Nano-FTIR (nanoscale Fourier transform infrared spectroscopy) is a scanning probe technique that utilizes as a combination of two techniques: Fourier transform infrared spectroscopy (FTIR) and scattering-type scanning near-field optical microscopy (s-SNOM). As s-SNOM, nano-FTIR is based on atomic-force microscopy (AFM), where a sharp tip is illuminated by an external light source and the tip-scattered light (typically back-scattered) is detected as a function of tip position. A typical nano-FTIR setup thus consists of an atomic force microscope, a broadband infrared light source used for tip illumination, and a Michelson interferometer acting as Fourier-transform spectrometer. In nano-FTIR, the sample stage is placed in one of the interferometer arms, which allows for recording both amplitude and phase of the detected light (unlike conventional FTIR that normally does not yield phase information). Scanning the tip allows for performing hyperspectral imaging (i.e. complete spectrum at every pixel of the scanned area) with nanoscale spatial resolution determined by the tip apex size. The use of broadband infrared sources enables the acquisition of continuous spectra, which is a distinctive feature of nano-FTIR compared to s-SNOM. Nano-FTIR is capable of performing infrared (IR) spectroscopy of materials in ultrasmall quantities and with nanoscale spatial resolution. The detection of a single molecular complex and the sensitivity to a single monolayer has been shown. Recording infrared spectra as a function of position can be used for nanoscale mapping of the sample chemical composition, performing a local ultrafast IR spectroscopy and analyzing the nanoscale intermolecular coupling, among others. A spatial resolution of 10 nm to 20 nm is routinely achieved. For organic compounds, polymers, biological and other soft matter, nano-FTIR spectra can be directly compared to the standard FTIR databases, which allows for a straightforward chemical identification and characterization.
Nano-FTIR does not require special sample preparation and is typically performed under ambient conditions. It uses an AFM operated in noncontact mode that is intrinsically nondestructive and sufficiently gentle to be suitable for soft-matter and biological sample investigations. Nano-FTIR can be utilized from THz to visible spectral range (and not only in infrared as its name suggests) depending on the application requirements and availability of broadband sources. Nano-FTIR is complementary to tip-enhanced Raman spectroscopy (TERS), SNOM, AFM-IR and other scanning probe methods that are capable of performing vibrational analysis.
Basic principles
Nano-FTIR is based on s-SNOM, where the infrared beam from a light source is focused onto a sharp, typically metalized AFM tip and the backscattering is detected. The tip greatly enhances the illuminating IR light in the nanoscopic volume around its apex, creating a strong near field. A sample, brought into this near field, interacts with the tip electromagnetically and modifies the tip (back)scattering in the process. Thus by detecting tip scattering, one can obtain information about the sample.
Nano-FTIR detects the tip-scattered light interferometrically. The sample stage is placed into one arm of a conventional Michelson interferometer, while a mirror on a piezo stage is placed into another, reference arm. Recording the backscattered signal while translating the reference mirror yields an interferogram. The subsequent Fourier transform of this interferogram returns the near-field spectra of the sample.
Placement of the sample stage into one of the interferometer's arms (instead of outside of the interferometer as typically implemented in conventional FTIR) is a key element of nano-FTIR. It boosts the weak near-field signal due to interference with the strong reference field, helps to eliminate the background caused by parasitic scattering off everything that falls into large diffraction-limited beam focus, and most importantly, allows for recording of both amplitude s and phase φ spectra of the tip-scattered radiation. With the detection of phase, nano-FTIR provides complete information about near fields, which is essential for quantitative studies and many other applications. For example, for soft matter samples (organics, polymers, biomaterials, etc.), φ directly relates to the absorption in the sample material. This permits a direct comparison of nano-FTIR spectra with conventional absorption spectra of the sample material, thus allowing for simple spectroscopic identification according to standard FTIR databases.
History Nano-FTIR was first described in 2005 in a patent by Ocelic and Hillenbrand as Fourier-transform spectroscopy of tip-scattered light with an asymmetric spectrometer (i.e. the tip/sample placed inside one of the interferometer arms). The first realization of s-SNOM with FTIR was demonstrated in 2006 in the laboratory of F. Keilmann using a mid-infrared source based on a simple version of nonlinear difference-frequency generation (DFG). However, the mid-IR spectra in this realization were recorded using dual comb spectroscopy principles, yielding a discrete set of frequencies and thus demonstrating a multiheterodyne imaging technique rather than nano-FTIR. The first continuous spectra were recorded only in 2009 in the same laboratory using a supercontinuum IR beam also obtained by DFG in GaSe upon superimposing two pulsed trains emitted from Er-doped fiber laser. This source further allowed in 2011 for the first assessment of nanoscale-resolved spectra of SiC with excellent quality and spectral resolution. At the same time, Huth et al. in the laboratory of R. Hillenbrand used IR radiation from a simple glowbar source in combination with the principles of Fourier-transform spectroscopy, to record IR spectra of p-doped Si and its oxides in a semiconductor device. In the same work the term nano-FTIR was first introduced. However, an insufficient spectral irradiance of glowbar sources limited the applicability of the technique to the detection of strongly-resonant excitations such phonons; and the early supercontinuum IR laser sources, while providing more power, had very narrow bandwidth (<300 cm−1). Further attempt to improve the spectral power, while retaining the large bandwidth of a glowbar source was made by utilizing the IR radiation from a high temperature argon arc source (also known as plasma source). However, due to lack of commercial availability and rapid development of the IR supercontinium laser sources, plasma sources are not widely utilized in nano-FTIR.
The breakthrough in nano-FTIR came upon the development of high-power broadband mid-IR laser sources, which provided large spectral irradiance in a sufficiently large bandwidth (mW-level power in ~1000 cm-1 bandwidth) and enabled truly broadband nanoscale-resolved material spectroscopy capable of detecting even the weakest vibrational resonances. Particularly, it has been shown that nano-FTIR is capable of measuring molecular fingerprints which match well with far-field FTIR spectra, owing to the asymmetry of the nano-FTIR spectrometer that provides phase and thus gives access to the molecular absorption. Recently, the first nanoscale-resolved infrared hyperspectral imaging of a co-polymer blend was demonstrated, which allowed for the application of statistical techniques such as multivariate analysis – a widely used tool for heterogeneous sample analysis.
Additional boost to the development of nano-FTIR came from the utilization of the synchrotron radiation that provide extreme bandwidth, yet at the expense of weaker IR spectral irradiance compared to broadband laser sources.
Commercialization
The nano-FTIR technology has been commercialized by neaspec – a Germany-based spin-off company of the Max Planck Institute of Biochemistry founded by Ocelic, Hillenbrand and Keilmann in 2007 and based on the original patent by Ocelic and Hillenbrand. The detection module optimized for broadband illumination sources was first made available in 2010 as a part of the standard neaSNOM microscope system. At this time, broadband IR-lasers have not been yet commercially available, however experimental broadband IR-lasers prove that the technology works perfect and that it has a huge application potential across many disciplines. The first nano-FTIR was commercially available in 2012 (supplied with still experimental broadband IR-laser sources), becoming the first commercial system for broadband infrared nano-spectroscopy. In 2015 neaspec develops and introduces Ultrafast nano-FTIR, the commercial version of ultrafast nano-spectroscopy. Ultrafast nano-FTIR is a ready-to-use upgrade for nano-FTIR to enable pump-probe nano-spectroscopy at best-in-class spatial resolution. The same year the development of a cryo-neaSNOM – the first system of its kind to enable nanoscale near-field imaging & spectroscopy at cryogenic temperatures – was announced.
Advanced capabilities Synchrotron beamlines integration Nano-FTIR systems can be easily integrated into synchrotron radiation beamlines. The use of synchrotron radiation allows for acquisition of an entire mid-infrared spectrum at once. Synchrotrons radiation has already been utilized in synchrotron infrared microscopectroscopy - the technique most widely used in biosciences, providing information on chemistry on microscales of virtually all biological specimens, like bone, plants, and other biological tissues. Nano-FTIR brings the spatial resolution to 10-20 nm scale (vs. ~2-5 μm in microspectroscopy), which has been utilized for broadband spatially-resolved spectroscopy of crystalline and phase-change materials, semiconductors, minerals, biominerals and proteins.
Ultrafast spectroscopy Nano-FTIR is highly suitable for performing local ultrafast pump-probe spectroscopy due to intereferometric detection and an intrinsic ability to vary the probe delay time. It has been applied for studies of ultrafast nanoscale plasmonic phenomena in Graphene, for performing nanospectroscopy of InAs nanowires with subcycle resolution and for probing the coherent vibrational dynamics of nanoscopic ensembles.
Quantitative studies The availability of both amplitude and phase of the scattered field and theoretically well understood signal formation in nano-FTIR allow for the recovery of both real and imaginary parts of the dielectric function, i.e. finding the index of refraction and the extinction coefficient of the sample. While such recovery for arbitrarily-shaped samples or samples exhibiting collective excitations, such as phonons, requires a resource-demanding numerical optimization, for soft matter samples (polymers, biological matter and other organic materials) the recovery of the dielectric function could often be performed in real time using fast semi-analytical approaches. One of such approaches is based on the Taylor expansion of the scattered field with respect to a small parameter that isolates the dielectric properties of the sample and allows for a polynomial representation of measured near-field contrast. With an adequate tip-sample interaction model and with known measurement parameters (e.g. tapping amplitude, demodulation order, reference material, etc.), the sample permittivity can be determined as a solution of a simple polynomial equation
Subsurface analysis Near-field methods, including nano-FTIR, are typically viewed as a technique for surface studies due to short probing ranges of about couple tip radii (~20-50 nm). However it has been demonstrated that within such probing ranges, s-SNOM is capable of detecting subsurface features to some extents, which could be used for the investigations of samples capped by thin protective layers, or buried polymers, among others.