GB2477817A - Spectroscopy on mutually incoherently luminescing quantum dots, optical read out of quantum troughs, and fabrication of a writable array of quantum troughs - Google Patents

Spectroscopy on mutually incoherently luminescing quantum dots, optical read out of quantum troughs, and fabrication of a writable array of quantum troughs Download PDF

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GB2477817A
GB2477817A GB1011618A GB201011618A GB2477817A GB 2477817 A GB2477817 A GB 2477817A GB 1011618 A GB1011618 A GB 1011618A GB 201011618 A GB201011618 A GB 201011618A GB 2477817 A GB2477817 A GB 2477817A
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diffraction
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Frank Michael Ohnesorge
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/645Specially adapted constructive features of fluorimeters
    • G01N21/6456Spatial resolved fluorescence measurements; Imaging
    • G01N21/6458Fluorescence microscopy
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/58Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances
    • G01N33/588Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances with semiconductor nanocrystal label, e.g. quantum dots
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01QSCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q30/00Auxiliary means serving to assist or improve the scanning probe techniques or apparatus, e.g. display or data processing devices
    • G01Q30/02Non-SPM analysing devices, e.g. SEM [Scanning Electron Microscope], spectrometer or optical microscope
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01QSCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/02Multiple-type SPM, i.e. involving more than one SPM techniques
    • G01Q60/06SNOM [Scanning Near-field Optical Microscopy] combined with AFM [Atomic Force Microscopy]
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01QSCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/18SNOM [Scanning Near-Field Optical Microscopy] or apparatus therefor, e.g. SNOM probes
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B21/00Microscopes
    • G02B21/0004Microscopes specially adapted for specific applications
    • G02B21/002Scanning microscopes
    • G02B21/0024Confocal scanning microscopes (CSOMs) or confocal "macroscopes"; Accessories which are not restricted to use with CSOMs, e.g. sample holders
    • G02B21/0052Optical details of the image generation
    • G02B21/0072Optical details of the image generation details concerning resolution or correction, including general design of CSOM objectives
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B21/00Microscopes
    • G02B21/0004Microscopes specially adapted for specific applications
    • G02B21/002Scanning microscopes
    • G02B21/0024Confocal scanning microscopes (CSOMs) or confocal "macroscopes"; Accessories which are not restricted to use with CSOMs, e.g. sample holders
    • G02B21/0052Optical details of the image generation
    • G02B21/0076Optical details of the image generation arrangements using fluorescence or luminescence
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B21/00Microscopes
    • G02B21/16Microscopes adapted for ultraviolet illumination ; Fluorescence microscopes
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B21/00Microscopes
    • G02B21/36Microscopes arranged for photographic purposes or projection purposes or digital imaging or video purposes including associated control and data processing arrangements
    • G02B21/365Control or image processing arrangements for digital or video microscopes
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/58Optics for apodization or superresolution; Optical synthetic aperture systems
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N2021/6417Spectrofluorimetric devices
    • G01N2021/6423Spectral mapping, video display

Abstract

A method of, video rate spectroscopy on a sample 1.8 of mutually incoherently luminescing quantum dots 6 where the geometry of the sample is known from scanning probe microscopies. For the case where /2 < =a (Mie scattering) A CCD-array 3, measures the intensity profile of the diffraction peaks of a structural detail of the sample, the Fourier transform of the known sample geometry is removed from the diffraction image, this difference is then fourier back transformed. Where /2 >> a (Rayleigh scattering) the scattered image of the sample is recorded, scattering theory is applied to the sample and is subtracted from the scattered image, this difference is then back calculated down to the positions of the quantum dots. In both cases, the image may be aperture-less in the far field. The sample may be a 2d or 3d array of quantum dots. The quantum dots may be memory cells. In an alternative embodiment, a method of fabricating an array of quantum dots is disclosed in which an array of metallic nanoparticles are deposited onto a lattice network of potentiometric leads. Optical read out of quantum troughs via scanning probe techniques is also disclosed.

Description

Concept for laterally resolved optical (far-field -/ Fresnel-regime but also near-field -) FTIR microscopy/spectroscopy below/beyond the lateral diffraction limit -applications for optical (but also electronical) fast read-out of ultra-small memory cells in form of luminescing quantum dots -as well as in biology/crystallography
Description:
The invention is about a technical principle and an aparative technique [an aparatus] Fig. 1 in several versions by means of which fast (time scale of digital video) optical spectroscopy with a lateral resolution below/beyond the general diffraction limit (i.e. < Xlighti'2) can be realized in the optical far field (or also Fresnel-regime/spherical wave approximation). As well the invention is about application examples for a new kind of digital data storage as well as for a microbiological analysis method. In combination with ordinary FTIR (Fourier transform infrared spectroscopy) all mentioned fields of application open up optimally by the this way enormously accelerated data acquisition rate.
The diffraction limit of optics says, that 2 point-like (structural) details cannot be resolved (separately), if their (light) diffraction patterns overlap too closely, to be resolved (i.e. separately visible) e.g. on a photographic film or a frosted glass screen. Fig. ib, 2a,2b explain the definition of the diffraction limit. This case occurs roughly, if the structural detail sizes to be imaged become smaller than the half wavelength of the light used for observing/microscopying, of course still depending on the numerical aperture of the imaging optics [objective lense(s)].
If now, however, this image displaying frosted glass screen is replaced by a CCD-sensor, which is able to quantitatively measure the,,shape" (i.e. the lateral intensitiy profile) of the diffraction peak of a structural detail of the sample -e.g. the Airy-diffraction pattern intensity distribution of a small disc a (for Xlight/2 < a or slightly > a [18] -Mie scattering) or its dipole respectively multipole radiation characteristics (for XjghtI2 >> a -Rayleigh scattering) -then the situation is different and then it could be said, that theoretically, in special cases, there is no diffraction limit of Xlrght/'2 anymore, even if one stays within the picture of linear optics; e.g. in aperture-less microscopy of the diffraction image, if the detector pixel array were almost infinitely large (large effective numerical aperture). Hereby, it is remarked that for Xght > a completely pronounced diffraction minima will not occur anymore. The structures can nevertheless be deconvoluted, since the CCD-camera is measuring intensitiy profiles of the diffraction peaks quantitatively -note that no frosted glass screen is used here. A further physical [deeper fundamental] reason for this statement is, however, that an array of arbitrarily small (nanometric) objects (especially -metallic), if irradiated by light of any wavelength A, they will always -due to non-linear optical (electromagnetic) effects -also emit light again (generally they will luminesce, or fluoresce, phosphoresce), however incoherently with respect to each other and they will also emit scattered electromagnetic radiation of a wavelength of fractions of the above X (Fourier expansion plus multipole expansion of the light emission by a scatterer < or << X) since such a nanometric (in particular if metallic) scatterer is -in a wider sense -always an antenna too. For these,,new", much shorter wavelengths than X, i.e. those A/i, i=1-oc, the diffraction limit holds again in the picture of linear optics and aperture-using microscopy. For the case of AIjght/2 >> a (Rayleigh scattering) instead of the Airy diffraction pattern the radiation characteristics of an antenna (Hertz dipole in the simplest case, or multipole) has to be applied; i.e. roughly proportional to a2sin2v/r2.
For the case of two neighboring microscopically small discs, which are to be imaged, the diffraction patterns of these discs would be two overlapping,,Airy-diffraction pattern functions" (Figs. lb, 2a,b).
If now the geometrical shape of these microscopic structural details is known, e.g. two little round discs, it can of course be calculated, that the resulting diffraction pattern (Fourier space: [equals] 2-dimensional Fourier transformation of the lateral absorption function (x,y)) of two such small discs (e.g. quantum dots) is the interfering overlap of two such Airy-diffraction pattern functions (Figs. 2a and 2b show in this case the envelope of the total intensity, see also Fig. lb which is simply the double slit experiment) and of course, it can be back-calculated [inverse transformed] to the diffracting [scattering] structural details (real space). In the envelope of these interfering Airy diffraction pattern functions, the near field information should still be contained (hypothesis I!), also even in the far field, at least in the Fresnel regime. Here, the reason would be, that partially incoherent light emanates from the [little] discs, because of which the Airy diffraction patterns also -to a small extent -overlap non-interferingly, i.e. they add to a small portion as scalars, also in the general case. For the case of completely independent of each other luminescing quantum troughs, which thus also radiate again completely incoherently with respect to each other, there is -except for the Airy diffraction patterns of the single discs themselves -no interference of the point light sources with respect to each other. Then the Airy diffraction pattern intensity profiles (for XIight/2 <a or slightly > a [18] -Mie scattering) respectively the dipole/multipole radiation characteristics (for XIrghtI2>>a, Rayleigh scattering) add up as scalars [as opposed to vectors] and can thus be deconvoluted more simply by subtraction and single Fourier back-transformation (of the single Airy disc diffraction patterns) afterwards (for Xlrght/2 <= a or slightly > a [18], Mie scattering). For the case of Xlrght/2 >> a (Rayleigh scattering) the Hertz dipole characteristics has to be calculated back to the scatterer (dipole/multipole).
Thus, if, by means of a CCD sensor (e.g. a video camera), the intensity profile of the diffraction image of an arbitrary sample is quantitatively measured, then, in principle, the [this] profile could be theoretically deconvoluted by a numerical computer using certain additional informations about the optical imaging/transformation (mapping of the imaging profile and transfer function of the microscope optics [lenses] regarding an infinitesimal small light point -i.e. the so-called,,point spread function"). The resolution is then only dependent on the light sensitivity and the dynamic range of the pixel of the CCD-camera, as well as on the lateral pixel size relative to the optical magnification of the optical image, but also with respect to the total number of pixels. For highest accuracy, non-linear effects, i.e. the light emission of the sample's nanometric scatterer[s] at additional other, especially smaller, wavelengths than that the sample is irradiated with -which however is still mostly dominating also in the scattered light -, would have to be considered when back-calculating/deconvoluting the optical image.
Due to lense imperfections (even just the finite lense diameter represents of course already a limitation/imperfection), a [simple] pin hole camera [camera obscura] would have advantages; thus, best would be of course an imaging method, which can completely leave out [avoid] any apertures, i.e. in the case if the pixel array is just of sample size, and of course has extremely small pixels, where the pixel size then represents the resolution limit for direct near field imaging in real space. Ideally the detector pixel array is, however, much larger with extremely many and extremely small pixels and the diffracted/scattered image ("Fourier/reciprocal space) of the sample is imaged in the Fresnel regime with taking account of higher diffraction orders (equivalent to smaller sample structure details) -i.e. with very high effective numerical aperture. The real space image is then obtained by numerical (Fourier) back-transformation, eventually numerically corrected for the spherical wave approximation in the Fresnel regime (for AIjghJ2 <=a, Mie scattering). Again in the case of XIight/2>>a (Rayleigh scattering theory has to be applied, i.e. in the simplest case dipole characteristics for every single quantum dot.
For the case that the microscope's optical beam path goes through an optical aparatus (with apertures and lenses), arbitrary structural details which shall be viewed in the optical far field beyond/below the diffraction limit, generally cannot practically be deconvoluted because of the interference, even if the point spread function of the system was determined accurately or could be determined accurately, and thus for instance lense aberrations could be corrected in a digital image acquisition system. However, optical super resolution in the far field by deconvolution should nevertheless be possible with restrictions, if sufficient additional information/[data] are available, for instance from combination with other microscopy methods. For instance, if in the most simple case it is known, that only 2 small discs of known diameter and position (size and distance beyond/below the diffraction limit) are to be imaged, then these 2 Airy-diffraction pattern functions (i.e. the diffraction pattern / diffracted intensity profile of an opaque (dark) disc) respectively the dipole characteristics can be relatively easily deconvoluted/back-calculated; if it is three well-defined discs within the diffraction limit, it is naturally already much more complicated, especially if their positions are unknown, and so forth. The more structural details (and the more ill-defined in shape) within[/below/beyond] the diffraction limit, the more difficult the deconvolution gets of course, if not impossible, since too many unknowns. The more unknowns, the more additional information / boundary values are needed (e.g. from scanning probe microscopies), in order to still make the deconvolution possible. As mentioned, for highest accuracy the non-linear optical effects in light scattering on nanometric structural details (especially metallic nanoparticles as nanometric antennas") have to be taken into account, i.e. besides the irradiated wavelength also the other emitted wavelengths -especially the smaller ones -have to be considered.
Here, the setup of the present invention is initially restricted to the spatially ultrahighly resolved spectroscopy (beyond/below the lateral diffraction limit) of a known sample geometry of incoherent point light sources, in which case the deconvolution becomes much simpler and non-ambiguous; basically here the deconvolution is reduced down to a simple subtraction in "Fourier"/reciprocal space, especially if the many structural details are not to dense [on the sample surface] -the entanglement" [folding] of the diffraction maxima of zeroth order of course becomes stronger, the closer the structural details lie next to each other within the diffraction limit: Thus, if the pixel detector is color sensitive, e.g. by splitting of the imaging light via a prism (as in commercial high quality video cameras usually the case) in three or more beam paths of different color, which are directed onto three or more CCD-sensors (one each for red, yellow[green] and blue), then optical spectroscopy can be preformed with extremely high spatial resolution, essentially only by using a high quality video camera and digital image processing (deconvolution/subtraction) -Fig. 2c. Alternatively, there is also color-CCD-arrays, whose spatial resolution of course is lower in principle (roughly 1/3 because of 3 CCD-pixels per image pixel) and eventually, by means of a tunable interference filter in front of the pixel detector, the spectroscopy can be performed; this latter version would, however, sacrifice partly the here in the present invention emphasized fast data aqcuisition rate advantage [by roughly a factor of three due to the serial acquisition of the 3 colors].
By constant (e.g. back and forth) movement of the CCD sensor, the lateral resolution of the CCD sensors itself could even be optimized to sub-pixel resolution [which is used in state of the art high resolution video microscopy [mentioned by V.Moy]], however, the deconvolution/back-calculation would then be immensely more difficult and more computation-time is needed.
[Obviously, FTIR (Fourier transform infrared spectroscopy) using the setup in Fig.1 would be the spectroscopy method of choice for optimizing a very fast data acquisition rate.] This way, spatially resolved luminescence spectrocopy on a 2-dimensional array of quantum dots is possible, [and it is possible] in the,,far field" (Fig. 2d, exaggeratedly drawn in near vicinity to the sample), i.e. without having to employ the very slow scanning optical near field microscopy for each spectroscopical picture; a scanning probe microscope is needed only once for the initial characterization of especially the geometry and number and ideally also the positions of the quantum troughs (often also named as quantum dots -not quite correctly, because their extent mostly is much larger than the Fermi wavelength of the electrons in the material). This functions especially since the luminescence of the quantum troughs makes them independent (incoherent) light sources with respect to each other, i.e. they do not interfere with each other and the single Airy-diffraction patterns (for Xlrghtl'2 <=a, "Mie") respectively the dipole! multipole characteristics (for ight/2>> a, "Rayleigh") add scalarly. By means of this, a new kind of optical memory can be read out (Fig. 2d, 3), which is based on [2-dimensional] arrays of quantum troughs and thus allows extreme storage density (about 100 times higher than realized so far, taking account of typical quantum trough dimensions[/sizes] of about 5 nm (plus roughly 10 nm mean distance) and nowadays customary structure widths of in micro electronics fabrication of at best roughly 45 nm for conventional microprocessors, DRAMs for instance -not to mention CD5 or DVDs. Moreover, quantum troughs can also be arranged in 3 dimensions[/3-dimensional arrays], not just in 2 dimensions [1,la]. Since the spectroscopy method of the present invention is also based on interferometry/phase contrast, also quantum troughs in somewhat depper lying [buried] layers can be read out -of course provided, they were deposited layer by layer and each layer was geometrically characterized before by mean sof scanning probe microscopy (e.g. AFM).
Writing" of such 3-dimensional arrays of quantum troughs would have to be realized in kind of shift register, as suggested in Fig. 3a,b for 2 dimensions, or scanning by means of scanning probe techniques (of course also [only] for 2 dimensions, for 3 dimensions by means of confocal interferometric methods). In the latter case, only very slow writing would be provided, which, however, could be accelerated by the many probe tips' millipede-concept [2], but still the fast areaV', i.e. not scanning optical read-out of the quantum trough arrays according to the present invention. A further method to electrically contact the quantum troughs, would be a vertically arranged quantum wire array in the electrically insulating substrate layer, according to the manufacturing method in [3] or [4] (CNT-array), as indicated in Fig.3a/ll.
The following Gedankenexperiment shall explain, that fundamentally/theoretically optical microscopy/spectroscopy beyond (below) the diffraction limit should be possible in principle not only in the near field, -even if practically difficult to realize (the main issue in this present patent application): As widely known, optical near field microscopy provides optical resolution far beyond/below the diffraction limit. There, the light coming from the sample (in reflexion or transmission) is recorded using an extremely sensitive photo detector (photon counter) through a tiny (<< light wavelength) aperture which is scanned across the sample, [this light recorded] as a function of the lateral position of the aperture on the sample and thus, a near field optical image of the sample is recorded. This has been proven many times experimentally, also theoretically (z.B. seit [5]), demonstrated many times and lateral resolutions down to a few nm have been achieved -[also using commercial instruments].
If a suitable matrix of pixels were at hand, i.e. a pixel array with extremely small, but extremely sensitive light detectors, which are placed at very small distances to each other, such that the sample could be directly prepared on that pixel array, then equivalently a near field image of the sample would be recorded without having to raster-scan the sample (patent claim 10). Of course, the pixel array has to be roughly of the same size as the sample itself, and each pixel detector would be a near field optical sensor[/detector] replacing the usual near field optical probe tip. In a customarily scanning near field optical microscope usually an extremely sharpened tip-end of a monomode glass fiber is used as a scanning aperture, which is taking up out of the near field regime the initially non-propagating exponentially decaying electromagnetic field (not quite a,,light wave") and is transmitting it via the monomode fiber over longer distances (0(m)) to the photodetector (e.g. a photomultiplier). That means, the light is indeed propagating again after tunneling through the,,layer thickness" of the aperture (diameter <X), even though extremely damped by the aperture (diameter <X); this is widely realized that way, it just is necessary to use an extremely sensitive photon counter (photo multiplier) as a detector. As an explanation: The electromagnetic wave cannot exist/propagate only in the aperture (diameter < X) and in the near field regime [(distance from the sample <X)] itself, or in other words respectively in those regimes a few X away from,,antenna"/the scattering particle [the emitting point of the electromagnetic field], this electromagnetic field is a quasistatic field, oscillating in time; but this field can in fact tunnel through those regimes (the amplitude of the electromagnetic [more accurately speaking the electric and the magnetic field vector which are out of phase] field vector decays roughly exponentially while passing through the aperture; behind the aperture, i.e. many Xs away, no matter whether in a suitable monomode fiber or in free space, the light wave can exist again, thus can also propagate. Now, if it were possible to bundle extremely many of such sharpened fiber tips, such that the bundle's cross section is roughly of the same size as the sample's surface area, a non-scanning optical near field microscope would be at hand, similar to patent claim 11, while of course at each fiber's back end an extremely senistive photo detector would have to be placed at. Such fiber bundles are possible in principle, the problem here would be of merely geometrical nature, because then the fiber length range [close to the probe tip] in which the fiber is (much) thinner than needed for undamped light propagation (of certain wave length, e.g. 633nm) would be very long and the propagating intensity fraction would be damped away rather rapidly, there would be too little intensity arriving at the detector -all this is of course a question of the detectors sesitivity and a question of stray light intensities, i.e. theoretically (in principle) possible but practically -to best of my knowledge -not feasable at present. Thus, a shadow throwing microscope in the far-field would be at hand, just with the difference that the propagating light is,,mediated" via monomode fibers to the detector. In the present invention it is now suggested, to simply omit this (strongly damping) hypothetical fiber bundle and to directly record using an extremely sensitive pixel array (for instance one as suggested in [6]) the admittedly extremely small intensity variations, which, however, still have to be modulated on top of propagating intensity portion (non-linear optical effects, thus Fourier expansion in the wave vector).
Of course, the near field information then becomes drastically "entangled" by the interference, but should -in priciple -still be present in the far field or at least the Fresnel-regime, even though minutely small, at least because of admitteldy very small incoherent luminescence portions in the reflected/transmitted light. These intensity fractions emanating from the quantum troughs thus add scalarly -e.g. the in the scattered light with respect to each other incoherently luminescing quantum troughs; for AIjgh]2 <= a or slightly >a (Mie) it is the Airy diffraction patterns of a small disc a, for XIightI2 >> a (Rayleigh) it is the multipole radiation characteristics, or in approximation the Hertz dipole characteristics.
Quantum mechanical effects (light dependent modulation of the current through quantum wires), in principle [/theoretically] should be able to reach the sensitivity of photo multipliers, perhaps comparable to highly sensitve liquid nitrogen cooled CCD-arrays, which can already detect single photons. The latter makes this possible traded off by the disadvantages of the extensive cooling (which reduces thermal noise) as well as relatively large, thus more sensitive but slow pixel detectors. A quantum electronic detector alone would not know these disadvantages. Especially, a very large (perhaps also hemispherical) light pixel array detector with extremely many and extremely small pixels would be suggested, which hence would in fact provide a very large effective numerical aperture for recording the samples diffraction image (for Ajght/2 <= a or slightly > a [18], Mie). For XIightI2 >> a it [should] provide sufficient intensity profiling of the dipole radiation characteristics of the single scatterers/quantum dots.
Problem and conceptually suggested solution: Optical microscopy and thus optical spectroscopy is diffraction limited in their lateral [spatial] resolution, the diffraction limit amounts to about half the wavelength of the imaging light, additionally dependent only on the numerical aperture of the imaging objective [lense(s)]. Scanning probe microscopies and electron microscopy overcome this (optical) resolution limit (electron microscopy of course only via the much shorter [de Broglie] wavelength of the imaging irradiation), but provide no optical spectroscopy [color] data though. Near field scanning optical microscopy is an exception, which can also provide optical spectroscopic data; however, it is extremely slow (one image in order of minutes to an hour).
The here invented concept shall overcome these limitations: Optically spectroscopic images can be provided at a lateral resolution of a scanning probe microscope and at the same time at the spectroscopical resolution (color) of a light microscope at a maximum picture rate comparable to that of [digital] video microscopy. The concept is based on using spatially highly resolved geometrical (topographcal) pre-information from scanning probe micrsocopies or similar methods, in order to back-calculate (to deconvolute, eventually by mere subtraction in Fourier space) the subsequent light microscope's color images "blurred" by the [lateral] diffraction limit of the same sample mathematically using a computer in real time. In the simplest case at low spatial resolution near the lateral diffraction limit of X/2, this should actually also function for actual real space images [17].
However, in the here primarily proposed concept (Fig.1) "merely" the diffraction image of the sample shall be recorded [optically] and shall then, by means of a computer, be compared with the Fourier-transformed respectively scattering theory-transformed (all sample quantum dots regarded as incoherent dipoles with respect to each other) scanning probe image of the sample and shall then afterwards be finally back-transformed by a computer (not lense-optically). This concept is very useful for the read-out of a new kind of quantum trough memory [cellsJ of extreme storage density -the sample just has to be characterized topographically once (e.g. via scanning probe microscopies or electron microscopy or similar techniques) and then can be rewritten on [electronically] over and over again and optically rapidly be read out over and over again. In this case of many independently of each other luminescing quantum troughs as mutually incoherent light sources the mutual interference of these point light sources will not occur and the many Airy diffraction pattern functions (for X/2<=a or slightly >a [18]) respectively the dipole/multipole radiation intensity profile characteristics (for X/2>>a) will add up as scalars. The deconvolution reduces then to a simple subtraction of these many Airy diffraction pattern profiles respectively dipole profile characteristics and their one by one Fourier back transformation respectivel scattering theoretical back calculation afterwards.
State of the art: Traditional interference/phase contrast microscopy provides vertically the very high spatial resolution of interferometry (i.e. far in the sub-nm regime); however with a lateral spatial resolution which is diffraction limited, i.e. roughly X/2.
An interference microscopical method aiming at a lateral optical resolution beyond/below the diffraction limit, is proposed in EP0776457B1 [7] and references therein. A further optical microscopy method, which however is based on a special kind of laterally varying fluorescence excitation, in which the optical diffraction limit is circumvented, is described in T.Klar et al [8], as well as its technical basic concepts in [9]. The latter is not affecting the present invention, for one reason because it [8,9] is also a slow [line wise] scanning method and for the other reason, since it is based on a locally defined and varying fluorescence excitation (slope steepness of the [fluorescence excitation] as a function of position (x,y) ,,<" diffraction limit) -it is thus related to near field optical microscopy, since it scans a tiny light spot (<X/2 [of the fluorescing -emanating-wavlength], diffraction limit) while also in Hell et al. [8,9] (by pulse illumination) a steep (<X/2 of the fluorescing/emanating light, <diffraction limit) fluorescence exciting light [intensity] slope is scanned [across the sample] (remark: if I understood [8,9] correctly: [there in [8,9] the incident exiting laser wavelength is probably significantly smaller than the fluorescing outgoing wavelength]), although however the data recording is performed in the far field (just as is mostly the case for the near field scanning opticaly microscopy NSOM as well). Nevertheless it is a sensational progress, if so to speak optical near field microscopy can be realized omitting the near field probe tip. The first imaging method [7], apparently also based on complicated mathematical back-calculation, could perhaps in combination with the presently invented concept provide a significant improvement of the microscopic image quality. However, it is unnecessary for the here proposed presently invented spectroscopy concept. A concept similar to the presently invented is proposed in [17], while there the aberrations and limitations of the lense and aperture system shall be reduced there via their point spread function by deconvoluting the real space image [whereas the present invention concerns the deconvolution of the Fourier/diffracted space image], but also using highly resolved scanning probe microscopy data.
FTIR (Fourier transform infrared spectroscopy) is a widely and for a long time used technique to realize particularly fast spectroscopy in the infrared regime [19, e.g. Wikipedia].
Solution with descriptive explanations of the patent claims: referring to patent claim 1: Microscopy/spectroscopy on,,quantum dots" (here representing any kind of nm-scale luminescence-fluorescence-, phosphorescence-objects, i.e. natural or artificial atoms/molecules/nano-particles) beyond/below the diffraction limit by means of optimized video microscopy in the Fresnel-regime or
even in the far field:
Video microscopy according to Fig. 1 (here interferometry-supported, but not essentially necessary for the present functional principle) could provide a direct image or diffracted image (scattering in the case of X/2>>a) of the array of,,quantum dots" at a [lateral] resolution below(beyond) the diffraction limit. Especially, if all lenses (eventually except one large diffusor lense in front of the CCD-detector) and apertures are omitted, this here invented interferometric (Michelson/Linnik-type) imaging procedure should provide extremely high optical resolution below the diffraction limit, however then, 1. a very high light intensity is necessary and 2. a very large CCD-array which thus provides a very high numerical aperture, with extremely small and extremely many pixels is needed, whose light sensitivity must be extremely high; for instance a liquid nitrogen cooled conventional CCD-camera would be an option, but especially also the in [6] proposed,,artificial retina" [high density light pixel array]. Ideally, the detector pixel array is, however, very much larger than the sample, with extremely many, extremely small pixels and the diffraction image of the sample is imaged in the Fresnel-regime taking account of higher diffraction orders respectively smaller structural details of the sample, i.e. imaging with very high effective numerical aperture. The real space image is then obtained essentially by (numerical) Fourier back-transformation, eventually (numerically) corrected for the spherical wave approximation in the Fresnel-regime, all this in the case of A/2<=a or slightly >a [18]. In the case A/2>>a the quantum dots' Airy diffraction pattern [of a small disc with diameter a] is replaced by its approximate dipole radiation characteristics; then the deconvolution is not anymore a Fourier back-transformation but it is a scattering theory's back-calculation to the dipole[/multipole] moment p qa of the quntum dots.
In case, due to unavoidable lense aberrations (even for Fresnel lenses [14]) and due to finite lense and aperture diameters, the resolution is not sufficient to image the quantum dots directly, then the diffraction "image" from the CCD-sensor has to be deconvoluted mathematically, i.e. the "blurred" interfering superimpositions of the in the ideal case (if the sample structures all possess the geometry of little discs of diameter a) many Airy-disc diffracted intensity profiles (for X/2<=a or slightly >a [18] respectivley dipole radiation characteristics for X/2>>a) are computed out /subtracted out; Fig. lb, 2a and 2b. The image information is always contained in the quantitative diffracted intensity profile of an arbitrary sample image, even in the far field (hypothesis (I), illustrated in Fig. 2d, exaggeratedly drawn for the regime,,close" to the sample); the only question is just whether one can always back-calculate/deconvolute to the [correct] sample geometry, which, for the case of many unknowns (various structural details, non-periodic distances -all beyond the diffraction limit) will become arbitrarily [very] complicated respectively the detector [pixel array] has to become infinitely large in order to quantitatively measure the Airy diffraction patterns respectively the dipole radiation profile characteristics. This back-calculating[/deconvoluting] to the sample's geometry is of course simpler possible, either if the pixel detector array were infinitely large (Fourier back transformation of the diffracted "image" respectively scattering theoretical back calculation of the scattered "image"), or if only 2 "Airy" sample-discs of known diameter and position (diameter and distance non-trivially smaller than the diffraction limit) is the sample; having 3 such "Airy-sample discs makes the situation already much more complicated etc. Here, it is particularly intended, to apply the presently invented technique on periodic 2-dimensional arrays of identical quantum dots of diameter a, which thus are luminescing independently [incoherently]of each other and thus their Airy diffraction patterns (for X/2<=a or slightly >a [18]) respectively their dipole characteristics for X/2>>a add only incoherently (scalarly) and do not mutually interfer with each other. Hence, the deconvolution reduces to a subtraction of [the quantum dots'] Airy diffraction pattern intensity profiles respectively dipole characteristics from the blurred diffracted/scattered image at the positions of the quantum troughs. By Fourier back transformation for various wavelengths of the separate differences, the real space color image of the separate quantum troughs is obtained, in the case X/2<=a or slightly >a [18]. In the case X/2>>a, the Airy diffraction patterns of the quantum dots are replaced by the approximate dipole characteristics; then the deconvolution is not anymore a Fourier back transformation, but the back calculation of the scattering theory to dipole moment p"qa of the quantum dots.
If the geometrical topographic structure of the,,quantum dot" array is known at all, then the deconvolution/subtraction is in particular also possible for the 3 different color components (Fig. 2c), by means of which the spectroscopic information about the quantum trough luminescence (representing any kind of luminescence, fluorescence, phosphorescence on the nm-scale) is then, in principle [theoretically], available at a lateral resolution of the scanning force microscope, for each new spectroscopical situation again using the fast far field optical (here invented) procedure, without having to employ each time a slow [scanning] near field method. For highest accuracy, however, non-linear optical effects in light scattering on nanometric (especially metallic) scatterers have to be considered, since during scattering of intensive electromagnetic radiation at a nanometric,,antenna" (like for instance a metallic nano-particle), there is -besides the dominating incoming wavelength -also many other wavelengths in the scattered light, especially shorter ones, which would allow higher resolution even within the diffraction limit [as expressed with respect to the incoming wavelength].
Then the deconvolution however [again] becomes much more complicated, since then for every sample detail (as known from scanning probe microscopy), i.e. practically each nano particle, complicated scattering theory has to be applied and has to be computed into the complete image.
By means of a phase contrast method (interferometry), which in principle [theoretically] provides a vertical (DC-)[wide bandwidth] resolution of about a 10th of an Angstrom (or roughly 1O Angstrom x Hertz2 for modulation methods), also 3-dimensional arrays of quantum troughs can be (luminescence) spectroscopically measured -i.e. can be read out -, since the phase of the [laser] light wave can be,,moved through" vertically [through the sample] at this high [spatial vertical] resolution.
Thus, a much higher storage densitiy is reachable as compared to having just 2-dimensional arrays of quantum troughs (and only these are accessible by highest resolving scanning probe methods, the 3-dimensional array of course for the initial topographical characterization as well, i.e. each layer once, while the 3-dimensional array is built layer by layer).
The here invented concept is fundamentally based on at best apertureless throwing a,,shadow" [absorption chart as a function of position of the sample] of a sample after illumination (in reflexion or transmission) by means of an eventually expanded/shaped laser beam onto a pixel [detector] array, which either possesses sufficiently high pixel density (with sufficiently small pixels) or, respectively, is large enough (with sufficiently many pixels) that by means of a single diffusor lense the expanded,,shadow" can be imaged interferometrically (i.e. with phase contrast) after Fourier back transformation respectively scattering theoretical back calculation with an optical [lateral] resolution far below the for "X/2" diffraction limit (quantum dots with 5 nm diameter and roughly lOnm distance). The inetrferometry is here only needed to cancel out the incoming (illuminating/luminescence exciting) light in the dark field and only to filter out the [small] signals of the incoherently luminescing quantum troughs. For this, besides the as small as possible pixel size, the [high] light sensitivity of the detector pixels is essential and therefore it is also essential, that they allow an as high as possible dynamic range, in case that the dynamic range of the light falling onto the detector cannot interferometrically be sufficiently compensated, i.e. in case that it is not possible to sufficiently measure on a dark fringe.
Fig. 1: The Gaussian intensity profile of a,,color-laser" (red-green-blue or tunable, there is nowadays already white,,laser light") -depending on sample size via a beam expander or compressor [or not] -falls onto a beam splitter (polarizing or not), from there for one path onto a mobile mirror of adjustable reflectivity (e.g. by means of an adjustable absorber in front of it) and for the other path onto the sample interferometry cavity. The latter can be formed between an objective lense (partly reflective at the interface side towards the sample) of high numerical aperture [of course] and the reflecting sample, or as well between the back-reflecting end of a very short monomode fiber and the reflecting sample. Third possibility is omitting the objective or the glass fiber respectively completely and just simply forming an interferometer cavity (tunable or bandwidth in the relevant wavelength range) by means of very thin,,silvered" [i.e. ,,mirrored", not necessarily using silver coatings] (reflectivity adjusted such that it is comparable to the expected sample reflectivity) plate [whose normal is parallel to that of the sample] in close distance to sample. This way, almost all apertures [except the sample size itself] would be avoided, however, the laser then has to illuminate the sample with very high intensity on its whole surface area, which in turn causes an increased portion of unwanted reflections at eventual other interfaces; furthermore, the detector has to become very large then, in order to take account of higher diffraction orders respectively in order to evaluate the 0th diffraction order quantitatively more accurately (for X/2<=a or slightly >a [18]) respectively in order to quantitatively measure the superimposed dipole profile characteristics sufficiently precisely (for for X/2>>a). For the case of using fiber optic interferometry, this part of the here invented setup (the fiber optical interferometry component for the mere measurement of smallest vertical distances, not for the image forming microscopy) is based on the invention in [10].
Ideally, the sample plane is exactly the focal plane of the objectiv lense, so that the light spot focussed (the focus can be relatively small, doesn't have to be though, since a larger spot means a larger imaged sample area) onto the sample is reflected exactly back into incoming beam path (i.e. into itself). In the case of illumination by means of a monomode fiber whose end surface is supposed to serve as a (partly reflective) mirror for the [interferometry] cavity, ideally ends in a rod lense [graded index lense] whose focal plane is exactly the sample plane.
In the proposed setup in Fig.1, three light rays interfere at the pixel detector, however, the 3rd ray, the reference ray, coming from the mobile mirror can basically be omitted, it only serves for the optimal adjustment of the detector signal on a dark fringe when averaged over the detector / image area, which is necessary for a good signal to noise ratio. This,,dark fringe" can also be adjusted directly by accurate adjustment of the distance/thickness (for the corresponding, e.g. 3 wavelengths/colors) of the upper partly mirrored surface of the interferometer cavity, which is formed by the sample surface and the exit face of the objective/glassfiber, as well as by the accurate adjustment of the reflected intensities (sample and objective/glass fiber exit face). This, however, is very complicated and elaborate -and of course has to be readjusted for different sample reflectivities -, in particular if this interferometer cavity is supposed to be filled with a liquid (e.g. for increasing the numerical aperture and/or for applications in biology) and thus, in Fig. 1 the (3) reference beam is introduced. Its possible but very elaborate elimination would have the significant advantage, that light of small coherence length (only a few interferometer cavity widths) could be used instead of a coherence length of the order of the length scale of the whole beam path (mirror -beam splitter -sample -detector), e.g. a LED instead of a laser diode as a light source), by means of which stray interferences of the useful light with unwanted reflections would be largely reduced, which becomes the more important, the more the signal to noise ratio, i.e. ultimately the resolution, has to be optimized for the corresponding application.
By suitable usage of A/4-waveplates or equivalent the polarizations are adjusted such that only the three desired laser beams interfere at the pixel array detector and stray reflections are largely eliminated. By means of the mirror position the relative phases of the laser beams are adjusted such that the measurement is performed by almost 100% on a dark fringe [averaged across the sample area]; the only photons that arrive at the CCD-array/pixel detector are the minute deviations of the light beam intensity profile from the incoming laser's ideal Gaussian intensity profile caused by the sample structure (Fig. 2d, [exaggeratedly] drawn for the regime near the sample). For the case of the fiber optic version it is remarked that 1. the [effective] inner diameter of a monomode fiber for 633 nm is about 4iim i.e. roughly same size as the expected sample size (for 5 nm quantum dots in 10 nm distance this would be already almost lOOkBits, even if just one quantum level is used) and 2. that this monomode fiber must be very short (<<O(lm)), since in an ideal monomode fiber deviations from the ideal Gaussian profile are rapidly damped. For large memory cell arrays, e.g. 1cm2 -which corresponds already, even if realized only in 2 dimensions, to a storage amount of about 400Gbits (at (lSnm)2 per quantum trough and one used quantum level) -one has to scan line-wise (laterally in 4iim steps), or a large objective lense or multimode fiber of larger diameter has to be used, or just that apertureless shadow-throwing technique mentioned above (patent claims 10, 11) using a very large detector pixel array -e.g. the,,artificial retina" [light pixel detector array of highest density] of 1cm2 from [6].
Because of the GauRian intensity profile of the laser beam in the middle of the beam a larger signal results than at the,,edges" [quotation marks because a Gaussian beam does not really have an edge] of the beam. This has to be additionally compensated, e.g. when using a CCD-array e.g. by according bias voltage of the single pixels, i.e. compensation of the Gaussian intensity profile by according pre-adjustment of the sensitivity of the pixels, increasingly from the middle of the beam towards the outer end of the beam. Accordingly profiled absorber plates can also be envisioned, however, they certainly would introduce disturbances (reflections, phase shifts) into the system and thus would further reduce the already very small useful signal. A further possibility [for this compensation] lies in that that the diffusor lense (refractive lense or,,suitable" Fresnel lense [14]) behind the pinhole is milled into such a shape, that it converts the known Gaussian beam profile exactly into a homogeneous light intensity distribution at the CCD-detector, i.e. such that it perfectly compensates the Gaussian beam profile -of course the small intensity variations of the useful signal remain contained, the more, the larger the aperture (the pinhole) in Fig. 1 is. [Reshaping the Gaussian beam profile into a homogeneous distribution will introduce new laterally varying phase shifts to be corrected, though, e.g. by means of a,,variable-&s." waveplate, similar to the above mentioned tailored absorber.] The here primarily proposed method to achieve spectroscopical (color) resolution is simply based on the technology of customary high quality video color cameras, namely to split the used signal via a prism (or a,,suitable" [14] optical grating) into the spectral colors and to record them with e.g. 3 or more pixel detectors (e.g. highly sensitive black and white CCD cameras, optimized for the according wavelength regime). Fig. 1 -inset.
Writing" onto such 2-3-dimensional arrays of quantum troughs would have to be of the kind of a 2 dimensional shift register, as suggested in Fig. 3, there however drawn for just 1 dimension, or scanned by means of scanning probe techniques. In the latter case, one would have only relatively slow writing, which, however, can be accelerated by the millipede concept using many probe tips [2], but still the here invented fast large area optical [simultaneous] read-out of the quantum trough arrays is available.
The presently invented technical principle is thus based on mathematical back-computation [,,deconvolution"] of the,,blurred" microscopic far field diffraction image (eventually parhaps only Fresnel -regime image -i.e. the intermediate range between near and far field, in which propagating spherical waves are present, but plane wave approximation as in the far field is not yet applicable - also for the case of using "suitable" Fresnel lenses [14]), that -because of incoherent light portions -in its diffracted intensity distribution also must contain the information about structural details below/beyond the diffraction limit of X/2 (Fig. 2d), by using partial or complete additional data on the sample's geometry/topography, which was obtained before by other highly resolving microscopy methods. Initially it appears of course trivial or only little useful respectively, to derive again -by means of a complicated procedure -an already completely known sample topography (e.g. from atomically resolving scanning force microscopy) from the blurred optical far field image, but in the light image of course many further spectroscopical-optical informations about the sample properties are contained, i.e. the colors which are of course not contained in the force microscopy image.
(Remark: There is of course also highly spatially resolved scanning probe spectrocopies, but these are firstly very slow, e.g. the optical near field microscopy/spectroscopy, however, these deliver in general additionally completely different spectroscopic informations, e.g. electrical or magnetic as well as elasticity-dependent effects.) And furthermore, the presently invented method will be of course, due to the omission of the timely raster-scanning procedure, primarily much faster, i.e. time scale of digital video microscopy.
The here invented apparative method for the highest spatially resolved (<<X/2) fast spectroscopy on an array of luminescing quantum troughs is based firstly on the principle of a highly resolving (laser) interference microscopes (Michelson-/Linnik-or Fizeau-type respectively, also fiber optics version) -by means of which the incoming light is eliminated at the detector in the dark field -under avoidance of lenses/apertures as far as possible, and secondly on a highest resolving pixel arrax detector (e.g. a CCD camera) with extremely small and many pixels -by means of which a very large effective "numerical aperture" for recording of the diffraction image is provided respectively the dipole characteristics of the quantum dots can be measured sufficiently quantitatively-, as well as thirdly on a fast digital image acquisition and image processing procedure which -with video data rate -subtracts the sample's topography image known from scanning probe microscopy (more precisely its Fourier transform i.e. its diffraction image of the interference of plain or spherical waves respectively [-multipole expansion]) ,,online" from the blurred optical (and e.g. split into the 3 fundamental colors) far field light image and then Fourier back-transforms these 3 images. In the for the present invention's concept signal-stronger Fresnel regime (intermediate range between near field and far field, at and up to a distance of about 100X from the sample, scatterer size of order X), where spherical waves have to be regarded, thus higher terms also in the multipole expansion have to be included, not just plane waves. These for instance 3 images obtained in this way then contain the correct color distribution of the sample at a spatial resolution of the supporting scanning probe microscopy (with which the sample geometry has to be determined only once) and at a time resolution and spectroscopical resolution of the [here invented optimized] video microscopy. Finally 4. the deconvolution is here relatively simply solvable in form of a subtraction [in Fourier space], since the quantum troughs should be luminescing mutually independently, thus should represent mutually incoherent point light sources; hence, the many Airy diffraction pattern intensity profiles (for X/2<=a or slightly >a [18], "Mie") respectively the dipole radiation characteristics (for X/2>>a, "Rayleigh) should simply add up scalarly and should not interfere mutually. The Airy diffraction pattern intensity profiles respectively the dipole characteristics of the single quantum dots are simply" subtracted from the "blurred" optical diffraction/scattered image for the according incoming wavelength at those positions as determined by scanning force microscopy and left over is the color information, however still in the form of Airy diffraction pattern profiles respectively dipole radiation characteristics of the quantum troughs. Every single quantum dot (its luminescence) can then be obtained in real space by Fourier back-transformation for the according luminescence wavelengths for the case X/2<=a or slightly >a [18] (Mie), [eventually (numerically) corrected for the spherical wave approximation in the Fresnel regime]. For the case X/2>>a, the Hertz dipole [/multipole] characteristics has to be back-calculated to the scatterer size [and form]. Even for the case, that the quantum dots would be coherent (e.g. phase-conservingly reflecting) light sources, there should be a small fraction of incoherent light [intensity], which then also adds up scalarly, even though the major portion of the (reflected) intensity interfers.
[In principle [theoretically speaking] this method should also work with usual digital light microscopy, the interference microscopy as well as the eventual additional digital calibration of the optical apparatus by evaluation of the point spread function of the image transforming system for the correction of lense/aperture aberrations can be employed as an option to increase the expected very small useful signal/contrast [17]]. For all deviations of the present invention from the usual video microscopy it is always an issue to omit as many lenses/apertures as possible, this holds even also for the ("suitable" [14]) Fresnel lenses.
referring to patent claim 2: Principle as in patent claim 1, further specified in that that the light source is a tunable laser. The interferometer cavity above the sample is adjusted in particular with respect to its width and eventually also its reflectivity (e.g. by means of electrically controllable/polarizable liquid crystal coatings) simultaneously with the tuning of the laser wave length; the wave length dependence of the detector pixels is calibrated and taken account of in the mathematical analysis. The Faraday isolator is either also simultaneously [wave length] tuned (for highest accuracy) or is a broad band isolator. This method provides highest accuracy (signal to noise ratio), however, sacrifices speed of the achievable image rate, which would not be too much of a problem for the read-out of quantum troughs as memory cells, since always only one (total) image (of all quantum troughs) is necessary (i.e. would be still fast enough). Sacrificing speed, however, would be of significant disadvantge when recording fluorescence microscopical movies on biological samples in vitro, unless, in this case, the image rate would be limited to the according extent anyhow by the [sometimes] necessarily simultaneously running much slower scanning probe microscopy; and unless, anyway only 1 or 2 or a few known fluorescence wavelengths are observed simultaneously.
referring to patent claim 3: Principle as in patent claim 1, further specified in that that the light source is a white (pulse) laser.
The Faraday isolator in this case necessarily is a broad band isolator. The pixel array detector is in this case the one of a commercial color video camera, either with a color CCD array or the white light is for instance split by a prism in 3 or more partial beams and recorded on several (wave length calibrated/tuned) pixel array detectors. This method provides the highest image rate, however, sacrifices signal to noise ratio, particularly because the interferometer cavity above the sample can only be adjusted for one wave length. This interferometer cavity, however, does possess a certain band width, which is only necessary, if the luminescence is to be imaged, i.e. if one wants to obtain a color image. Particularly for the fluorescence microscopy which is relevant in the,,in vitro" biology, in principle [theoretically], the very narrow bandwidth of the interferometer cavity should be sufficient, since there only 2 or in the case of some few fluorescence molecules only a few wave lengths play a role, which firstly are relatively adjacent to each other and secondly can be selected at the detector/several detectors by filters. I.e. specific (perhaps also differential/non-linear) analysis of the light absorbed by the fluorescence molecules with respect to the light emitted by them.
referring to patent claim 4: As in patent claim 1, further specified in that that the complete beam path is built up in a fiber optical manner. The whole (Michelson-/Fizeau-) interferometer is then built up merely fiber-optically, then reflexions at interfaces/transitions are further significantly minimized, furthermore there is no beam paths going through free space (i.e. no stray reflections/refraction by air currents) and thus the signal to noise ratio of the apparatus is further improved, All necessary phase shift adjustments, e.g. for the 3rd,, reference beam, can, as in [10], be realized by stress birefringence of the fiber, i.e. by bending of the fiber in a plane with appropriate angle to the polarization plane of the light; the X/4-waveplates for the 90°-polarization rotation (twice 45° polarization rotation in the same direction on the light path back and forth [through the bent fiber portion]) can as well be realized by bending of the fiber in a suitable plane as in [10]. The polarizing beam splitter will eventually be still a more or less customary polarizing glass beam splitter cube, however, at its faces the 4 fibers will be connected via an integrated system (e.g. commercially available from [11]), which eliminates reflexions and free [space] beam paths. By using rod lenses (graded index lenses) in coupling optics to and from the monomode fibers, these rod lenses could be directly glued to the beam splitter cube (by means of index matching epoxy -[ha]), which practically eliminates all reflexions at interfaces and unguided beams are reduced to the (small) space within the beam splitter cube. In the future there will certainly be beam splitter cubes with fiber optic connectors realized on a single chip.
Such a system would have, at perhaps a worse signal to noise ratio (which would still have to be evaluated in the case of realization by means of integrated optics -here by usage of,,suitable" [14] Fresnel-lenses, while in read-write heads of commercial CD-/DVD read-write devices "normal" Fresnel lenses are used), however, the advantage of highest compaction, usability, portability and pricing.
referring to patent claim 5: As patent claim 4, further specified in that that even the beam splitter is realized purely light wave guide optically, preferably by measn of integrated optics with the advantage of highest compaction, portability and cost effectiveness in case of suitable micro technical manufacturing methods. Regular commercial fiber-optic polarizing and non-polarizing beam splitters (fused fibers out of two or more glass fibers) have many disadvantages, for instance that stray reflections, if they occur, cannot be eliminated or it is extremely difficult to eliminate them via the above mentioned A/4-'trick" and that there are strong back reflections back into the light source, which destabilize their intensity, which also the Faraday isolator can only eliminate to a certain extent.
referring to patent claim 6: As patent claim 1, further specified in that that there is of course quantum troughs that have no or only little topographical structures (embedded local material alterations, as typical for quantum troughs that are realized in semiconductor structures), which then cannot be ideally characterized by AFM. In this case, however, practically always a suitable scanning probe method can be found particularly for the geometrical (but eventually also for the electronic) characterization of the quantum troughs, for instance scanning elasticity/capacitance/conductivity/magnetic force probe microscopy, or as well the near field optical microscopy itself, which then provide the additional data, which are necessary for the deconvolution/subtraction/back-calculation of the optical far field image.
referring to patent claim 7: The optical read-out of the quantum troughs can of course also be done via scanning probe techniques, in particular, here in the present invention it is proposed, to deposit a thin DLC-layer (about lOOnm) as in EP1096569A1 [3] onto an AFM-probe tip made of highly doped Si and then by impact of a single heavy ion to generate a single electrically conducting quantum wire at the end of the tip (as in [3]), whose quantummechanical conductivity is also light sensitive [6]. By means of the so prepared scanning probe tip the excitation states of the here suggested layer of,,quantum dots" can be written on (electronically) as well as read-out (optically) (Fig. 3b). Since as in Fig. 2c in [6] the highest occupied level of the according quantum trough,,scans" (Voltage modulation/scanning of the I-V curve) the quantum conductance peaks (1-dimensional transmission in the quantum wire in the probe tip) enumerably -which corresponds to electronical writing. Secondly the photons emitted from a quantum trough lowering ist excitation state cause a change in the light sensitive current through the [single] quantum wire from [6] in the AFM-tip -optical read-out. The light sensitive quantum wire current is desirable but not absolutely necessary, since an for near field optics suitably sharpened (i.e. much smaller than X) photo sensor has already been realized in conventional manner (regular photo effect, e.g. preliminary experiments in [13], but also various others already much more professional) and are possibly already commercially available.
referring to patent claim 8: The read-out of the quantum troughs can also be realized in an purely electronical manner, in particular it is suggested here, by means of the quantum wires as described in patent claim 7 and in [3,6], which are here, as in patent claim 7 generated on an AFM tip, to use the measuring method shown in Fig. 2c from [6] in order to read-out the excitation states of the quantum troughs (Fig. 3b).
Counting the sharp quantum conductance peaks relative to the voltage applied then provides the information about the excitation states of the,,quantum dots." referring to patent claim 9: Generation of an electronically writable array of quantum troughs consisting of an array of metallic nanoparticles, e.g. deposited by Langmuir-Blodgett technique [12,12a,12b] or by other (e.g. imprinting") methods [12c] onto a lattice network of potentiometric resistive conducting leads, e.g. from thin graphitic carbon or semi conductors with relatively high resistivity respectively (Fig. 3a).
Between the conducting leads and the quantum troughs there is a thin insulating spacer (either an insulating oxide-/DLC-layer additionally deposited, or simply in case of the LB-deposition technique the amphiphile molecules which carry the metal nanoparticles or embedd these respectively), which only allows a very high ohmic tunneling contact between the resistive lead network and the quantum troughs, thus the write-on into these quantum troughs would be possible by means of quantitative voltage pulses and thus the the quantum troughs can hold their charging state in principle in a non-volatile manner. For how long they remain in their charging state, remains to be investigated in further measurements and is of course dependent on the value of the high-ohmic resistance of the tunneling contacts, as well as of course dependent on the screening towards outer influences as radiation and temperature.
Hereby, the problem will be to place exactly one quantum trough onto each crossing of the resistive conducting lead lattice network; initially, by adjustment of the size of these cross points to the size of the metallic nanoparticles, it will be only feasable, to obtain one quantum trough per crossing point on average. Furthermore, the quantum troughs (in an LB-film) could be packed much more densely than the initially reachable size/distance of conducting lead crossings, such that on each crossing point there will be several/many (<Snm in size) nano particles. Their quantum levels will all lie at the same energy/voltage values if they all have the same size, only the (tiny) current pulse, in order to raise them all at once into a certain excited state, i.e. to,,write-on" them, would have to be stronger proportional to their number, which, however, would have to be calibrated for each quantum trough array after ist manufacturing, but indeed can really be calibrated.
In principle [theoretically] the read-out of such a quantum trough array by means of such a resistor cascade as mentioned above would be possible also, if the conducting lead sections were transmission lines, i.e. every connection between the quantum troughs were a RC-component. R would be the ohmic resistance of the conductin lead section (a kind of a very small potentiometer strip) between the quantum dots, where conducting lead and quantum troughs are not directly [electrically] connected, only via a tunneling contact (of certain capacitance C1) and C would be the capacitance of the horizontal tunneling contact between the quantum troughs. The calibration of such an addressing would be an extremely high effort, but similar to a DRAM, shift register, CCD-array and supposedly also flash RAM.
Langmuir-Blodgett layers can be deposited in multiple layers too, thus multi layers can be formed in a simple way, and thus a 3-dimensional array of quantum troughs (e.g. [la]); formation of the addressing conducting lead matrix then becomes very difficult though, at most it could be realized 2-dimensionally in each layer; vertical conducting leads which would connect the quantum troughs in the 3rd dimension can probably hardly be realized, unless it were possible to embed the quantum troughs into a matrix material, which by impact of single high energy particles would form [electrically] conducting particle tracks. (similar to [3]).
Another possibility of choice would be of course, if the amphiphilic molecules, which carry the metallic nanoparticles as part of their,,head group" respectively envelope the nanoparticles, themselves would have electrically conducting hydrophobic chains -that does exist (double bonds/unsaturated fatty acids! poly acetylenes) -and the head group of the molecule it self would be the highly ohmic (pseudo insulating) tunneling contact to the nanoparticle.
referring to patent claim 10: Optical microscopy far beyond the diffraction limit, just by usage of a pixel detector array with extremely small pixels and extremely small pixel separation. For instance the,,artificial retina" [light pixel array of extreme density] from [6] could be used hereby (pixelsize about 5nm, mean pixel separation down to 1O-3Onm) -Fig. 3a/'ll. The sample, e.g. molecules, bacteriae, cells, but also quantum dots are directly prepared onto the pixel array chip and by almost trivial shadow throwing onto the pixel detectors they are imaged in the near field. For thin samples not even a lot of light is necessary, since quantum effects are always extremely sensitive.
Such an,,artificial retina" [light pixel array of highest density] as suggested in [6] with extremely small and extremely many pixels would solve all resolution problems in color microscopy/spatially resolved spectroscopy, the spatial resolution being only limited by the pixel size (quantum wire diameters are about mm, mean separations of about lOnm are thinkable as in [6] and [3] aimed at; the time resolution would be limited by the circuitry to the pixels of the,,artificial retina" [6], since quantum electronic effects in quantum wires (ohmic resistance practically 0) occur instantaneously.
Spectroscopic resolution should already be possible in a single quantum wire, since such quantum mechanical mechanisms (excitation events of quantum mechanicals states) always are depending on the photon energy -i.e. depending on the light frequency -but to quantify the latter, the electronic properties of the quantum wires from [3] would have to be studied much more accurately.
referring to patent claim lOa: Aperture-and lense-less microscopy as in patent claim mU, characterized in that that the pixel detector array is located approximately at a distance of mo-moo X from the sample, m7 so that the diffraction image of the sample is recorded in the Fresnel regime, that the also ordinary (CCD-) pixel detector array or the quantum wire pixel array as in patent claim is of much larger area than the sample itself and thus provides a very high effective numerical aperture for the mere diffraction "image! scattered "image, that in the case for X/2<=a or slightly >a [18] (Mie) the real space image is obtained by Fourier back transformation for various wavelengths, corrected [numerically] for the Fresnel spherical wave approximation or is obtained in further approximation by mere Fourier back transformation for various wave lengths, that in the case X/2>>a (Rayleigh) the scatterer [form] is derived by back-calculation of the superimposed dipole radiation characteristics.
referring to patent claim lOb: As patent claim lOa, characterized in that that the pixel detector array is semispherically concave and the sample is located in its center point.
referring to patent claim 11: A non-scanning near field microscope with a 2-dimensional array of many near field probe tips would be in complete analogy to patent claim 10, which in principle can be achieved by bundeling many customary monomode fibers sharpened into near field apertures and transmitting the light in each fiber towards a photomultiplyer/photon counter, as described in the Gedankenexperiment above; this basically is the parallel usage of many optical near field microscopes, which would make the raster-scanning of the sample obsolete. The problem is a geometrical one, because when bundeling many fine sharpened glass fiber tips that regime of the fibers would be fairly long, in which their diameter is much smaller than necessary for almost undamped light propagation (at a certain wave length, e.g. 633nm), thus the light collected by the near field optical tips would be extremely damped, before it hits the detector; thus, the signals might not be detectable anymore, especially because of stray light intensities -single photon counter would be [commercially] available though.
referring to patent claim 12: Time resolution and,,color" of the optical (far field) microscopy at simultaneous spatial resolution of the scanning probe techniques in biology! crystallography / physical chemistry etc.: Using the here invented spectroscopical technique of course also fluorophores (always representative for luminescence, fluorescence and phosphorescence, which can be regarded as fully equivalent for the here invented concept) in biology/crystallography/physical chemistry can be spectroscopically imaged. Also these -just like quantum troughs -are regarded as mutually independent point light sources, which do not interfere with each other; their Airy diffraction pattern intensity profiles for A<=a or slightly >a (Mie) respectively their dipole radiation characteristics for A >> a (Rayleigh) will add up as scalars in the diffracted/scattered image. For instance fluorophores that are bound directly or in immediate vicinity (on a molecular scale) of proteins often are indicators for the function of such biomolecules (or as well for recrystallization events e.g. in Langmuir Blodgett films). The AFM could localize these luminescence or fluorescence particles (e.g. metallic nano particles with or without attached fluorescence molecules) and the here invented optical spectroscopy then is able to prove biochemical functions e.g. on a cell / bacteria /virus surface, all with the spatial resolution of the scanning force microscope and the color of the optical diffraction/scattering imaging microscopy. The time resolution can be better than that of scanning probe techniques and can be almost equal to that of the optical video microscopy, since nowadays' computers are very powerful, while the scanning probe microscopy just provides markers/marker-images in time containing the necessary additional [image] information on their own time scale of (nowadays) up to 10 images per second.
As an example, proposed is this method e.g. for the imaging of the surface of living cells/bacteriae/viruses in vitro on a molecular scale and the physiological processes on them: Scanning force micrsocopy already provides,,movies" with a resolution of down to about lOnm laterally at up to one frame per second [13]; based on that spatial resolution the here invented fast (much faster than the 1 image per second of scanning force microscopy in biology) spectroscopy could then follow luminescence / fluorescence markers at a much higher image rate and thus could image [kinematic and] dynamic biochemical processes in color and could identify them.
In fact monoclonal antibodies labelled with 5 nm gold [or other metallic] nano particles (which are also available with attached fluorescence molecules) against certain proteins could be imaged by means of the here invented optical (color) microscopy on the surface of viruses (e.g. vaccination strains), while these viruses attach to cell surfaces or while newly formed [progeny] virions leave the [host] cell through the cell wall, and thus certain viruses can be identified unambiguously.
Equivalently of course generally certain proteins in the cell membrane could be labelled unambiguously by such [fluorescence] labelled monoclonal antibodies and thus biochemical processes can be followed on a molecular scale in a well defined manner, and all that with the time resolution of the optical microscopy, if the spatial changes within [below/beyond] the diffraction limit (above the diffraction limit optical microscopy sees it anyway of course) are only slow -order of the time resolution of the AFM, 1 image per second). Spatially fixed processes, e.g. protein motion / enzymatic activity, which for instance can quench the fluorescence of a marker molecule, can of course be imaged with the time resolution of the here invented optical microscopy /spatially resolved spectroscopy -i.e. for instance with the time resolution of a highest quality color camera, there is high speed cameras with over 100000 images per second (depending on the number of pixels of course) [reference Slomotec: http://www.slomotec.de/productview.php?article=99] . The artificial retina" (light pixel array of highest density) as hypothetically suggested in [6] could perhaps be even faster in the future due to the there exploited quantum effects. All of course given extremely fast efficient computer / numeric software technology. A few single well-defined marker (illuminated) points, i.e. a few single (2-3 pieces) fluorophores placed within the diffraction limit can be followed of course (in principle/theoretically) directly -even in 3 dimensions -with the here invented method, without needing another supporting highly resolving (,,black and white") microscopy like scanning probe microscopy [as mentioned above].
The,,back-calculation" of the lateral resolution of the optical (far field) microscopy would then tolerate relatively slow and relatively minor spatial changes (order of magnitude of the scanning force microscopy resolution) of the structural details, while the scanning force microscopy is refreshing these data continuously at 1 image frame per second. Spatial changes of these structural details may as well be of order of a few AFM-spatial resolutions (i.e. some 10 nm), since as mentioned above, it should be sufficient for the back-calculation of the spectroscopy image of well-defined,,points" (,,Airy-discs"), to know their number and their approximate position within the optical diffraction limit. The for this necessary fast numerical (real-time) procedures are initially not issue of the present invention, they exist however possibly in an adaptable manner e.g. in the field of image! object recognition in electron microscopy or also in [17].
It is remarked, that the here invented spatially resolved spectroscopy can of course besides AFM be combined with other highly resolving microscopy techniques, such as electron microscopy or photonic force microscopy, which is claimed [reference] to provide 3d-images for instance also from the inside of a cell in vitro. The latter would be interesting here, since also the here invented method also could provide 3-dimensional spatial information due to the possibility of using a phase contrast procedure.
referring to patent claim 13: The here invented concept from patent claim 1 to overcome the diffraction limitation of wave optical imaging techniques is of course basically applicable to all wave optical microscopies! telescopies, such as electron microscopy (there of course magnetic electron beam optics is used) or such as the imaging using infrared (KBr-lenses or,,suitable" Fresnel lenses [14]) or microwaves (directed microswave-! radar-optics, ,,suitable" [14] Fresnel lenses or parabolic mirrors) -the electronically readable pixel detector just has to be suitablej'sensitive for the according wave length. In the case of micro waves, the laser in Fig. 1 is replaced by a maser, all lenses/'apertures are largely omitted (perhaps rudimentary beam shaping by directed micro wave optics, i.e. ,,suitable" Fresnel lenses [14] or parabolic mirrors respectively, polarisation rotations by Faraday [or Kerr] effects), and since then parallel,,light" is used, the sample can also be located in a large distance. This would lead to a concept of a highly resolving radar-telescopes, imaging mechanism according to Fig 2d, i.e. by circumvention of the wave optical diffraction limit by numerical back-computation/'deconvolution, eventually also in order to obtain spectroscopical data, in that case perhaps by means of pre-information about the geometrically known samplej'objects to be observed! to be imaged.
In the case of a telescope, of course the interferometer cavity on the sample's side can hardly be realized, only in rare special cases -it will be restricted to the reference mirror in Fig. 1 to adjust to a dark fringe and to level out the Gaussian intensity profile (see patent claim 1). Under circumstances -depending on the requirements for sensitivity and resolution capability and depending on the expected contrast from the,,sample" -one could possibly omit the whole interferometry amplification, which as mentioned above in principle is not necessarily needed for circumventing the diffraction limit of the wave optical imaging mechanism. In principle [theoretically] a suitable electronically! digitally readable pixel detector array is sufficient as well as suitable beam shaping and suitable numeric software and of course sufficient pre-information on the sample or the far away observed object; just the signal strength of the,,sub-diffraction limit contrast" will practically rarely suffice, to be made visible without further,,tricks". [Microwave "x-ray" scanners can obviously be also envisioned this way: Different materials are differently transparent for microwaves just as for x-rays, i.e. a microwave,,x-ray" apparatus can be realized that way too.] referring to patent claim 14: The here suggested microscopy method with ultrahigh spatial resolution is combined with the long known Fourier transform infrared spectroscopy (FTIR): The laser light source (1.1) is replaced by an optimally collimated (ideally" parallel light) light source, which emits non-coherent infrared light. An ultrahighly spatially resolved spectrum is recorded by pixel-wise performing the Fourier transformation of the time-dependent intensity signal from time space into frequency space of the because of the periodic modulation of the vertical -in beam direction -position of the mirror (1.3) or of the CCD-array (3). Furthermore, such a spatially resolved spectrum is eventually obtained by 3-dimensional Fourier transformation: I.e. firstly a i-dimensional Fourier transform from time space into frequency space of the because of the periodic mirror position modulation time dependent intensity signal and afterwards secondly a 2-dimensional Fourier transform of the laterally ultrahighly resolved [diffracted] "intensity images" for all frequencies of the spectrum.
Drawings: Fig. 1: High resolution CCD-camera (with a big dynamic range) could read out the quantum troughs spectroscopically (i.e. image their,,color-excited state"), by quantitatively deconvoluting/subtracting the (approximately) Airy-diffraction patterns of each,,quantum dot", particularly if their position and also their shape is known (characterization by scanning probe microscopy). The here invented interferometric set-up in Fig. 1 however could already theoretically in prinicple provide lateral opticaly resolution beyond the diffraction limit, at least in certain, in the patent claims specified special cases. In particular by computer aided image processing (deconvolution by appropriate numerical,,scanning" of an Airy-function across the whole image, under the provision that the quantum dots are little discs of known size, i.e. a kind of cross correlation of the diffraction image with one (or suitable groups of) airy functions) a real space image of the array of tiny (about Snm) quantum dots could be generated.
By using a phase contrast method (interferometry), which has a vertical resolution of order of 0.1 Angstrom, also 3-dimensional arrays (Fig. lb) of quantum troughs can be spectroscopically investigated this way -i.e. read-out -, because the light phase can be,,moved through" vertically at this high resolution. This way, a much higher storage density than just with 2-dimensional quantum trough arrays is possible (only just these are accessible by high resolution scanning probe techniques).
The Gaussian intensity profile of a color laser (red-green-blue or tunable) falls on a beam splitter (polarizing or not), from there one beam falls onto a movable mirror with adjustable reflectivity (e.g. by means of an adjustable absorber in front of it -e.g. via electrically controllable liquid crystals) and the other beam falls onto the with respect to distance (and also reflectivity) adjustable/modulateable sample interferometer cavity. The latter can be formed between an (at the sample side partly reflecting) high numerical aperture objective and the (reflecting) sample (which eventually can be scanned in 3 dimensions, perhaps also with a rotation as for a HDD/DVD/CD) or between the reflecting end of very short mono-/multi-mode fiber and the (reflecting) sample. By suitable usage of X/4-waveplates or equivalent, the polarizations are adjusted such that 3 laser beams come to interference on the detector, e.g. the CCD-camera. By means of the position of the mirror the relative phases of the laser beams are adjusted such that the measurement is almost to a 100% performed on a dark fringe, i.e. the only photons that hit the CCD-array are those caused by the sample structure causing minute deviations of the light beam intensity profile from the ideal Gaussian profile of the incoming laser (Fig. 2d). For the case of the fiber optic version it is remarked, that 1. The [effective] inner diameter of a monomode fiber for 633 nm is about 4 lim, i.e. roughly of the same size as the expected sample area (at 5nm quantum dots in 10 nm distance this would result already in almost lOOkbits, if only one quantum level is used), that 2. This monomode fiber has to ber very short (of order << O(lm)), since in an ideal monomode fiber, deviations from the Gaussian profile are damped rapidly. For large memory cell arrays, e.g. (1cm)2 which, only realized in 2 dimensions, would already correspond to a storage size of 400 GigaBits (at (l5nm)2 per quantum trough and only one used quantum level) a line-wise raster scan is then needed (roughly in 4iim steps, i.e. roughly the inner diameter of the monomode fiber), or a large objective lense has to be used. This objective ought to be a,,suitable" [14] Fresnel lense, since the by the present invention exploited effect should be much more significant in the Fresnel-approximation (spherical wave approximation -Fresnel diffraction optics, scatterer size X) in the regime close to the sample up to X away from the sample, than in the far field approximation (plane wave fronts -Fraunhofer diffraction optics); in particular such a here invented system could be analogue to the laser write/read heads of a CD/DVD player/burner manufactured integrated on a chip, under usage of suitable" Fresnel lenses [14].
For further improvement of the signal to noise ratio by further reduction of stray reflections also the beam splitter can be realized fiber optically and thus the whole system including the,,3." reference beam (if used at all) as described in patent claim la -phases and polarization adjustment by means of stress birefringence of the fiber as in [10].
Fig 1 inset: The here primarily proposed method in order to obtain spectroscopical (color) resolution simply is based on the technology commercially available high quality color video cameras, namely to split the use-signal beam coming from the beam splitter by a prism (or a,,suitable" optical grating [14]) into the spectral colors and to record them with e.g. 3 or more pixel detectors (e.g. highly sensitive black and white cameras, optimized for the according wavlength regime) eventually via a wavelength filter.
Fig. 2a: Diffraction limit 2 Airy functions, if the,,quantum dots" are small discs, at the,,conventional" (Sparrows definition) diffraction limit.
The diffraction pattern, which corresponds to every single,,quantum dot" (e.g. roughly disc geometry) can be reconstructed (calculated/deconvoluted); if the disc separation is slightly above the diffraction limit, the maxima of the diffraction patterns of the single discs could be even resolved separately on a frosted glass screen/photographic film.
Furthermore, a CCD-camera can quantify the intensity profile (as a function of x and y, the lateral extent) of the diffracted light resulting from the superimposition of the diffraction patterns from single quantum dots.
Fig. 2b: Below (beyond) the diffraction limit Superimposed intensity profiles, if the quantum troughs are very close to each other (Airyl, Airy2), i.e. far beyond (below) the conventional (Sparrows definition) diffraction limit. By knowing 2 Airy functions Airyl and Airy2 precisely, because the disc geometry of the,,quantum dots" is precisely known for instance from scanning force microscopy, a computer can easily,,deconvolute" (not really deconvolute but rather just subtract in the simpler case). The same holds of course for arbitrary geometries of the structural details to be imaged, since the single diffraction image always is (in the far field) the Fourier-transform (in the Fresnel regime, i.e. scatterer size A and detector distance some, finitely many (roughly 100) As, with consideration of higher order terms in the multipole expansion -spherical wave approximation) of the light absorption (as a function of x,y) of the structural details. General deconvolution, meaning direct video microscopy without SPM-support, can also be envisioned, while however many pre-informations from other highly resolving microscopies are needed (e.g. how many structural details, which mean size and distance etc., accurate imaging transfer functions / point spread functions of the perhaps used lense system.
Fig. 2c: Spectroscopy: The resulting diffraction pattern of the 2,,quantum dots" in close vicinity, i.e. the diffracted light, is split into for instance red-yellow-blue by means of a prism and recorded by a corresponding CCD-array sensor each. The,,deconvolution" (subtraction) is then performed for each color (wave length). Thus, the spectroscopy can be spatially resolved at each quantum dot by back-calculation.
Fig. 2d: 2 dimensional array of quantum troughs (drawn here in projection only of course), illuminated by the Gaussian beam profile of a laser. Even below/beyond the diffraction limit lateral modulations occur in the intensity profile of the,,shadow", which will hardly show maxima and minima, as drwan here in an exaggerated manner in a regime in close vicinity to the sample where not yet entanglement [folding] of the intensity variations caused by the diffraction at the sample structure details occurs (only such would be visible for the eye on a frosted glass screen /photographic film), there are however measurable deviations from the ideal Gaussian profile and the diffraction limited blurred shadow respectively. A CCD-camera can of course quantitatively measure the intensity incident on the [single] pixels, and not only distinguish between bright and dark -a [photographic] film has of course the same capability, but it cannot amplify for the eye (and particularly cannot deconvolute) and turn the many densely packed folded/entangled inflection points into maxima and minima. The PC, which is hooked up to the electronic pixel detecting camera is capable of this though. An ultrahighly resolved,,regular" photograph could of course even in retrospect be (via the here invented concept similarly ultrahighly resolved) be scanned in, and be deconvoluted by a PC, if the transfer function of the used (two) lense systems are known, if the film processing method had taken account of these (ultra fine) photographic grains and if the scanner exhibits the same resolution capability, or the negative/the film format was large enough.
Fig. 3a: Large ordered or as well statistically distributed array of quantum troughs (e.g. metallic islands in the nm-size regime) between two electrodes, eventually connected again (via tunneling contacts each) by means of a resistor cascade just like in a shift register/CCD-array/DRAM or contacting by measn of the quantum wire array from [3] or as suggested in [6] respectively (Fig. 3a/ll).
Manufacturing of 2-dimensional arrays of,,quantum dots" by positioning of e.g. Snm colloidal Au-, Ag-(or many other materials) nano particles -either statistically deposited from suspension onto a suitable substrate, or positioned with the AFM, or at best, by using Langmuir Blodgett films [12,12a,12b], where such,,nano spheres" can be linked chmically to the amphiphilic (e.g. lipid-) molecules ([12] and references therein, [12a,b]) or these nano spheres can be enveloped by these amphiphilic molecules. Other (e.g. ,,imprinting-") methods can as well be envisioned [12c]. By transfer of the crystalline or partly crystalline LB-films onto a suitable substrate a ordered layer of such for instance gold nano particles is generated. Consequently, an according Langmuir Blodgett deposition of multilayers leads to a 3-dimensional array of such nano spheres (quantum troughs) [la].
Fig. 3b: Optically (spectroscopically) read-out (or write-on) of the stored information (luminescence excitation states of the quantum troughs) in the far field, supported by interferometry by means of the here invented set-up in Fig. 1. Furthermore, at the otherwise [electrically] insulating AFM probe tip a single quantum wire has been generated (procedure as in [3]), by means of which the quantum troughs can be (electronically) written on (charged [/excited]) but this way they also can be electronically read out as well as optically; the latter because the current through a quantum wire is [has been found to be] light sensitive [6].
Legend: 1 prism or,,suitable" [14] optical grating 1.1 Laser 1.2 Faraday isolator + beam shaper/expander 1.3 Mirror 1.4 Beam splitter 1.5 X/4 -wave plate 1.6 Very short monomode glass fiber or strong objective lense with high numerical aperture 1.7 Optical cavity 1.8 Sample 1.9 Laser intensity profile -incident 1.10 Laser intensity profile -reflected 1.11 Resulting intensity profile in the dark field / in destructive interference 2 expander-(diffusor-) lense, perhaps with an aperture (pin hole) in front of it 3 high resolution pixel camera (e.g. CCD-camera chip) 4 disc shaped structural details (>> ,,Airy discs") resulting diffracted intensity profile with dispersion (superimposition of 2 Airy-functions with dispersion spreading[/splitting], where the 2 diffracting structural details lie within/beyond/below the Sparrow's definition of the diffraction limit) 6 quantum troughs, e.g. metal film islands 6a quantum troughs, which are loaded with 1,2 or 3 electrons. Note: A quantum trough charged with 3 electrons will exhibit a resonance at a different wave length, than the same quantum trough which is charged only with one electron -for various reasons.
7 electrodes for,,linear charging" of the quantum troughs 8 electrically insulating layer (e.g. insulating DLC or Si02) 9 electrically conducting substrate (e.g. highly doped Si-wafer) Spectroscopy-respectively microscopy laser (focus diameter/beam waist respectively beam diameter expanded[/tailored] to sample size) 11 Ideal Gaussian intensity profile of the laser (dotted line in the range where it deviates) 12 Deviation from the ideal Gaussian profile (drawn exaggeratedly: Below/beyond the diffraction limit, the intensity profile l(x,y) will not exhibit minima/maxima, but will remain a monotonous function, will, however, measurably deviate locally from the perfect Gaussian profile.
13,,resistive wire" -potentiometric conducting lead with well defined R and C (not just stray capacitances/resistances) 14 Electrically insulating substrate (e.g. 5i02-layer/wafer) Tunneling contacts 16 Electrically insulating DLC-layer with embedded vertical quantum wires (manufacturing method as in [3] or US-sowieso) -on average every quantum trough is contacted by one or a few quantum wires.
17 Wiring matrix -as in a DRAM/FIa5hRAM/shift register etc respectively as suggested in [6] 18 AFM detection laser 19 AFM cantilever spring with probe tip Single quantum wire (eventually a few parallel quantum wires) vertically embedded in an otherwise electrically insulating (e.g. diamond-) AFM-probe tip.
21 Protective resistor (of suitable size) 22 Highly sensitive (pico-femto-) amperemeter (e.g. IVC plus electrometer volt meter) 23 Cuircuit for optional electronic read out of the quantum troughs by means of the quantum wire in the AFM tip 24 Cuircuit for optional electronic,,loading" of the quantum troughs by means of the quantum wire in the AFM probe tip (with small alteration also for optional read-out of the quantum troughs by means of the quantum wire in the AFM probe tip) References: 1. P.M. Petroff, G. Medeiros-Ribeiro, MRS Bulletin 21(4), 50 (1996) la. Xuehua Zhou, Chunyan Liu, Zhiying Zhang, Long Jiang, Jinru Li "Formation of a 3 dimensional (3D) structure of nanoparticles using Langmuir Blodgett method"; Chemistry Letters 33(6), 710 (2004) 2. U55835477,G.Binnig,H.Rohrer,P.Vettiger,"Mass-storage applications of local probe arrays" 3. EP1096569A1, F. Ohnesorge et al. 4. US6566704B2 Wun-bong Choi et al. 5. H.A.Bethe, Phys.Rev.66(7,8),163(Oct. 1944); C.L.Pekeris,Phys.Rev.66(11,12),351(1944) 6. Patentanmeldung beim DPMA Az:102008015118.1-33, vom 10.03.2008, F. Ohnesorge 7. [P 0776457B1, C.H.F. Veizel et al. 8. T.A. KIar, S. Jakobs, M.Dyba, A. Egner, S. Hell, PNAS 97(15), 8206 (2000) 9. DE10154699A1, S. Hell et al. 10. D.Rugar,H.i.Mamin,R.Erlandsson,i.E.Stern,B.D.Terris,Rev.Sci.lnstr.59(11), 2337 (1988) 11. z.B. Fa. Schäfter-Kirchhoff ha. z.B. Fa. Epotec 12. C.P.Collier, R.J.Saykally, J.J.Shiang, S.E.Henrichs, J.R.Heath, Science 277, 1978 (1997) 12a. J.R. Heath, C.M. Knobler, D.V. Leff, J.Phys. Chem. BlOl, 189 (1997) 12b. U56159620A, J. Heath, D. Leff, G. Markovic 12c. U56294401 J.M. Jacobson, B.N. Hubert, B. Ridley, B. Nivi, S. Fuller 13. Dissertation, F. Ohnesorge, Juni 1994, LMU München 14. Here it is remarked that there is a danger of confusion: A Fresnel lense (diffraction lense) usually also works with Fraunhofer diffraction (i.e. in the Fraunhofer-regime/plane wave approximation of diffraction), but eventually -depending on the size scales -also in the Fresnel regime of diffraction (spherical wave approximation). Furthermore, it is emphasized, that for diffraction limited optics any refraktive lense can be replaced by a Fresnel lense. In the here invented concept, a,,normal" Fresnel lense would unwantedly filter away the information below/beyond the diffraction limit. A for the here invented concept,,suitable" Fresnel lense would have to contain much finer gratings, than the usualy wave length order of magnitude, in order to take account of higher orders /shorter wavelength contributions (non-linear optical effects); or the Fresnel lense would have to have suitably shaped gratings, i.e. roughly Gaussian shaped, in order not to mix information of higher order (eventually shorter wave length contributions) with the,,ringing" from diffraction at cornered or arbitrarily shaped edges of a usual[/customary] grating. The evaluation of the,,point spread function" could here only partly and then only theoretically provide,,relief", since then in fact 2 diffraction limits are superimposed; one occurs by imaging of the sample itself and the other at the diffractive lense; this blurred image will hardly ever be reconstructable by computation, at least not to my present imagination. A refractive lense does not have this limitation in principle [theoretically], but does have of course -as any lense -further other aberrations (e.g. the deviation of the lense curvature from a polynomial 4th order or perhaps higher orders). The lense error,,finite diameter", i.e. finite numrical aperture, both lense types have in common.
15. The here invented concept, I already have proposed in Sept. 1996 for a reasearch fund's application (confidential, of course not published) at the Alexander v. Humboldt foundation and thus, I claim the Urheber-Recht at this date. Furthermore in part in the deemd withdrawn patent application Az. 10019037.5 at the DPMA of 18.04.2000 (not published, is considered withdrawn).
Abbreviations: AFM -atomic force microscopy DLC -diamond like carbon SPM -scanning probe microscopy SNOM/NSOM -scanning near field optical microscopy/near field scanning optical microscopy LB-film/LB-technique -Langmuir Blodgett film / Langmuir Blodgett technique
Summary:
The invention is about a technical principle and an aparative technique [an aparatus] (Fig. 1) in several versions by means of which fast (time scale of digital video) optical spectroscopy with a lateral resolution below/beyond the general diffraction limit (i.e. <Xlrght/2) can be realized in the optical far field (or also Fresnel-regime/spherical wave approximation). Also the invention is about application examples for a new kind of digital data storage as well as for a microbiological/crystallographic analysis method.
The data storage is to be realized by means of 2-or even 3-dimensional arrays ofmutually incoherently luminescing quantum troughs, whose excitation/charging state is to be read out by means of highly spatially resolved luminescence spectroscopy (eventually interferometry supported).
The analysis methods in biology and crystallography are based on the same spatially resolved spectroscopy method, while here fluorescence marker molecules are to be imaged. These two primary applications use geometric pre-information from other highly spatially resolving microscopy methods such as SPM.
This concept is in principle [theoretically] transferable to all wave-optic imaging methods, i.e. applicable for instence to the Infrared-or micro wave regime.
The diffraction limit of optics says, that 2 point-like (structural) details cannot be resolved (separately), if their (light) diffraction patterns overlap too closely e.g. on a photographic film or a frosted glass screen (Fig. lb, 2a,b). This case occurs roughly, if the structural detail sizes to be imaged become smaller than X/2 of the light used for observing/microscopying, of course still depending on the NA of the imaging optics [objective lense(s)].
If now, however, this image displaying frosted glass screen is replaced by a CCD-sensor, which is able to quantitatively measure the lateral intensitiy profile of the diffraction peak of a structural detail of the sample -e.g. the Airy-diffraction pattern intensity profile function of a small disc a [16] (X/2<=a or slightly >a [18], Mie case) or its dipole (multipole) characteristics (X/2>>a, Rayleigh case) then it could be said, that practically there is no diffraction limit anymore, for instance for the case of aperture-less microscopy of the (mere) diffraction image, if the pixel detector array were infinitely large (high effective numerical aperture). Further here important physical reason for this statement is, however, that an array of arbitrarily small (nanometric) objects (especially metallic), if irradiated by light of any wavelength X, they will always -due to non-linear optical (electromagnetic) effects -also emit light again (generally they will luminesce), but then mutually incoherently. For the case that X/2>>a, instead of the Airy diffraction pattern the characteristics of a Hertz dipole rather has to be applied, i.e. a2(sin2u)/r2.
Note further, the quantum troughs will also emit scattered electromagnetic radiation of a wavelength of minute fractions of the above X (Fourier expansion plus multipole expansion of the light emission by a scatterer < or << A) since such a nanometric (in particular if metallic) scatterer is -in a wider sense -always an antenna too. For these,,new", much shorter wavelengths than X, i.e. those Vi, i=1-oo, the diffraction limit holds again in the picture of linear optics.
If now the geometric shape of two microscopic structural details is known, e.g. small round discs, it can of course be calculated, that the resulting diffraction pattern (Fourier space: 2-dimensional Fourier transformation of the lateral absorption function (x,y)) of two such discs (e.g. quantum dots) is the interfering superimposition of two so-called Airy-diffraction pattern functions (Fig.lb, 2a and 2b in this case show the envelopes of the total intensity profile) for X/2<=a or slightly >a [18] respectively dipole characteristics for X/2>>a and it can of course be back-calculated to the shape of the diffracting structural details respectively scattering structural dipolar (multipolar) details (real space) -i.e. Fourier back transformation or back calculating scattering theory if for instance a CCD-camera has measured these Airy-diffraction "functions" (the diffracted intensity profile, the Airy diffraction pattern) quantitatively. In case the quantum dots are luminescing at least partially mutually incoherently, then the interference does not occur at least partially and the Airy-diffraction profiles (for X/2<a or slightly >a [18]) respectively dipole characteristics (for X/2>>a) add up scalarly just like the envelope curve in Fig. 2a,b is drawn; thus these single Airy diffraction patterns can be deconvoluted by mere subtraction followed by Fourier back-transformation in the case of for X/2<=a or slightly >a [18]. For the case X/2>>a the dipole (multipole) characteristics has to be back-calculated to the scattering dipole (multipole).
In the here invented set-up, the method is initially limited to the ultra highly spatially resolved spectroscopy (beyond/below the diffraction limit of A/2) of a known sample geometry, which makes the deconvolution [subtraction in Fourier space] much more simple and unambiguous.
GB1011618A 2010-02-10 2010-07-12 Spectroscopy on mutually incoherently luminescing quantum dots, optical read out of quantum troughs, and fabrication of a writable array of quantum troughs Withdrawn GB2477817A (en)

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