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Scanning SFG Spectrometer

Picosecond Scanning Sum Frequency Generation (SFG) Vibrational Spectrometer
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  • Characterisation of vibrational bonds of molecules at surfaces or interfaces
  • Intrinsically surface specific
  • High spectral resolution
  • Wide range of accessible (molecular) vibrations: 625 – 4300 cm⁻¹
SFG spectrometer

Sum Frequency Generation (SFG) Vibrational Spectroscopy

ADVANTAGES

  • Sensitive and selective to the orientation of molecules in the surface layer
  • Intrinsically surface specific
  • Selective to adsorbed species
  • Sensitive to submonolayer of molecules
  • Applicable to all interfaces accessible to light
  • Nondestructive
  • Capable of high spectral and spatial resolution

APPLICATIONS

  • Investigation of surfaces and interfaces of solids, liquids, polymers, biological membranes and other systems
  • Studies of surface structure, chemical composition and molecular orientation
  • Remote sensing in hostile environment
  • Investigation of surface reactions under real atmosphere, catalysis, surface dynamics
  • Studies of epitaxial growth, electrochemistry, material and environmental problems
 

Sum Frequency Generation Vibrational Spectroscopy (SFG-VS) is powerful and versatile method for in-situ investigation of surfaces and interfaces. In SFG-VS experiment a pulsed tunable infrared IR (ωIR) laser beam is mixed with a visible VIS (ωVIS) beam to produce an output at the sum frequency (ωSFG = ωIR+ ωVIS). SFG is second order nonlinear process, which is allowed only in media without inversion symmetry. At surfaces or interfaces inversion symmetry is necessarily broken, that makes SFG highly surface specific. As the IR wavelength is scanned, active vibrational modes of molecules at the interface give a resonant contribution to SF signal. The resonant enhancement provides spectral information on surface characteristic vibrational transitions.

Vibrational sum frequency generation (SFG) spectroscopy holds several important advantages over traditional spectroscopy methods for the molecular level analysis of interfaces, including (i) surface sensitivity, (ii) vibrational specificity, and (iii) the possibility to extract detailed information on the ordering and orientation of molecular groups at the interface by analysis of polarization-dependent SFG spectra.

 

Comparison of Narrowband and Broadband SFG Spectrometers

 

NARROWBAND PICOSECOND SCANNING SFG SPECTROMETER

In order to get SFG spectrum during measurement wavelength of narrowband mid-IR pulse is changed point-by-point throughout the range of interest. Narrowband SFG signal is recorded by the time-gated photomultiplier. Energy of each mid-IR, VIS and SFG pulse is measured. After the measurement, the SFG spectrum can be normalised according to IR and VIS energy. Spectral resolution is determined by the bandwidth of the mid-IR light source. The narrower mid-IR pulse bandwidth, the better the SFG spectral resolution. Separate vibrational modes are excited during the measurement.

BROADBAND FEMTOSECOND SFG SPECTROMETER

A broadband mid-IR pulse is mixed with a narrowband VIS pulse. The result is broadband SFG spectrum which is recorded using a monochromator and a sensitive CCD camera. The full spectrum is acquired simultaneously by integrating signal over time. Spectral resolution is determined by the bandwidth of the VIS pulse and on the monochromator-camera combination. The narrower the bandwidth of VIS pulse, the better the SFG spectral resolution.

 

COMPARISON OF DIFFERENT SFG SPECTROMETRES

Narrowband Picosecond Scanning Spectrometer Broadband Femtosecond High Resolution Spectrometer
Narrowband mid-IR excitation, only one band is excited. Coupled states can be separated. Simultaneous exsitation and recording of broad vibration spectrum with high resolution.
High mid-IR pulse energy. Less influence of IR absorbtion in the air. High mid-IR intensity at low pulse energy – suitable for biological or other water containing samples.
No reference spectrum needed, IR energy measured at each spectral point. Optically coupled IR and VIS channels. Reduced complexity and increased stability of the system.
System is more simple, lower ambient conditions requirements, easier to maintain. Hight repetition rate up to 1 kHz.
 

Features and Design

The SFG spectrometer developed by Ekspla engineers is a nonlinear spectrometry instrument, convenient for everyday use. Ekspla manufactures SFG spectrometers, which are used by chemists, biologists, material scientists, and physicists. The spectrometer has many features that help to set up measurements and to make successful vibrational spectroscopy studies. For chemical and biochemical laboratories, this makes the Ekspla SFG spectrometer a reliable workhorse with a broad spectral region, automatically tuned from 1,000 to 4,300 cm-1, a high spectral resolution (2 or 6 cm-1), and easily controlled adjustment of polarisation optics.

The Ekspla SFG system is based on a mode-locked Nd:YAG laser with a 29 ps pulse duration, with 30 – 40 mJ pulse energy at 1,064 nm and a 50 Hz repetition rate. The VIS channel of the SFG spectrometer consists of part of a laser output beam, usually with doubled frequency (532 nm) up to 0.5 mJ. The main part of the laser radiation goes to an optical parametric generator (OPG) with a difference frequency generation (DFG) extension. The IR channel of the spectrometer is pumped by the DFG output beam with energy in the range of ~40 – 200 μJ. Infrared light can be tuned in a very broad spectral range from 2.3 up to 10 (optionaly up to 16) μm. The bandwidth is 2 or 6 cm-1 (depending on the selected OPG model) and it is one of the main factors of SFG spectrometer spectral resolution. The second beam (VIS) is also narrowband at <2 cm-1.

The spectrometer detection system has a temporal gate. It reduces noise collection and ambient light influence, which allows the spectrometer to be used even in a brightly illuminated room. The spectrometer does not have any acoustic noise because the laser is pumped by diodes. The spot size of the IR beam is adjustable. In this way, the appropriate energy density is achieved to avoid damaging the sample. Spectrum scanning, polarisation control and VIS beam attenuation are controlled from a computer. The spectrometer has a motorized polarisation switch for the IR, optionaly for the VIS, and optionaly the generated SFG light beams . Special detectors continuously monitor the energy of the VIS and mid-IR laser pulses, so IR energy is checked at each measurement point. This makes it easy to normalize the resulting SFG vibrational spectrum.

SYSTEM COMPONENTS

  • Picosecond mode-locked Nd:YAG laser
  • Multichannel beam delivery unit
  • Picosecond optical parametric generator
  • Spectroscopy module
  • Monochromator
  • PMT based signal detectors
  • Data acquisition system
  • Dedicated LabView® software package for system control
 
 

SPECTROSCOPY MODULE, SAMPLE COMPARTMENT

A large sample compartment can be customised and enables the use of various extensions and additional instruments for simultaneous control of the sample conditions, including a Langmuir-Blodgett trough for air/water and lipid/air interface studies, temperature and humidity-controlled cells, and other instruments.

 
 

SPECTRAL RANGE OF THE SFG SPECTROMETER

The spectral range of the infrared beam determines available vibrational spectra and the spectral range of the spectrometer.

The main modification of the spectrometer enables a spectral range of 1,000 to 4,300 cm-1.

SFG Spectrometer available with a shorter spectral range 2,500 to 4,300 cm-1.

SFG spectrometer with extended vibrational frequency range. Using an additional crystal in the laser light source, the range of the spectrometer expands by up to 625 cm-1. This opens a fingerprint spectral region for the analysis of many inorganic compounds, the vibrations of ions and biomolecules.

 

SAFETY OF THE SFG SPECTROMETER

The spectrometer is safe to use: all high energy pulsed beams are enclosed. In addition, the sample area also has a special cover. During the measurements, it is possible to close the sample compartment so that radiation cannot penetrate outside. The automatic change of polarisation and energy attenuation makes it possible to perform measurements without opening the spectrometer. Laser safety precautions are required only for the alignment of the laser beams on the studied surface.

Modifications and Options

MODIFICATIONS

  • Double resonance SFG spectrometer – allows investigation of vibrational mode coupling to electron states at a surface
  • Phase sensitive SFG spectrometer – allows measurement of the complex spectra of surface nonlinear response coefficients

OPTIONS

  • Single or double wavelength VIS beam: 532 nm and/or 1064 nm
  • One or two detection channels: main signal and reference
  • Second harmonic generation surface spectroscopy option
  • High resolution option – down to 2 cm-1
  • Motorized VIS and IR beams alignment system
  • Motorized polarisation control for VIS and SFG beams
  • Larger SFG box for Langmuir trough

Double resonance SFG spectrometer

Both IR and VIS wavelengths are tunable in Double resonance SFG spectrometer model.

This two-dimensional spectroscopy is more selective than single resonant SFG. Double resonant SFG allows investigation of vibrational mode coupling to electron states at a surface. Double resonance enables the use of another wavelength for VIS beam if the sample has strong absorption at 532 nm and 1064 nm. A range 420 – 680 nm is typically used for VIS beam.

Two outputs PL2230 laser is used for this spectrometer.

Phase-sensitive SFG spectrometer

SFG spectrometer with additional phase sensitive measurements option. A phase sensitive spectrometer allows the measurement the phase of nonlinear susceptibility χ(2). Reference and test samples are used and the SFG phase difference between them is scanned. The real and imaginary parts of second order susceptibility are calculated from the experimental results. Such an approach enables the unambiguous determination of the orientation of molecular groups at the interface.

PHASE SENSITIVE MEASUREMENTS WITH SPECTRAL RESOLUTION UP TO 6 CM⁻¹ (2 CM⁻¹).

In conventional SFG-VS intensity of SF signal is measured. It is proportional to the square of second order nonlinear susceptibility ISF ~ | χ(2) |2. However, χ(2) is complex, and for complete information, we need to know both the amplitude and the phase. This will allow us to determine the absolute direction in which the bonds are pointing and characterize their tilt angle with respect to the surface. Measurement of the phase of an optical wave requires an interference scheme. Mixing the wave of interest with a reference wave of known phase generates an interference pattern, from which the phase of the wave can be deduced.

In practice Phase-sensitive SFG experimental setup includes two samples generating SF signal simultaneously. One sample (usually called local oscillator) has well known and flat spectral response. Second one is investigated sample. The excitation beams are directed to first sample, where SFG beam is generated. Later all three beams are retranslated to the second sample, where another SFG beam is generated. Due to electromagnetic waves coherence both SFG beam are interfering. Setup contains the phase modular located on the SFG beam path between samples. We are able to change the phase of SFG beam by rotating it. This way we are recording two-dimensional interfererogram with wavelength and phase shift on x and y axis. Using fitting algorithms we are able to calculate the amplitude and phase of SF signal.

PHASE SENSITIVE SFG + CLASSIC SFG SPECTROMETER IN ONE UNIT

Interference measurements of SFG signals from reference sample and the investigated sample for Phase-sensitive configuration.

Switchable setup. Phase sensitiv / “Classic” (“Advanced”) ; Top/ Bottom configuration. Switch: VIS beam manual. IR mirrors motorised, BaF₂ lens manual. Path length to the sample is same in all configuration. Motorised polarisation control. VIS beam 532 nm. IR 2.3 – up to 10 (16) µm.

OPTIONS

  • Spectrometer has “classic” and “Phase-sensitive” properties
  • Easy switching between setups
  • Adjustable spot size for classic configuration
 

Narrowband SFG system <2 cm-1

Spectral resolution in of narrowband SFG is determined by light source – OPA. Monochromator is used only as filter.

Light source for IR: PG511. Line width of mid-IR < 2 cm-1.

Synchronously pumped optical parametric generator with OPO with long focal length resonator.

Components & Optional Accessories

PICOSECOND MODE-LOCKED ND:YAG LASER

The heart of the spectrometer is solid-state picosecond laser. Its reliability is critical to perfect spectrometer operation and relevance of measured data. Two standard models of high energy lasers are dedicated for SFG spectrometers. Model PL2230 is fully diode pumped, which means that master oscillator and all following amplification stages are diode pumped. It features great long term parameters stability and minimal maintenance requirements.

This model provides up to 40 mJ per pulse output energy, which in most cases is enough for pumping OPG and VIS channel of SFG spectrometer. Model PL2230 is available for double resonance SFG. This model usually is used for pumping of two independent OPG’s. Such configuration is used in double resonance SFG version.

MULTICHANNEL BEAMS DELIVERY UNIT

Fundamental laser radiation needs to be split into several channels and converted to different wavelenghts. Tunable IR radiation is generated in picosecond optical parametric generator (OPG). Large portion of laser output is converted into second or third harmonics and used for OPG pumping. Residual beam is spatially filtered, delayed and directed into SFG spectrometer as VIS channel. Usually it is converted into second harmonic (532 nm), but in some cases can be used also at fundamental wavelength (1064 nm) or tunable in visible range, when second OPG is used.

Multichannel beams delivery unit SFGHX00 series provides all these features. Additionally it contains automatized VIS channel input energy monitoring and control. The VIS channel wavelength (if double wavelenght option is included) is changed manually. Setup also includes all needed separators and filters to block residual radiation and prevent it from reaching a sample.

PICOSECOND OPTICAL PARAMETRIC GENERATOR

PG501 series picosecond optical parametric generator (OPG) feature high pulse energy and narrow linewidth. It is used for generation of tunable wavelength in broad spectral range. In SFG spectrometer it provides middle infrared radiation for IR channel. DFG stage extends tuning range to mid IR, which corresponds to molecular vibrational fingerprints. Depending of OPG model, DFG output can cover spectral range 2.3 – 10 µm or 2.3 – 16 µm. All residual wavelengths are carefully filtered preventing residual radiation from reaching a sample.

Visible laser pointer is installed inside each unit and aligned in-line with IR beam. It helps to manage invisible mid IR radiation and direct it through multiple optical elements into a sample. Some SFG-VS studies require better than 6 cm-1 spectral resolution. In such cases Ekspla offers unique design PG511 series OPG. In this system seed is generated in synchronously pumped optical parametric oscillator (SPOPO), which is temporally synchronized with laser regenerative amplifier. In this configuration radiation spectral width is narrowed down to 2 cm-1 in mid IR range.

STANDARD GEOMETRIES

However, in some experiments one layer of the sample can be transparent only for VIS beam, but not for IR beam and vice versa. In such case experimental setup requires different geometries. This problem can be solved, if we can access interface from different sides, for example directing VIS beam from the top and IR beam from the bottom. Ekspla offers several standard geometries: top side, bottom side, top-bottom side and total internal reflection. All of them can be implemented in single spectroscopy unit and easy interchangeable. The special design of SFG spectrometer provides possibility to change angles of interaction. This feature together with different polarization combinations helps better understand molecular dipoles orientation.

In our spectrometer we use large aperture parabolic mirror. The sample is places in focal point of parabolic mirror. Such solution makes optical system extremely simple in operation, because it guarantee the same beams position on the sample surface and perfect overlap, when incidence angle is changed.
Sample surface and beams overlap can be monitored using camera installed above sample area. This utility is integrated into every SFG spectrometer. On a special request sample visualization system can be combined with motorized beams adjustment. This allows to align SFG spectrometer from PC, even being physically far from it. It essentially solves safety issues and opens new possibilities for multiple long time experiments without accessing spectroscopy box.

SFG SPECTROMETER ACCESSORIES

  • Six axis sample holder
  • Sealed temperature controlled sample chamber
  • Larger sample area- space for Langmuir trough
  • Motorisation of polarisation control of VIS and IR beams, polarisation analyser for SFG signal
 

Polarisation Control Options

SIMULTANEOUS MEASUREMENT OF S AND P POLARISATION

S and P polarisation of the SFG signal are detected during the same measurement in the dual polarisation detection system.

MOTORIZED POLARISATION CONTROL OF SFG, VIS, IR

The SFG spectrometer has a motorized polarisation switch for the IR, VIS, and the generated SFG light beams. The automatic change of polarisation and energy attenuation makes it possible to perform measurements without opening the spectrometer.

  • Motorized switching of IR – standard
  • Motorized control in small steps of SFG, VIS – optionally
 

Specifications

Version 1) SFG Classic SFG Advanced SFG Double Resonance SFG Phase Sensitive
SYSTEM (general)
Spectral range 1000 – 4300 cm-1 625 – 4300 cm-1 1000 – 4300 cm-1 1000 – 4300 cm-1
Spectral resolution <6 cm-1
(optional <2 cm-1)
<10 cm-1 <6 cm-1
(optional <2 cm-1)
Spectra acquisition method Scanning
Sample illumination geometry Top side, reflection (optional: bottom side, top-bottom side, total internal reflection)
Incidence beams geometry Co-propagating, non-colinear (optional: colinear)
Incidence angles Fixed, VIS ~60 °, IR ~55 ° (optional: tunable) Fixed, VIS ~60 °, IR ~55 °
VIS beam wavelength 532 nm
(optional: 1064 nm)
532 nm and
tunable 420 – 680 nm
532 nm
Polarization (VIS, IR, SFG) Linear, selectable “s” or “p”, purity > 1:100
Beam spot on the sample Selectable, ~150 – 600 µm Fixed
Sensitivity Air-water spectra Solid sample
PUMP LASERS 2)
Model PL2231-50 PL2231A PL2231-50
Pulse energy Optimised to pump PG
Pulse duration 29 ± 5 ps
Pulse repetition rate 50 Hz
OPTICAL PARAMETRIC GENERATORS
IR source with standard linewidth (<6 cm-1) PG501-DFG1 PG501-DFG2 PG501-DFG1
IR source with narrow linewidth (<2 cm-1) PG511-DFG PG511-DFG2 inquire PG511-DFG
UV-VIS source for Double resonance SFG PG401
For standard specifications please check the brochure of particular model
PHYSICAL DIMENSIONS (footprint)
Standard 2700 × 1000 mm 3000 × 1500 mm 2700 × 1200 mm
Extended (with special options or large accessories) 2800 × 1200 mm 3000 × 1500 mm 2800 × 1200 mm
  1. Due to continuous product improvements, specifications are subject to changes without advance notice.
  2. Laser is optimised for pumping parametrical generator, maximum output energy may be different than specified for stand alone application.

Publications

Found total :
25 articles, 25 selected
Application selected :
All Applications

Structure Determination of Hen Egg-White Lysozyme Aggregates Adsorbed to Lipid/Water and Air/Water Interfaces

Related applications: Laser Spectroscopy SFG

Hydrogen bonding interactions of H2O and SiOH on a boroaluminosilicate glass corroded in aqueous solution

Related applications: Laser Spectroscopy SFG

Vibrational Relaxation Lifetime of a Physisorbed Molecule at a Metal Surface

Related applications: Laser Spectroscopy Pump-probe Spectroscopy SFG

Reconfiguration of interfacial energy band structure for high-performance inverted structure perovskite solar cells

Related applications: Laser Spectroscopy SFG

Heavy Anionic Complex Creates a Unique Water Structure at a Soft Charged Interface

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Vibrational fingerprint of localized excitons in a two-dimensional metal-organic crystal

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Aggregation States of Poly(4-methylpentene-1) at a Solid Interface

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Segregation of an amine component in a model epoxy resin at a copper interface

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High-performance graphdiyne-based electrochemical actuators

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Sum Frequency Generation Vibrational Spectroscopy for Characterization of Buried Polymer Interfaces

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Structure of the Fundamental Lipopeptide Surfactin at the Air/Water Interface Investigated by Sum Frequency Generation Spectroscopy

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A structural and temporal study of the surfactants behenyltrimethylammonium methosulfate and behenyltrimethylammonium chloride adsorbed at air/water and air/glass interfaces using sum frequency generation spectroscopy

Related applications: Laser Spectroscopy SFG

Discovery of Cellulose Surface Layer Conformation by Nonlinear Vibrational Spectroscopy

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Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues

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The complex nature of calcium cation interactions with phospholipid bilayers

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Platelet-adhesion behavior synchronized with surface rearrangement in a film of poly(methyl methacrylate) terminated with elemental blocks

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Retrieval of complex χ(2) parts for quantitative analysis of sum-frequency generation intensity spectra

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Quantitative Sum-Frequency Generation Vibrational Spectroscopy of Molecular Surfaces and Interfaces: Lineshape, Polarization, and Orientation

Related applications: Laser Spectroscopy SFG

Unified treatment and measurement of the spectral resolution and temporal effects in frequency-resolved sum-frequency generation vibrational spectroscopy (SFG-VS)

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Alkanethiols as Inhibitors for the Atmospheric Corrosion of Copper Induced by Formic Acid: Effect of Chain Length

Related applications: Laser Spectroscopy SFG

Simultaneous measurement of magnitude and phase in interferometric sum-frequency vibrational spectroscopy

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Phase measurement in nondegenerate three-wave mixing spectroscopy

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Investigating buried polymer interfaces using sum frequency generation vibrational spectroscopy

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Probing the Orientation and Conformation of α-Helix and β-Strand Model Peptides on Self-Assembled Monolayers Using Sum Frequency Generation and NEXAFS Spectroscopy

Related applications: Laser Spectroscopy SFG

Study of self-assembled triethoxysilane thin films made by casting neat reagents in ambient atmosphere

Related applications: Laser Spectroscopy SFG


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