Single molecule mapping of the optical field distribution of probes for near-field microscopy

The most difficult task in near-field scanning optical microscopy (NSOM) is to make a high quality subwavelength aperture probe. Recently, we have developed high definition NSOM probes by focused ion beam (FIB) milling. These probes have a higher brightness, better polarization characteristics, better aperture definition and a flatter end face than conventional NSOM probes. We have determined the quality of these probes in four independent ways: by FIB imaging and by shear-force microscopy (both providing geometrical information), by far-field optical measurements (yielding throughput and polarization characteristics), and ultimately by single molecule imaging in the near-field. In this paper, we report on a new method using shear-force microscopy to study the size of the aperture and the end face of the probe (with a roughness smaller than 1.5 nm). More importantly, we demonstrate the use of single molecules to measure the full three-dimensional optical near-field distribution of the probe with molecular spatial resolution. The single molecule images exhibit various intensity patterns, varying from circular and elliptical to double arc and ring structures, which depend on the orientation of the molecules with respect to the probe. The optical resolution in the measurements is not determined by the size of the aperture, but by the high optical field gradients at the rims of the aperture. With a 70 nm aperture probe, we obtain fluorescence field patterns with 45 nm FWHM. Clearly, this unprecedented near-field optical resolution constitutes an order of magnitude improvement over far-field methods like confocal microscopy.     

Single molecule mapping of the optical field distribution of probes for near-field microscopy

The most difficult task in near-field scanning optical microscopy (NSOM) is to make a high quality subwavelength aperture probe. Recently, we have developed high definition NSOM probes by focused ion beam (FIB) milling. These probes have a higher brightness, better polarization characteristics, better aperture definition and a flatter end face than conventional NSOM probes. We have determined the quality of these probes in four independent ways: by FIB imaging and by shear-force microscopy (both providing geometrical information), by far-field optical measurements (yielding throughput and polarization characteristics), and ultimately by single molecule imaging in the near-field. In this paper, we report on a new method using shear-force microscopy to study the size of the aperture and the end face of the probe (with a roughness smaller than 1.5 nm). More importantly, we demonstrate the use of single molecules to measure the full three-dimensional optical near-field distribution of the probe with molecular spatial resolution. The single molecule images exhibit various intensity patterns, varying from circular and elliptical to double arc and ring structures, which depend on the orientation of the molecules with respect to the probe. The optical resolution in the measurements is not determined by the size of the aperture, but by the high optical field gradients at the rims of the aperture. With a 70 nm aperture probe, we obtain fluorescence field patterns with 45 nm FWHM. Clearly, this unprecedented near-field optical resolution constitutes an order of magnitude improvement over far-field methods like confocal microscopy.     

Image contrast of dielectric specimens in transmission mode near-field scanning optical microscopy: imaging properties and tip artefacts

Near-field scanning optical microscopy (NSOM) is a scanned probe technique utilizing a subwavelength-sized light source for high-resolution imaging of surfaces. Although NSOM has the potential to exploit and extend the experimental utility of the modern light microscope, the interpretation of image contrast is not straightforward. In near-field microscopy the illumination intensity of the source (probe) is not a constant value, rather it is a function of the probe–sample electronic environment. A number of dielectric specimens have been studied by NSOM to elucidate the contrast role of specimen type, topography and crystallinity; a summary of metallic specimen observations is presented for comparative purposes. Near-field image contrast is found to be a result of lateral changes in optical density and edge scattering for specimens with little sample topography. For surfaces with considerable topography the contributions of topographic (Z) axis contrast to lateral (X,Y) changes in optical density have been characterized. Selected near-field probes have also been shown to exhibit a variety of unusual contrast artefacts. Thorough study of polarization contrast, optical edge (scattering) contrast, as well as molecular orientation in crystalline specimens, can be used to distinguish lateral contrast from topographic components. In a few cases Fourier filtering can be successfully applied to separate the topographic and lateral contrast components.     

Diffraction of circularly polarized light from near-field optical probes

Diffracted fields from 100-nm aperture near-field scanning optical microscopy (NSOM) probes and uncoated tapered fibres are measured and analysed. Using a solid angle scanner, the two-dimensional intensity distribution and polarization state of the diffracted light are resolved experimentally. Polarization analyses show that circularly polarized input light does not maintain its polarization state for all diffraction angles, and is completely filtered into linearly polarized light at large polar diffraction angles. This drastic decomposition originates from the vector nature of light diffracted by the sub-wavelength aperture. There is a fundamental difficulty in generating circularly polarized light near the aperture of NSOM probes owing to polarization-dependent diffraction in the near-field regime. This is illustrated by the Bethe-Bouwkamp model using circularly polarized input light.     

Evanescent field excitation and measurement of dye fluorescence in a metallic probe near-field scanning optical microscope

We introduce a method of dye fluorescence excitation and measurement that utilizes a near-field scanning optical microscope (NSOM). This NSOM uses an apertureless metallic probe, and an optical system that contains a high numerical aperture (NA) objective lens (NA= 1.4). When the area which satisfies NA < 1 is masked, the objective lens allows for the rejection of possible transmitted light (NA < 1) through the sample. In such conditions, the focused spot consists of only the evanescent field. We found that this NSOM system strongly reduces the background of the dye fluorescence and allows for the measurement of the fluorescence intensity below the diffraction limit of the excitation source.     

Diffraction of circularly polarized light from near-field optical probes

Diffracted fields from 100-nm aperture near-field scanning optical microscopy (NSOM) probes and uncoated tapered fibres are measured and analysed. Using a solid angle scanner, the two-dimensional intensity distribution and polarization state of the diffracted light are resolved experimentally. Polarization analyses show that circularly polarized input light does not maintain its polarization state for all diffraction angles, and is completely filtered into linearly polarized light at large polar diffraction angles. This drastic decomposition originates from the vector nature of light diffracted by the sub-wavelength aperture. There is a fundamental difficulty in generating circularly polarized light near the aperture of NSOM probes owing to polarization-dependent diffraction in the near-field regime. This is illustrated by the Bethe-Bouwkamp model using circularly polarized input light.     

Evanescent field excitation and measurement of dye fluorescence in a metallic probe near-field scanning optical microscope

We introduce a method of dye fluorescence excitation and measurement that utilizes a near-field scanning optical microscope (NSOM). This NSOM uses an apertureless metallic probe, and an optical system that contains a high numerical aperture (NA) objective lens (NA = 1.4). When the area which satisfies NA < 1 is masked, the objective lens allows for the rejection of possible transmitted light (NA < 1) through the sample. In such conditions, the focused spot consists of only the evanescent field. We found that this NSOM system strongly reduces the background of the dye fluorescence and allows for the measurement of the fluorescence intensity below the diffraction limit of the excitation source.     

Photoluminescence imaging of phosphor particles using near-field optical microscope with UV light excitation

We have developed fibre probes suitable for 325 nm UV light excitation and a photoluminescence near-field scanning optical microscope (NSOM) and demonstrated the photoluminescence imaging of phosphor BaMgAl10O17:Eu2+ (BAM) particles. The probe was fabricated by a two-step-etching method that we developed. The probe had a large taper angle at the top of the probe and a small taper angle at the root. The NSOM image was different from the topographical structure but roughly reflected the corresponding features of the particles. The inhomogeneity of the photoluminescence intensity between BAM particles was observed in the NSOM image. The photoluminescence intensity with various bandpass filters showed differences between the individual particles, which means that they have different spectra.     

Photoluminescence imaging of phosphor particles using near-field optical microscope with UV light excitation

We have developed fibre probes suitable for 325 nm UV light excitation and a photoluminescence near-field scanning optical microscope (NSOM) and demonstrated the photoluminescence imaging of phosphor BaMgAl₁₀O₁₇:Eu²⁺ (BAM) particles. The probe was fabricated by a two-step-etching method that we developed. The probe had a large taper angle at the top of the probe and a small taper angle at the root. The NSOM image was different from the topographical structure but roughly reflected the corresponding features of the particles. The inhomogeneity of the photoluminescence intensity between BAM particles was observed in the NSOM image. The photoluminescence intensity with various bandpass filters showed differences between the individual particles, which means that they have different spectra.     

Spectroscopy with scanning near-field optical microscopy using photon tunnelling mode

We have demonstrated Raman spectroscopy using scanning near-field optical microscopy (SNOM). Photon tunnelling mode was employed, in which the sample is illuminated using an attenuated total reflection (ATR) configuration and the evanescent wave perturbed by the sample is picked up by a sharpened optical fibre probe. By this experimental arrangement Raman scattering from the optical fibre probe was greatly reduced, therefore we were able to excite the sample using more intense laser light compared to the illumination mode SNOM. Raman spectra of copper phthalocyanine (CuPc) were obtained in the off-resonance condition and without using surface-enhanced Raman scattering (SERS).     

Inducing superconductivity at a nanoscale: photodoping with a near-field scanning optical microscope

The local modification of an insulating GdBa2Cu3O6.5 thin film, made superconducting by illumination with a near-field scanning optical microscope (NSOM), is reported. A 100-nm aperture NSOM probe acts as a sub-wavelength light source of wavelength lambda(exc) = 480-650 nm, locally generating photocarriers in an otherwise insulating GdBa2-Cu3O6.5 thin film. Of the photogenerated electron-hole pairs, electrons are trapped in the crystallographic lattice, defining an electrostatic confining potential to enable the holes to move. Reflectance measurements at lambda = 1.55 microm at room temperature show that photocarriers can be induced and constrained to move on a approximately 200 nm scale for all investigated lambda(exc). Photogenerated wires present a superconducting critical temperature Tc= 12 K with a critical current density Jc = 10(4) A cm(-2). Exploiting the flexibility provided by photodoping through a NSOM probe, a junction was written by photodoping a wire with a narrow (approximately 50 nm) under-illuminated gap. The strong magnetic field modulation of the critical current provides a clear signature of the existence of a Josephson effect in the junction.     

Near-field effects in single molecule emission

We present the first experimental proof of the influence of a nearby nano-sized metal object on the angular photon emission by a single molecule. A novel angular sensitive detection scheme is implemented in an existing near-field scanning optical microscope (NSOM). The positioning accuracy (∼1 nm) of the NSOM allows a systematic investigation of the intensity ratio between two different half-spaces as a function of the position of the metal–glass interfaces of the probe with respect to the single emitter. The observed effects are shown to be particularly strong for molecules that are excited mainly below the rims of the aperture. An excellent agreement is found between experiments and numerical simulations for these molecules. The observed angular redistribution of the angular emission of a single molecule could explain the alteration of the emission polarization observed for certain molecules in earlier experiments (Veerman et al. (1999) J. Microsc. 194 , 477–482).     

Near-field fluorescence imaging of single molecules with a resolution in the range of 10 nm

We demonstrate fluorescence imaging of single molecules, by near-field scanning optical microscopy (NSOM), using the illumination-collection mode of operation, with an aperture probe. Fluorescence images of single dye molecules were obtained with a spatial resolution of 15 nm, which is smaller than the diameter of the aperture (20 nm) of the probe employed. Such super-resolution may be attributable to non-radiative energy transfer from the molecules to the coated metal of the probe since the resolution obtained in the case of conventional NSOM is limited to 30–50 nm due to penetration of light into the metal.     

Large-area topography analysis and near-field Raman spectroscopy using bent fibre probes

We present a method for combined far‐field Raman imaging, topography analysis and near‐field spectroscopy. Surface‐enhanced Raman spectra of Rhodamine 6G (R6G) deposited on silver nanoparticles were recorded using a bent fibre aperture‐type near‐field scanning optical microscope (NSOM) operated in illumination mode. Special measures were taken to enable optical normal‐force detection for control of the tip–sample distance. Comparisons between far‐field Raman images of R6G‐covered Ag particle aggregates with topographic images recorded using atomic force microscopy (AFM) indicate saturation effects due to resonance excitation.     

The role of tip plasmons in near-field Raman microscopy

The enhancement in electric field strength in the vicinity of a metal tip, through the excitation of plasma modes in the tip, is investigated using the finite difference time domain method; such tip enhancement has significant potential for application in scanning near-field Raman microscopy. To represent an experimentally realistic geometry the near-field probe is described by a conical metal tip with a spherical apex, with radii 20 nm and 200 nm considered, in close proximity to a glass substrate. Illumination through the substrate is considered, both at normal incidence and close to the critical angle, with the polarization in the plane of incidence. By modelling the frequency dependent dielectric response of the metal tip we are able to highlight the dependence on the scattering geometry of the nature of the electromagnetic excitations in the tip. In particular, the strongest electric field enhancement with the greatest confinement occurs for the excitation of modes localized at the tip apex, excited only for off-normal incidence. Bulk modes excited in the tip also produce enhancement, although over a larger area and with significantly less enhancement than that of the localized modes; however, the excitation of bulk modes is independent of the angle of incidence.     

Study of the focused laser spots generated by various polarized laser beam conditions

In this work, three‐dimensional near‐field imaging of the focused laser spot was studied theoretically and experimentally. In the theoretical simulation, we use the electromagnetic equivalent of the vectorial Kirchhoff diffraction integral to calculate the intensity distribution of the focal region, and a high depolarization is found in high numerical aperture systems (NA = 0.85). The experimental set‐up is based on a near‐field scanning optical microscope (NSOM) system. A high‐NA objective lens is used to focus incident light of various polarizations, and a tapered near‐field optical fibre probe of the NSOM system is used to determine the intensity of the focal field. The results show an asymmetric distribution of the focused intensity with the linear polarized laser beam.     

Moulded photoplastic probes for near-field optical applications

The inexpensive fabrication of high-quality probes for near-field optical applications is still unsolved although several methods for integrated fabrication have been proposed in the past. A further drawback is the intensity loss of the transmitted light in the 'cut-off' region near the aperture in tapered optical fibres typically used as near-field probes. As a remedy for these limitations we suggest here a new wafer-scale semibatch microfabrication process for transparent photoplastic probes. The process starts with the fabrication of a pyramidal mould in silicon by using the anisotropic etchant potassium hydroxide. This results in an inverted pyramid limited by < 111 > silicon crystal planes having an angle of ∼ 54°. The surface including the mould is covered by a ∼ 1.5 nm thick organic monolayer of dodecyltrichlorosilane (DTS) and a 100-nm thick evaporated aluminium film. Two layers of photoplastic material are then spin-coated (thereby conformal filling the mould) and structured by lithography to form a cup for the optical fibre microassembly. The photoplastic probes are finally lifted off mechanically from the mould with the aluminium coating. Focused ion beam milling has been used to subsequently form apertures with diameters in the order of 80 nm. The advantage of our method is that the light to the aperture area can be directly coupled into the probe by using existing fibre-based NSOM set-ups, without the need for far-field alignment, which is typically necessary for cantilevered probes. We have evidence that the aluminium layer is considerably smoother compared to the 'grainy' layers typically evaporated on free-standing probes. The optical throughput efficiency was measured to be about 10⁻⁴. This new NSOM probe was directly bonded to a tuning fork sensor for the shear force control and the topography of a polymer sample was successfully obtained.     

The effects of probe boundary conditions and propagation on nano-Raman spectroscopy

Raman spectra obtained in the near‐field, with collection of the Raman‐shifted light in reflection, show selective enhancement of vibrational modes. We show that the boundary conditions for an electric field near a metal surface affect propagation of the reflected signal and lead to this selection. The enhancement of certain Raman forbidden vibrations is explained by the presence of an electric field gradient near the metal‐apertured fibre probe.     

Tapping-mode tuning-fork near-field scanning optical microscopy of low power semiconductor lasers

The newly developed inverted tapping-mode tuning-fork near-field scanning optical microscopy (TMTF-NSOM) is used to study the local near-field optical properties of strained AlGaInP/Ga_0.4In_0.6P low power visible multiquantum-well laser diodes. In contrast to shear-force mode NSOM, TMTF-NSOM provides the function to acquire the evanescent wave intensity ratio | I (2ω)|/| I (ω)| image, from which the evanescent wave decay coefficient q can be evaluated for a known tapping amplitude. Moreover, we probe the near-field stimulated emission spectrum, which gives the free-space laser light wavelength λ_o and the index of refraction n _r of the laser diode resonant cavity. Once q , λ_o, and n _r are all measured, we can determine the angle of incidence θ_o of the dominant totally internally reflected waves incident on the front mirror facet of the resonator. Determination of such an angle is very important in modelling the stability of the laser diode resonator.     

Nondestructive measurement of machining-induced amorphous layers in single-crystal silicon by laser micro-Raman spectroscopy

Laser micro-Raman spectroscopy was used to examine silicon wafers precision machined by diamond tools, and the results were compared with transmission electronic microscopic results. It was found that near-surface amorphous layers were generated by machining and there was a strong correlation between the thickness of the amorphous layer and the Raman intensity ratio of the amorphous phase to the crystalline phase. This finding provides the feasibility of a fast, inexpensive, nondestructive and quantitative measurement approach for subsurface damages of semiconductor materials by using laser micro-Raman spectroscopy. The effective measurement range was experimentally investigated and the sensing limits were theoretically discussed from the aspect of light scattering and light absorption with a double-layer material model.