RU170927U1 - ATOMICALLY POWER MICROSCOPE PROBE WITH PROGRAMMABLE SPECTRAL PORTRAIT OF A RADIATING ELEMENT BASED ON QUANTUM POINTS OF THE NUCLEAR SHELL STRUCTURE - Google Patents

Abstract

The utility model relates to measuring technique and can be used in probe scanning microscopy and atomic force microscopy to diagnose and study nanoscale structures. The essence of the utility model is that the cantilever is connected to a probe needle, the tip of which is fixed in one of the cone-shaped nanopores of the polymer sphere, containing an ordered array of cone-shaped nanopores of different diameters, filled with corresponding quantum dots with different discrete emission spectra and non-radiative spheres, using a combination of combinations of diameters of which the general spectral portrait of radiation is programmed. The technical result is the possibility of simultaneous combination of electromagnetic multi-wave with a programmable spectrum of radiation exposure with the measurement of the mechanical reaction to this stimulating effect at one common point on the surface of the diagnostic object without affecting neighboring areas. 4 ill.

Description

The utility model relates to measuring technique and can be used in probe scanning microscopy and atomic force microscopy to diagnose and study nanoscale structures.

A known atomic force microscope probe with a nanocomposite emitting element doped with quantum dots of the core-shell structure, including a cantilever connected to a probe needle, the tip of which is fixed in one of the nanopores of the glass sphere, the remaining nanopores are filled with quantum dots of the core-shell structure without leaving their shells behind the perimeter of the glass sphere coated on the outside with a protective transparent layer, an external source of excitation of quantum dots directed to the center of the glass sphere (patent RU 2541422 C February 1, 10/10/2015 G01Q 60/24, B82Y 35/00 A probe of an atomic force microscope with a nanocomposite emitting element doped with quantum dots of a core-shell structure / Linkov VA, Vishnyakov NV, Litvinov V.G. .).

A disadvantage of the known technical solution is the lack of the possibility of simultaneously combining an electromagnetic multi-wave effect with a programmable emission spectrum with measuring a mechanical reaction (elastic modulus) on this stimulating effect at one common point on the surface of the diagnostic object without affecting neighboring areas.

The closest in technical essence is an atomic force microscope probe with a nanocomposite emitting element based on quantum dots of the core-shell structure, including a cantilever connected to a probe needle, the tip of which is fixed in one of the nanopores of the polymer sphere, the remaining nanopores are filled with quantum dots of the core structure a shell without exiting their shells beyond the perimeter of the polymer sphere coated on the outside with a protective transparent layer, an external source of excitation of quantum dots aimed at prices p of the polymer sphere (utility model patent RU 140229 U1, 05/10/2014 G01Q 60/24. Probe of an atomic force microscope with a radiating element based on quantum dots of the core-shell structure / Linkov V.A., Vishnyakov N.V., Litvinov V.G.).

A disadvantage of the known technical solution is the lack of the possibility of simultaneously combining an electromagnetic multi-wave effect with a programmable emission spectrum with measuring a mechanical reaction (elastic modulus) on this stimulating effect at one common point on the surface of the diagnostic object without affecting neighboring areas.

The difference between the proposed technical solution and the above is the use of a programmable nanocomposite emitting element in the form of a polymer sphere containing an array of groups of cone-shaped nanopores that are uniformly distributed over its surface, filled with a combination of nonradiative nanospheres and quantum dots of the core-shell structure, forming queue, a code combination of emitted and forbidden wavelengths, together forming a given spectral portrait radiation. This makes it possible to program various spectral radiation patterns in polymeric spheres with identical universal ordered nanopore structures by combining combinations of quantum dots of the core-shell structure and nonradiative nanospheres, each of which, when inserted into nanopores of the same diameter, generates radiation with a wavelength determined by its diameter , or prohibits the generation of this wavelength. This also allows us to achieve repeatability of the spectral patterns of the radiating elements of the probes during their replication.

The technical result is the possibility of simultaneous combination of the electromagnetic multi-wave with a programmable radiation spectrum of the impact with the measurement of the mechanical reaction (elastic modulus) on this stimulating effect at one common point on the surface of the object of diagnosis without affecting neighboring areas.

The technical result of the proposed utility model is achieved by a set of essential features, namely, an atomic force microscope probe with a programmable spectral portrait of a radiating element based on quantum dots of a core-shell structure, including a cantilever connected to a probe needle, the tip of which is fixed in one of the nanopores of the polymer sphere, the remaining nanopores of which are filled without leaving their shells beyond the perimeter of the polymer sphere, by quantum dots of the core-shell structure coated on the outside a protective layer, an external electromagnetic source of excitation of quantum dots of the core-shell structure, the polymer sphere contains an array uniformly distributed over its surface, consisting of more than two cone-shaped nanopores with different diameters with an equal number of cone-shaped nanopores of the same diameter in each nanoscale group, non-radiative nanospheres with diameters equal to the diameters of the used quantum dots of the core-shell structure, the total number of nonradiative nanospheres in the sum with the quantum dots of the core-shell structure is equal to the number of cone-shaped nanopores filled with them, the number of nanoscale groups of which is equal to the maximum number of discrete wavelengths emitted by quantum points of the core-shell structure that are embedded in cone-shaped nanopores corresponding to their diameter, and a programmable combination of combinations of quantum diameters points of the core-shell structure and nonradiative nanospheres embedded in cone-shaped nanopores corresponding to their diameter a sequence of combinations of emitted and non-emitted discrete wavelengths that together form a given spectral portrait of the radiation of an atomic force microscope probe with a programmable spectral portrait of a radiating element based on quantum dots of the core-shell structure.

The essence of the utility model is illustrated in FIG. 1, which shows a probe of an atomic force microscope with a programmable spectral portrait of a radiating element based on quantum dots of a core-shell structure (remote element A is shown in Fig. 2). In FIG. Figure 2 shows an extension element A (10: 1) on an enlarged scale and in section, illustrating the construction of a probe of an atomic force microscope with a programmable spectral portrait of a radiating element based on quantum dots of a core-shell structure. In FIG. Figure 3 shows schematic images of the mating surfaces of a quantum dot and a cone-shaped nanopore and their dimensional tolerances that do not violate the repeatability of spectral portraits when replicating probes. In FIG. Figure 4 shows a schematic depiction of the step-by-step programming of cone-shaped nanopores by quantum dots of the core-shell structure or nonradiative nanospheres.

The phrase “nanoscale group” used in the text means the following: nanoscale group n is a set of nanospheres or cone-shaped nanopores having the same nominal dimensions, respectively, of external and internal diameters, where: n is the serial number of the nanoscale group, assigned depending on the nominal dimensions of the diameters of the elements forming a group (for example, 1, 2, 3, ... n, n + 1).

An atomic force microscope probe with a programmable spectral portrait of a radiating element based on quantum dots of the core-shell structure of FIG. 1 consists of a cantilever 1 connected to a probe needle 2, on top of which a polymer sphere 3 is fixed with conical nanopores 4, 6, 8, 10, 12, 14, 16 filled with quantum dots 5, 7, 11, 13, 15, 17, the core-shell structure, the excitation of which is carried out by an external electromagnetic source of excitation of quantum dots 18 (for example, a laser diode), located at the base of the cantilever 1 with the radiation direction, oriented to the center of the polymer sphere 3 with cone-shaped nanopores, also in FIG. 1 shows the diagnosed object 19, placed on the substrate 20 at the moment of its contact with the polymer sphere 3 with cone-shaped nanopores (elements 4-17 are shown on an enlarged scale in Fig. 2).

On the extension element A (10: 1) of FIG. 2 shows elements in a section, where the probe needle 2, a polymer sphere with cone-shaped nanopores 3; a conical nanopore 4 and a quantum dot of the core-shell structure 5 embedded in it with a diameter included in the first nanoscale group; a conical nanopore 6 and a quantum dot of the core-shell structure 7 embedded in it with a diameter included in the second nanoscale group; a cone-shaped nanopore 8 and a non-radiating nanosphere 9 embedded in it with a diameter included in the third nanoscale group; a cone-shaped nanopore 10 and a quantum dot of the core-shell structure 11 embedded in it with a diameter included in the fourth nanoscale group; cone-shaped nanopores 12 in one of which a quantum dot of the core-shell structure 13 with a diameter included in the fifth nanoscale group is embedded, and the top of the probe needle 2 is fixed in another cone-shaped nanopore 12, also included in the fifth nanoscale group; a cone-shaped nanopore 14 and a quantum dot of the core-shell structure 15 embedded in it with a diameter included in the sixth nanoscale group; a cone-shaped nanopore 16, and a quantum dot of the core-shell structure 17 embedded in it with a diameter included in the seventh nanoscale group; an external source of electromagnetic radiation for exciting quantum dots of the core-shell structure 18, a diagnostic object 19; substrate 20 on which the diagnostic object 19 is located.

The large arrows in FIG. 2, the direction of the incoming electromagnetic radiation is indicated for the excitation of quantum dots of the core-shell structure λ0 and the radiation converted by the wavelength λ1, λ2, _, λ4, λ5, λ6, λ7, where: λ1, λ2, _, λ4, λ5, λ6, λ7 - the luminescence wavelength of quantum dots of the core-shell structure, respectively, of the first, second, fourth, fifth, sixth, seventh nanoscale.

The wavelength λ3 in this example is not generated as a result of embedding in the cone-shaped nanopore 8 of the nonradiative nanosphere 9 when programming the spectral portrait of the polymer sphere 3 with cone-shaped nanopores according to the technical specifications.

The small arrows in FIG. 2, the direction of the output total radiation f (λ) is indicated, where: f (λ) = (λ1, λ2, _, λ4, λ5, λ6, λ7) is the radiation spectrum of the polymer sphere 3 with cone-shaped nanopores formed by the total radiation of all quantum dots of the structure core-shell.

In FIG. Figure 3 shows schematic representations of the mating surfaces of a quantum dot and a cone-shaped nanopore and their tolerance deviations of sizes that do not violate the frequency of spectral portraits when replicating probes.

Fragment A) (Fig. 3) shows the technical requirements for the tolerance of the diameter of quantum dots of the structure of the core-shell of the nanoscale group n, which can fluctuate by a value Δ from the nominal size dn-Δ downwards for pairing with cone-shaped nanopores of the nanoscale group n.

Fragment B) (Fig. 3) shows the technical requirements for the diameter of the cone-shaped nanopores of the nanoscale group n, where: a cone-shaped nanopore, the diameter of which at a depth Η along the axial line from the base of the cone is equal to the radius (1/2 of the diameter) of the quantum dot of the core-shell structure dn + Δ / 2 of the nanoscale group n, varies by Δ from the nominal size Dn + Δ upwards for conjugation with quantum dots of the core-shell structure of the nanoscale group n.

Fragment B) (Fig. 3) shows the fulfilled conjugation specifications presented for a pair consisting of a quantum dot 11 of the core-shell structure (fragment of FIG. 2) embedded in a cone-shaped nanopore 10 included in one nanoscale group No. 4, where: The quantum dot 11 of the core-shell structure with diameters d4-Δ embedded in the corresponding nanopore with diameters D4 + Δ without the output of a quantum dot shell beyond the perimeter of the surface of the polymer sphere 3 with conical nanopores is presented. The arrows indicate, respectively, the input wavelength of the excitation of the quantum dot λ0 and the converted wavelength λ4. Where: d is the nominal size of the outer diameter of the quantum dot of the core-shell structure; D is the nominal size of the inner diameter of the conical nanopore; n is the number of the nanoscale group; Δ is the maximum size of the variation in diameters, taking into account the temperature drift, at which the repeatability of the spectral portraits is preserved (i.e., the quantum dot belonging to one group No. n is excluded from the nanopores No. n + 1 belonging to another adjacent nanoscale group).

In FIG. Figure 4 shows a schematic depiction of the step-by-step programming of cone-shaped nanopores by quantum dots of the core-shell structure or nonradiative nanospheres.

In fragment A) (Fig. 4), a spectral portrait of the radiation of the polymer sphere 3 with cone-shaped nanopores is presented, where: at the coordinate Υ-OE are the relative units of radiation intensity; at the coordinate X - λ (nm) is the radiation wavelength in nanometers, λ1, λ2, λ3, λ4, λ5, λ6, λ7 are the discrete radiation wavelengths of quantum dots, respectively, of quantum dots 5, 7, 11, 13, 15, 17, shell, radiation with a wavelength of λ3 is absent, because when programming, instead of a quantum dot, a non-radiative 9 nanosphere is embedded, f (λ) = (λ1, λ2, _, λ4, λ5, λ6, λ7) is the total spectrum that forms the spectral portrait of the radiation.

In fragment B) (Fig. 4), the stepwise filling of conical nanopores with 4, 6, 8, 10, 12, 14, 16, quantum dots of the core-shell structure 5, 7, 11, 13, 15, 17 and non-radiating nanosphere 9 is shown schematically. The vertical curly pointing arrows show the schematic trajectories of the movement of quantum dots (from fragment B to fragment B) when writing logical “1” and the trajectory of moving nanospheres (from fragment G to fragment B) when writing logical “0” during step-by-step programming of cone-shaped nanopores.

Fragment B) (Fig. 4) shows a series of quantum dots of the core-shell structure with successively increasing diameters emitting discrete wavelengths λ1, λ2, λ3, λ4, λ5, λ6, λ7, respectively, included in the first, second, third, fourth , fifth, sixth, seventh nanoscale groups. Each embedded quantum dot in the corresponding cone-shaped nanopore is encoded as a logical “1” of a certain discharge with a certain wavelength.

Fragment D) (Fig. 4) shows a series of non-emitting nanospheres with successively increasing diameters included in the first, second, third, fourth, fifth, sixth, and seventh nanoscale groups, respectively. Each non-radiating nanosphere embedded in a cone-shaped nanopore instead of a quantum dot is encoded as a logical “0” of a certain discharge.

In fragment D) (Fig. 4), the code identification word “1101111” (spectrum signature) is shown as an example, according to which sequential step-by-step programming is performed from larger diameters to smaller diameters by quantum dots of the core-shell structure or non-emitting nanospheres due to the introduction a certain combination of them into cone-shaped nanopores of the polymer sphere 3 corresponding in diameter. Each logical “1” or “0” corresponds to the on or off of a particular wavelength, the aggregate whose combination set determines the general spectral portrait of the radiating element f (λ) = (λ1, λ2, _, λ4, λ5, λ6, λ7), made by programming conical nanopores 4, 6, 8, 10, 12, 14, 16 polymer sphere 3 with cone-shaped nanopores.

Fragment G) (Fig. 4) shows the numbers (Nos. 1, 2, 3, 4, 5, 6, 7) of nanoscale groups, which include cone-shaped nanopores, quantum dots, nonradiative nanospheres with diameters compatible with tolerances and fits.

Fragment 3) (Fig. 4) shows the step numbers (S1, S2, S3, S4, S5, S6, S7), and the horizontal curly pointing arrows show the direction of filling the cone-shaped nanopores with quantum dots of the core-shell structure from a larger diameter to a smaller one.

The excitation wavelength λ0 of the quantum dots 5, 7, 11, 13, 15, 17 of the core-shell structure and the wavelengths of the converted radiation λ1, λ2, _, λ4, λ5, λ6, λ7 of the quantum dots 5, 7, 11, 13, 15 , 17 core-shell structures are determined by their diameter (mainly from 2 to 20 nm), a combination of core material and shell material, their percentage, the transmission spectrum of the protective transparent polymer film and the manufacturing technology of the quantum dot of the core-shell structure. The wavelength of electromagnetic radiation of quantum dots, aimed at the object of diagnosis, can be located both in the optical range and beyond, from the ultraviolet to infrared radiation spectrum. With the same external diameter of a quantum dot, the wavelength of its radiation can be adjusted by changing the ratio of the diameter of the core and the thickness of the surrounding shell.

The core of quantum dots 5, 7, 11, 13, 15, 17 of the core-shell structure may, for example, include at least one material selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS , PbSe, AglnZnS, and ZnO, but not limited to. The shell of quantum dots 5, 7, 11, 13, 15, 17 of the core-shell structure may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but these options are not limited.

To implement the utility model, in addition to classical quantum dots of the core-shell structure, core-multiband quantum dots can also be used (Patent Application Publication Pub. No .: US 20120315391 A1 Pub. Date: Dec. 13, 2012, QUANTUM DOTS HAVING COMPOSITION GRADIENT SHELL STRUCTURE AND MANUFACTURING METHOD THEREOF).

The manufacture of a nanocomposite emitting element is carried out by doping the polymer sphere 3 with cone-shaped nanopores, quantum dots 5, 7, 11, 13, 15, 17 of the core-shell structure and is performed due to the penetration of quantum dots of the core-shell structure and non-radiating nanosphere 9 into the cone-shaped nanopores 4, 6, 8, 10, 12, 14, 16, polymer sphere 3 with cone-shaped nanopores. For example, the doping process can be carried out according to the known method technology by immersing an element of glass with nanometer pores in a solution of two or more quantum dots, followed by drying in air and filling the voids between the quantum dots with resin (patent Application Publication Pub. No .: US 20130011551 A1 Pub. Date: Jan. 10, 2013, QUANTUM DOT-GLASS COMPOSITE LUMINESCENT MATERIAL AND MANUFACTURING METHOD THEREOF).

As nonradiative nanospheres, polymer or glass nanospheres transparent to the programmed emission spectrum can be used, which are in colloidal solutions with identical geometric characteristics of colloidal solutions with quantum dots of the core-shell structure.

An atomic force microscope probe with a programmable spectral portrait of a radiating element based on quantum dots of the core-shell structure works as follows: before starting work, the radiating polymer sphere 3 with conical nanopores is programmed (Fig. 2). The radiation spectrum is programmed by sequentially immersing the polymer sphere 3 with cone-shaped nanopores, pre-connected to the tip of the needle 2 in colloidal solutions of quantum dots with specific diameters corresponding to the radiation wavelength λn for writing logical “1” or by immersing in colloidal solutions with nonradiative nanospheres of identical diameter to write a logical “0” (to exclude generation with a wavelength of λn). The maximum size deviations of the mating elements, which do not affect the repeatability of the spectral patterns, are shown in FIG. 3. After each immersion of the polymer sphere 3 with cone-shaped nanopores in the next colloidal solution, the quantum dots of the core-shell structure fill in all the cone-shaped nanopores into which they can penetrate, that is, during the first immersion, quantum dots of the core-shell structure of the largest diameter fill the cone-shaped nanopores of the largest diameter, but cannot penetrate into the cone-shaped nanopores of the following groups of smaller diameter; during the second immersion, quantum dots of a core-shell structure of a smaller diameter are filled with cone-shaped nanopores of a smaller diameter, but cannot penetrate into cone-shaped nanopores of a smaller diameter and already filled with a larger diameter, and so until the cone-shaped nanopores of a minimum diameter are completely filled with the corresponding quantum dots of the core-shell structure or non-radiating spheres of minimum diameter, as illustrated in FIG. 4. The sequence of logical “0” and “1” is determined by a given identification code word, on the basis of which this or that spectral portrait of the radiation of the polymer sphere 3 with cone-shaped nanopores is formed, which is necessary for studying the diagnostic object 19.

At the end of the programming stage, an atomic force microscope probe with a programmable spectral portrait of a radiating element based on quantum dots of the core-shell structure works as follows: a cantilever 1 with a probe needle 2 is brought to the diagnostic object 19 located on the substrate 20 and presses on it with a polymer sphere 3 with cone-shaped nanopores, receiving data on the elastic properties of the diagnostic object 19, before turning on and after turning on the external electromagnetic excitation source 18 quanta O points core-shell structure with wave length λ0. As a result, quantum dots 5, 7, 11, 13, 15, 17 excite the surface of the diagnosed object 19 by a combination of wavelengths f (λ) = (λ1, λ2, _, λ4, λ5, λ6, λ7) according to the spectral radiation pattern formed during programming specified by the identification code binary word, for example, "1101111". Depending on the required modes, the diagnostics can take place both in the continuous luminescence mode and in the pulsed fluorescence mode (i.e., illumination of the local part of the diagnosed object with only radiation of the spectral picture f (λ) by quantum dots in the interval equal to the time of their fluorescence after switching off external optical source 18 in order to eliminate extraneous illumination and interference).

The proposed design of an atomic force microscope probe with a programmable spectral portrait of a radiating element based on quantum dots of the core-shell structure provides, when scanning the surface of a diagnostic object with an atomic force microscope, the topological distribution of changes in the Young's modulus depending on the stimulating effect of a certain spectrum of electromagnetic multi-wave radiation on each point with coordinates Χ, Y directly located under zluchayuschey polymer spheres with nanopores konusobraznymi. The possibility of programming the radiation spectrum using nonradiative nanospheres and quantum dots of the core-shell structure also makes it possible to identical reproducibility of spectral portraits when replicating probes. All this makes it possible to detect and study individual photosensitive sections of biological objects and nanostructures that change their mechanical properties and sizes under the influence of only a strictly defined code set of wavelengths of electromagnetic radiation directed to a certain point without exposure to the surrounding sections of the studied object, which previously could not be realized probes.

Claims (1)

An atomic force microscope probe with a programmable spectral portrait of a radiating element based on quantum dots of a core-shell structure, including a cantilever connected to a probe needle, the tip of which is fixed in one of the nanopores of the polymer sphere, the remaining nanopores of which are filled without leaving their shells around the perimeter of the polymer sphere quantum dots of the core-shell structure coated on the outside with a protective layer, an external electromagnetic source of excitation of quantum dots of the core-shell structure, distinct The fact that the polymer sphere contains an array uniformly distributed over its surface, consisting of more than two cone-shaped nanopores of different diameters with an equal number of cone-shaped nanopores of the same diameter in each nanoscale group, nonradiative nanospheres having diameters equal to the diameters of the used quantum dots of the structure core-shell, the total number of nonradiative nanospheres in total with quantum dots of the core-shell structure is equal to the number of cones filled by them shaped nanopores, the number of nanoscale groups of which is equal to the maximum number of discrete wavelengths emitted by quantum dots of the core-shell structure that are embedded in cone-shaped nanopores that correspond to their diameter, with a programmable combination of diameters of quantum dots of the core-shell structure and nonradiative nanospheres embedded in the corresponding their diameter cone-shaped nanopores, determines the sequence of combinations of emitted and non-emitted discrete wavelengths, in total forming a predetermined minute portrait spectral radiation probe of an atomic force microscope with programmable spectral portrait radiating element on the basis of quantum dots core-shell structure.

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