situ transportable resistive crucibles for deposition of organic materials, SP STM tip preparation Images Caption: From left to right. Binary information encoded in single Co atoms with up/down spin represented by yellow/red colors. The same chain with contrast reversed. Example of energy resolution in quantum spectra (Co atoms over Cu 2 N monolayer). Ni 3 C 4 over a Ni (111) surface stabilized by a partial pressure of 10 6 mbar propene at 500 ºC. Example of atomic manipulation to build the logo of Tercer Milenio 20 using 44 atoms.

43 2. Low Temperature STM in UHV Ordesa Instrument This equipment is devoted to investigate metal on metal epitaxy of rare earths. It is specially oriented to the growth of magnetic thin films and nanostructures. The instrument runs at a base temperature of 4 K and has been optimized for deposition of rare earth metals on tungsten substrates. What kind of information can be obtained with this instrument? Energy spectra of the density of states of atomic scale objects. Electronic and structural properties of surfaces with atomic resolution. Atomic manipulation. Sample requirements Preferably grown in situ. Metallic, semiconducting or ultra thin (3 monolayer) insulating surfaces. Surface roughness < 1 nm. Substrate or specimen maximum size: 3 mm thick and 10 mm wide.

44 Technical Specifications Low Temperature STM (internally called Ordesa) Sample preparation Low temperature (5K) UHV STM. Vendor Omicron GmbH Metal epitaxy, and LEED/Auger characterization facilities. Images a) b) c) (a) Atomic manipulation: Tm adatoms on W(110) (b) A quasi-hexagonal Tm monolayer (ML) on W(110), showing some Tm adatoms on it. (c) Tm nanowires, single-atom width, on a Tm ML/W(110).

45 3. Low temperature STM/AFM in UHV Ainsa Instrument This set up includes the last development in UHV non contact AFM. Working at a base temperature of 4.5 K, the use of a qplus sensor allows to simultaneously acquire electron tunneling signal and forces in the piconewton range. Measurement of both forces and conductance is especially interesting in the field of molecular physics on surfaces. Force microscopy is also especially suitable to work on insulating surfaces. This experimental set up has been equipped with various methods to deposit organic materials on inorganic surfaces. The research lines are oriented to molecular interactions, self assembly and magnetic, electronic and structural properties of hybrid metal organic films. What kind of information can be obtained with this instrument? Energy spectra of the density of states of atomic scale objects. Electronic and structural properties of surfaces with atomic resolution. Engineering functional nanostructures by atomic manipulation. Atom resolved structural characterization of macromolecular complexes. Mapping of electronic charge (surface potential) down to submolecular resolution. Preparation and characterization of metalorganic networks. Sample requirements Preferably grown in situ. Conducting or insulating samples.

46 Surface roughness < 1 nm. Substrate or specimen maximum size: 3 mm thick and 10 mm wide.

47 Technical Specifications Low Temperature STM/AFM (internally called Ainsa) Low temperature (4.5 K) UHV STM equipped with a tunning fork head for simultaneous STM and high resolution AFM. Sample preparation 1 fast reload Molecular Beam Epitaxy pocket, 1 Knudsen cell and 1 fast reload crucible for sublimation of organic material, cryogenic sample preparation stage. Images Caption: From left to right. STM topography of a 3 layer thick stacked FePc film. Zoom into one of the layers. STM topography and simultaneous force map of a Ruthenium based complex. Atomically resolved force map of a Mn Tetracyanobenzene coordinated network.

48 Laboratory of Scanning Probe Microscopy with high magnetic fields and low temperature This laboratory offers the possibility of combining probe measurements with low temperatures and a high vector magnetic field. The SPM with high magnetic fields and low temperature is especially designed for combination of local probe and magneto transport measurements as, for example, scanning gate microscopy. Therefore, it runs research lines oriented towards low temperature magnetism, transport through nanodevices, spintronics, and superconductivity. The instrument is composed by a large liquid helium cryostat holding a vertical bore superconducting magnet reaching 8 T (one axis) / 2 T (2D vectorial) magnetic field and a variable temperature controller (2 K 300 K). The equipment has a quick load facility, allowing an easy sample replacement. The system is also equipped with two different piezos in order to get the best features in resolution and stability, and a low noise voltage amplifier keeping the conditions to get the best signal/noise ratio. What kind of information can be obtained with this instrument? These features allow performing many of the STM/AFM related techniques: Surface morphology. Topography with resolution below 1 nm. Electrical conductivity (c AFM). Quantitative local electrical resistance measurements. Local electrical potential (KPM). Qualitative measurements of local charge distribution. Magnetic properties (MFM). Magnetic properties analysis under magnetic fields. Piezo electric properties (PFM). Using the tip as electrode and deformation sensor. Thermal dependence. Capacity to measure in the 2 to 500 K range. Topography based in low vacuum Scanning Tunnel Microscopy (STM).

49 Sample requirements The sample should be immobilized onto a flat substrate The sample should exhibit a roughness lower than the range of the piezo scanner. The size of the sample should be small enough to fit inside of the microscope, around 1cm 2 and a maximum thickness of 0.5 cm. The sample should be compatible with low temperature and vacuum conditions. Technical Specifications AFM/MFM head with interferometric sensor. STM/Tuning Fork head. Variable temperature insert (1.5 K 300 K) cryostat. 8 T (vertical) and 2 T (in plane) superconducting magnet, that combined with a rotating platform allows to apply vector fields in three dimensions. Compatible chip carrier with dual beam and pulsed field facilities. Images Topography and magnetic signal from a permalloy nanowire Topography and piezoresponse map from a piezoelectric material thin film. 1000nm 1000nm

50 Scanning Probe Microscopies (SPM) in environmental conditions Scanning Probe Microscopies are key enable techniques in Nanosciences and Nanotechnologies, supporting a wide range of multidisciplinary activities. The LMA has a special room with outstanding vibration isolation stages dedicated to hold the SPM instruments in environmental conditions. In addition, a highly specialized technical scientist is in charge of the support to external users, training of frequent and experienced users, and maintenance of the equipment. Two environmental SPM microscopes are available for internal and external users at LMA: 1. Cervantes Fullmode SPM from Nanotec Electrónica S.L. AFM (Atomic Force Microscope) / MFM (Magnetic Force Microscope) / STM (Scanning Tunnelling Microscope) equipped with variable magnetic field and a liquid cell. The jumping mode is especially suitable to measure soft samples in liquid. 2. Multimode 8 from Veeco Bruker. Scanning Probe Microscope equipped with KPM (Kelvin Probe Microscopy), c AFM (conductive AFM), liquid and electrochemistry cells, PicoForce module for force spectroscopy measurements, variable temperature controller, Torsion mode head and QNM (Quantitative Nanomechanical Property Mapping) Peak Force mode. What kind of information can be obtained with these instruments? The following information can be obtained with our SPM instruments: Surface morphology. Topography with resolution below 1 nm. Electrical conductivity (c AFM). Quantitative local electrical resistance measurements. Mechanical properties (QNM Peakforce). Quantitative local measurement of the elastic modulus, adhesion, stiffness, energy dissipation and deformation on surfaces. Local electrical potential (KPM). Qualitative measurements of local charge distribution.

51 Magnetic properties (MFM). Magnetic properties analysis under magnetic fields. Nanomechanical studies by using Single Molecule Force Spectroscopy. Pullpush experiments for inter and intra molecular force measurements, with 1 pn resolution. Electro chemical properties (EC SPM). Study of chemical reactions on surfaces under controlled environments. Piezo electric properties (PFM). Using the tip as electrode and deformation sensor. Thermal dependence. Capacity to measure in the 250 K to 500 K range. Topography based in ambient Scanning Tunnel Microscopy (STM). Sample requirements The sample should be immobilized onto a flat substrate (for instance, biomolecules should be immobilized onto a mica surface via adsorption or via a covalent procedure). The sample should exhibit a lower roughness than the range of the piezo scanner. The size of the sample should be small enough to fit inside of the microscope, around 1 cm 2 in surface and 0.5 cm in thickness. Types of samples that can be studied with the environmental SPMs include: Biological samples (DNA, proteins and peptides; cells, viruses and bacteria; biological tissues, etc.). Organic and inorganic thin films. Nanostructures. Nanoparticles. Gels and Polymers. Technical Specifications Enviroment Bruker Multimode 8 Air, liquid and electrochemical cell Nanotec Cervantes Air and liquid Temperature range [ 35, 200] C Room temperature Piezos range Magnetic field 200 µm x 200 µm x 5 µm 12 µm x 12 µm x 3 µm No 10 µm x 10 µm x 3.5 µm Out of plane, pulsed (1 s max.) In plane continuous up to 0.15 T

52 Topography and magnetic signal from a focus ion beam fabricated nanostructure. Topography and electrical conductivity from nanoelectrodes. Graphene layers deposited on mica

53 Topography and elastic modulus map from a polymer 20nm Liquid ambient topography from proteins deposited on mica

54 Rates LMA offers access to the equipment and support of our teamm via: Proposal (write a small research project) Without Proposal (just apply for the use of the equipment) ICTS use (apply for the use of the equipment to the joint ELECMI ICTS; a proposal is also required). This type of access will be enabled soon. The access rates are differentt in each case. The rates also vary depending on the type of users, which are classified as: members of the t University of Zaragoza (UNIZAR), members of public research institutions (OPI) or private companies (INDUSTRY). In the following tables the rates for the LMA equipment are described. TEM services ( /day) Equipment Titan High Base Titan Low Base F30 UNIZAR with proposal UNIZARR withoutt proposal OPI with proposal OPI without proposal INDUSTRY with proposal INDUSTRY without proposal DUAL BEAM services ( /day) Equipment Helios 600 Helios 650 Nova Quanta Inspect XPS XRD UNIZAR with proposal UNIZARR OPI withoutt with proposal proposal OPI without proposal INDUSTRY with proposal INDUSTRY without proposal

55 SPM services ( /day) Equipment Environmental SPM: Nanotec Fullmode Environmental SPM: Bruker Multimode 8 SPECS* Moncayo/Aran OMICRON* Ordesa OMICRON* Ainsa High Magnetic Fields STM/AFM/MFM UNIZAR with proposal UNIZAR without proposal OPI with proposal OPI without proposal INDUSTRY with proposal INDUSTRY without proposal *Due to the peculiarity of these facilities of ultra high vacuum and low temperatures, which sometimes require time consuming experiments, when an experiment takes more than two weeks, only those first two weeks will be charged in terms of equipment time. For the duration of the experiment, only the consumable expenses will be charged (helium, substrates, etc.).

56 Sample Preparation Services ( /sample) Equipment UNIZAR OPI INDUSTRY Fixation/Dehydration Ultramicrotomy Embedding Thin sections/staining Ultrathin sections Ultrathin sections (without preparation and with user s knife) Negative staining Grid Cross section/tripod (without ion milling) TEM Cross section/grinder dimpler (without ionmilling) Planar view/tripod (without ion milling) Planar view/grinder dimpler (without ion milling) Ion beam polishing (Ion Milling) Mechanical polishing SEM Coating (gold, platinum, carbon) Osmium tetroxide (ampoule) Other Please ask for quotation: lma@unizar.es

57 Access Protocol Access without Proposal To gain access to the LMA facilities without proposals you justt have to fill on line the form available in the LMA web site. You will get an e in a few working days informing you about the dates in which you can use the instrument you demanded in your application. Access with Proposal To gain access to the LMA facilities with proposal, have to submit a research proposal describing their requirements. A standardized proposal formm is available in the LMA website and can be filled on line. You will get an in a maximum of ten working days with the outcome of your proposal. If your proposal p hass been accepted you will be informed about the dates in which you cann use the instrumentt you requested in your application. The research proposal to gain access will contain thee administrative location of the requesting person or group leaderr and will describe: The scientific aim of the project, including The state of the art The expected output The potential industriall applications Possible special requests (for example: use of particular stages, precautions, low temperature, gas atmosphere, low voltages ) The requested instrument(s) ) including measuring conditions and sample preparation facilities, if needed. The requested access time to the instrument and sample s preparation time (if any) The preferred datess for the measurements. The requested time for computing / data treatment and a analysiss time (if any). There will be a permanently open call for submission of proposals. Successful proposals will be then allocated for a measuring slot as soonn as possible. For every successful proposal, the area leader of the LMA will select a technician in house correspondent (local contact). The applicant will be then notified