• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    Micro- and nanostructured semiconductor material, obtaining procedure and use as a calibration standard. The present invention relates to a micro- and nano-structured semiconductor material that serves as a calibration standard, particularly as a spatial calibration and conductive pattern in measurements with conductive atomic force microscopes. Furthermore, the present invention relates to the method of manufacturing said material by means of the technique of periodic surface structuring induced by laser and the use of a mask. Therefore, the present invention could be framed in the field of sample analysis and characterization techniques. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2644586A1
    申请号:ES201630556
    申请日:2016-04-29
    公开日:2017-11-29
    发明作者:Esther Rebollar González；Álvaro RODRÍGUEZ RODRÍGUEZ；Tiberio Ezquerra Sanz；Mari Cruz GARCÍA GUTIÉRREZ
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

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    Semiconductor micro- and nanostructured material, procedure for obtaining and using as a calibration standard
    DESCRIPTION
    The present invention relates to a micro- and nanostructured semiconductor material that serves as a calibration pattern, particularly as a spatial and conductor calibration pattern in measurements with conductive atomic force microscopes. In addition, the present invention relates to the process of manufacturing said material by means of the technique of periodic surface structuring induced by laser and the use of a mask. Therefore, the present invention could be framed in the sector of analysis techniques and sample characterization.
    STATE OF THE TECHNIQUE
    Atomic Force Microscopy (AFM) has become a very powerful tool in recent years in visualizing matter at the nanometric and even sub-nanometer scale [Schonherr H, Vancso G. "Scanning force microscopy of polymers." Heidelberg: Springer; 2010]. More recently, AFM technology has gone beyond simple visualization ["Assessment and Formation Mechanism of Laser-Induced Periodic Surface Structures on Polymer Spin-Coated Films in Real and Reciprocal Space" Rebollar E, Perez S, Hernandez JJ, Martln-Fabiani I, Rueda DR, Ezquerra TA, Castillejo M, Langmuir, 27 (9), 5596-5606 (2011)] and has evolved to become a true discipline that uses the physics and chemistry of the levers (“cantilevers”) of the AFM for the evaluation on a nanoscopic scale of a large number of physical quantities, among which the mechanical properties (Elastic modulus, deformation, adhesion) are worth mentioning ["Quantitative Mapping of Mechanical Properties in Polylactic Acid / Natural Rubber / Organoclay Bionanocomposites as Revealed by Nanoindentation with Atomic Force Microscopy "DE Martlnez-Tong, A.S. Najar, M. Soccio, A. Nogales, N. Bitinis, M.A. Lopez-Manchado, T.A. Ezquerra, Composites Science and Technology 104 (2014) 34], the piezoelectric properties [“Improving information density in ferroelectric polymer films by using nanoimprinted gratings" Martlnez-Tong DE, Soccio M, Garcla-Gutierrez MC, Nogales A, Rueda DR, Alayo N, Perez-Murano F, Ezquerra TA, Applied Physics Letters 102 (19), 191601 (2013)], electrical conductivity [“Elucidating the nanoscale origins of organic electronic
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    function by conductive atomic force Microscopy ’’ J.M. Mativetsky, Y.L. Loob, P. Samoric, J. Mater. Chem. C, 2014, 2, 3118] and thermal properties ["Diameter-dependent melting behavior in electrospun polymer fibers", W. Wang, A. H. Barber, Nanotechnology 21 (2010) 225701] among others.
    One of the problems that usually occurs when using the AFM technique is calibration. Although, for spatial calibration, there are different types of standard samples, which are generally supplied by AFM equipment manufacturers, the same is not true for the calibration of the other measurement modalities that can be accessed with the AFM. In particular, when the AFM is used for the measurement of electric currents, it is called the conductive atomic force microscope (c-AFM), it is quite common that no standard samples are available to let you know if the system is working perfectly.
    Therefore, it is necessary to develop new calibration standards for the different types of measurements that can be performed using AFM.
    DESCRIPTION OF THE INVENTION
    The present invention relates to a sheet of a semiconductor material deposited on a conductive substrate comprising a characteristic micro- and nanostructured surface where the micrometric structures serve to carry out the gross spatial calibration of the micrometric scale in measurements with force microscopes Atomic and where the nanometric structures serve to perform the fine spatial calibration of the nanometric scale.
    Said sheet of a micro- and nanostructured semiconductor material is also characterized by having well-defined micrometric and nanometric structures that exhibit electrical conductivity, whereby said sheet can also be used as a conductor calibration pattern in measurements with conductive atomic force microscopes.
    The present invention is, therefore, a sheet of a semiconductor material with a micro- and nanostructured surface that serves as a pattern of spatial and conductive calibration in measurements of atomic force microscopes, particularly in conductive atomic force microscopes.
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    The present invention also relates to the process of manufacturing said sheet of a semiconductor material. The procedure is based on the surface structuring of a semiconductor material determined by the laser induced periodic surface structuring technique, the "laser induced periodic surface structuring" LIPSS, and the use of a mask.
    The LIPSS technique consists in the repetitive irradiation of a material with a linearly polarized laser beam so that it results in the formation of linear periodic structures on the surface of the material, parallel to the polarization of the laser and with sizes of the order of the length of irradiation wave This technique allows the nanostructuring of materials with a simple experimental assembly being able to modify areas of a size of up to square centimeters on a short time scale (of minutes) and by using low energy densities (below a few tens of mJ / cm2) taking place the superficial modification without ablation or ejection of material. A limitation of the technique, however, is that it requires the use of a material that absorbs the wavelength of irradiation and that said material has little roughness on the nanometric scale so that the mechanism of interference and feedback responsible for the formation of the LIPSS be effective This feedback mechanism is related to the use of hundreds or thousands of laser pulses depending on the material, so that there are cycles of heating and cooling of the material that give rise to the rearrangement of the same. Examples of these materials are polymers, metals, dielectrics, semiconductors, etc ...
    The present invention relates to the simultaneous micro- and nanostructuring of the surface of a semiconductor material by irradiation through a mask of a certain size and shape, using the irradiation conditions that lead to the formation of induced periodic surface structures by laser (LIPSS structures), that is, by employing low energy densities of the laser pulses, below a few tens of mJ / cm2.
    The mask located at a certain distance from the surface of the semiconductor material produces several distinctive zones in the semiconductor material. On the one hand, the shape and size of the mask define the shape and size of a cell. On the other, it induces the formation of a Fresnel diffraction pattern inside said cell with maximum and minimum intensity and determined separation, of
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    so that the local variations of the laser intensity produced by said effect give rise to the microstructuring of the semiconductor material.
    Fresnel diffraction is a near-field effect produced when the incident wave source or the observation point from which they are observed, or both, are at a finite distance from the aperture or obstacle that produces the diffraction, in this Case the mask. In particular, for an electromagnetic wave crossing a screen, there is a Fresnel diffraction when the ratio a2 / LA is greater than the unit, being at the size of the opening, L the distance from the opening to the screen and A the length of electromagnetic wave In the present invention, the screen is the surface of the semiconductor material. Due to the phenomenon of diffraction, maximum and some minimum intensity (diffraction pattern) are obtained, so the local energy that reaches the screen is not the same at all points. The maximum and minimum intensity (diffraction pattern) can be calculated from the opening geometry, the distance from the opening to the screen and the electromagnetic wavelength.
    In the present invention, the mask used in the manufacturing process is micrometric in size, so that both the size of the cell that is produced on the surface of a semiconductor material and the Fresnel diffraction pattern that is produced in the Inside said cell are of the micrometric order.
    The shape of the mask of the present invention is variable, from a polygon to a calculation, obtaining different diffraction patterns on the surface of the semiconductor materials. In the reference “Fresnel diffraction and fractal patterns from polygonal apertures" JG Huang, JM Christian, and GS McDonald J. Opt. Soc. Am. A, Vol. 23, No. 11 you can see the different Fresnel patterns that can be Obtain depending on the polygonal opening or polygonal mask used.
    The sheet of a micro- and nanostructured semiconductor material of the present invention is further characterized by having well-defined micrometric and nanometric structures that exhibit electrical conductivity; These are the valleys or minimum levels of current that have electrical conductivity and therefore can be used as a conductor calibration pattern in measurements with c-AFM microscopes, both for coarse calibration and fine calibration.
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    Finally, the present invention refers to the use of the material of the invention as a calibration pattern in AFM and c-AFM measurements.
    Therefore, in a first aspect, the present invention relates to a material (from here "the material of the invention") characterized in that it is a semiconductor material with a roughness of between 0.1 nm and 10 nm capable of absorb light between 30 nm and 1100 nm, and because it comprises a surface with at least one cell, where said cell comprises a representative magnitude of micrometer size, and, inside said cell, a first zone and a second zone are located zone,
    • where said second zone is registered in the first zone,
    • where said first zone has a period of decreasing oscillation, a decreasing amplitude and a distance between two equivalent points within the period of oscillation of the micrometric order, between 0.5 pm and 5 pm,
    • where the second zone has a period of constant oscillation and a distance between two equivalent points within the period of oscillation of the nanometric order, between 20 nm and 1000 nm,
    • and where the valleys of the period of oscillation of said first zone and of said second zone have electrical conductivity between 2 pA and 1 pA when a potential difference -10 V and 10 V is applied.
    The material of the invention is a semiconductor material that exhibits little roughness, between 0.1 nm and 10 nm so that the interference and feedback mechanism responsible for the formation of the LIPSS is effective. It is selected from a polymer, a fullerene, a derivative of fullerene or a combination thereof.
    In the present invention, "fullerene derivative" is understood as that compound that retains the exceptional physical and chemical properties of precursor fullerenes.
    In a preferred embodiment, the material of the invention is poly (3-hexylthiophene), also known as P3HT.
    In another preferred embodiment, the material of the invention is phenyl-C71-butyl acid
    methyl ester, also known as PC71BM.
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    The material of the invention is also capable of absorbing light of any wavelength between 30 nm and 1100 nm from a laser source, whereby any laser source operating in the range of said corresponding wavelengths can be used at the beginning of the X-rays and whose limit is the near IR.
    Preferably, the material of the invention is a semiconductor material capable of absorbing the wavelengths at which an Nd: YAG laser operates: 1064 nm, 532 nm, 355 nm, 266 nm and 213 nm.
    Inside the cell of the material of the present invention a first zone and a second zone can be distinguished,
    or where said second zone is inscribed in the first zone, or where said first zone has a period of decreasing oscillation, a decreasing amplitude and a distance between two equivalent points within the period of oscillation of the micrometric order, between 0.5 pm and 5 pm, or where the second zone has a period of constant oscillation and a distance between two equivalent points within the period of oscillation is of the nanometric order, between 20 nm and 1000 nm, and where the oscillation period valleys of said first zone and of said second zone have electrical conductivity between 2 pA and 1 pA when a potential difference -10 V and 10 V is applied.
    The first zone corresponds to a Fresnel diffraction pattern characterized by having a period of decreasing oscillation, a decreasing amplitude and a distance between two equivalent points within the period of oscillation of the nanometric order, for example, the two equivalent points are valley- valley or ridge-ridge.
    The Fresnel diffraction pattern that can be distinguished on the surface of the semiconductor material is produced by the use of a mask. Since the mask used in the manufacturing process is micrometric in size, both the size of the cell that is produced on the surface of the semiconductor material and the Fresnel diffraction pattern that is produced inside said cell are of the micrometric order . The representative magnitude of said cell corresponds to a representative dimension of the mask, for example, with a side of a polygon or the diameter of a calculation. This representative magnitude of the cell is the origin of the Fresnel diffraction.
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    The second zone corresponds to the LIPSS pattern. Said second zone is registered in the first zone.
    In a preferred embodiment, the material of the invention is capable of absorbing light of 266 nm and where the second zone of the cell has a period of constant oscillation and a distance between two equivalent points within the period of oscillation of 190 nm and 210 nm .
    In another preferred embodiment, the material of the invention the semiconductor material is capable of absorbing light of 532 nm and where the second zone has a period of constant oscillation and a distance between two equivalent points within the period of oscillation of 410 nm and 470 nm .
    In another preferred embodiment, the semiconductor material is capable of absorbing light of 213 nm and where the second zone of the cell has a period of constant oscillation and a distance between two equivalent points within the period of oscillation of 150 nm and 190 nm.
    In addition, the material of the invention is characterized in that it comprises a surface with at least one cell. The surface size of the material of the invention should be such that it can be placed in the visualization zone of a sample by atomic force microscopy, particularly by conductive atomic force microscopy, therefore, a size of about 1 cm 2.
    The cell mentioned above comprises a representative magnitude of micrometric size.
    "Representative magnitude" means, in the present invention, that micrometer size dimension that serves to perform the spatial gross calibration in atomic force microscopes, that is, micrometric calibration. Said representative magnitude corresponds to the representative magnitude according to the shape and size of the mask used during the procedure of obtaining the material.The shape of the mask varies from any polygon to even a circle; in the first case a side of the polygon characterizes it the significant magnitude of the cell and, in in the second case, the diameter of the circle would be the representative magnitude.
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    In a preferred embodiment, the cell is a calculation and the representative magnitude is the diameter of said calculation that varies between 50 pm and 500 pm.
    In another preferred embodiment, the cell comprises a first representative magnitude and a second representative magnitude, where the first representative magnitude and the second magnitude are orthogonal to each other, and where the first representative magnitude and the second representative magnitude are micrometric in size.
    More preferably, the cell is a square and the sides or the first and second magnitude representative of said square measure between 50 pm and 500 pm.
    More preferably, where the cell is a rectangle and a first side or first representative magnitude measures between 40 pm and 100 pm and the second side or second representative magnitude measures between 100 pm and 500 pm.
    Inside the cell of the material of the present invention a first zone with a period of decreasing oscillation (Fresnel diffraction zone) and a second zone with a constant oscillation period and where the valleys of the oscillation period of can be distinguished said first zone and said second zone have electrical conductivity.
    The measurements of the electric current in a conductive atomic force microscope (c-AFM) are carried out by applying a potential difference between the substrate and the tip, normally a potential difference between -10 V and 10 V.
    In the material of the present invention, the valleys of the first zone and the second zone have electrical conductivity between 2 pA and 1 pA when a potential difference -10 V and 10 V is applied, sufficient quantity for the material of The present invention can be used as a spatial calibration pattern and driver of a c-AFM conductive atomic force microscope.
    Another aspect of the invention relates to the process of fabrication of the material of the invention (from here the process of the invention) comprising the following steps:
    a) preparing a sheet of a semiconductor material with a roughness of between 0.1 nm and 10 nm and of thickness between 100 nm and 200 nm, capable of absorbing light between 30 nm and 1100 nm on a conductive substrate by techniques of deposition,
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    b) place a mask parallel to the surface of the semiconductor material sheet obtained in step (a) at a distance between 100 pm and 500 pm,
    c) irradiating the sheet of semiconductor material covered with a mask of stage (b) perpendicular to the surface of the semiconductor material sheet with a pulsed laser, d) peeling off the mask of the sheet of the micro- and nano semiconductor material - structured obtained in step (c).
    Step a) refers to the preparation of a sheet of semiconductor material with low roughness between 0.1 nm and 10 nm and a thickness between 100 nm and 200 nm that is capable of absorbing light between 30 nm and 1100 nm on a conductive substrate. Examples of conductive substrates are conductive silicon, pyrolltic graphite oxidium indium and tin also known as ITO, metals such as gold or platinum and substrates coated with a metallic layer of gold or platinum.
    Step (a) can be carried out by any conventional polymer deposition technique. Preferably step (a) is carried out by the centrifugation deposition technique (in English "spin-coating") or by the deposition and evaporation technique.
    The "spin coating" technique consists in depositing a certain volume of a solution of the material in the center of the substrate, and this is rotated so that the material diffuses due to the centrifugal force covering the entire substrate. The solvent used is volatile and evaporates during rotation.
    The deposition and evaporation technique consists in depositing a certain volume of a solution of material on a substrate and waiting until the solvent evaporates completely.
    In step (b) of the process of the invention, a mask is placed parallel to the surface of the sheet of semiconductor material obtained in step (a) at a distance between 100 pm and 500 pm.
    In the present invention, "mask" is understood as that material comprising an opening of a size and shape determined through which the light from a laser passes through. The mask of the present invention is made of a material that does not absorb the wavelength of irradiation laser or not
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    decomposes or deteriorates at the creep that the irradiation laser operates during the process of obtaining the material of the invention, that is, that it has a modification and / or ablation threshold higher than the creep used in the process of the invention so that Stay intact.
    In the present invention, "creep" is understood as the energy per unit area (J / cm2) that is adjusted in the intense pulsed light or laser equipment.
    Preferably, in step (b) of the process of the invention, the distance between the mask and the surface is between 100 pm and 120 pm when the mask is between 15 and 20 pm thick.
    Step (c) of the process refers to the irradiation of the semiconductor material sheet covered with a mask of stage (b) perpendicular to the surface of the semiconductor sheet with a pulsed laser, preferably the laser pulses they are of the order of nanoseconds, between 4 ns and 15 ns, although said duration of the pulse is not limiting being able to use femtosecond lasers with laser pulses between 30 fs and 500 fs
    Step (c) of the process of the invention is carried out by irradiating perpendicularly to the surface of the semiconductor sheet so that the Fresnel diffraction is effectively translated into the first area of the cell of the material of the invention.
    In a preferred embodiment, step (c) of the process of the invention is carried out with a pulsed laser, with laser pulses between 4 ns and 15 ns, operating at a wavelength of 266 nm and at a creep of between 12 mJcm-2 and 15 mJcm-2. The number of pulses used is between 2000 and 6000.
    For this preferred embodiment, a mask can be used, for example, of copper, metal that although absorbs the light of 266 nm does not deteriorate at the flow of operation during the process of the invention, which are between 12 mJcm-2 and 15 mJcm-2.
    In another preferred embodiment, step (c) of the process of the invention is carried to
    out with a pulsed laser, with laser pulses between 4 ns and 15 ns, which operates at
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    a wavelength of 532 nm and a creep of between 25 mJcm-2 and 35 mJcm-2. The number of pulses used is between 2000 and 12000.
    In another preferred embodiment, step (c) of the process of the invention is carried out with a pulsed laser, with laser pulses between 4 ns and 15 ns, operating at a wavelength of 213 nm and a creep of between 10 mJcm-2 and 15 mJcm-2. The number of pulses used is between 2000 and 6000.
    Step (d) of the process of the invention tries to peel off the mask from the sheet of micro- and nanostructured semiconductor material of the present invention manually or with the aid of tweezers.
    The last aspect of the invention refers to the use of the material of the invention as a calibration pattern of a microscope. Preferably as a calibration pattern of an atomic force microscope.
    In another preferred embodiment of the present invention it refers to the use of the material of the invention as a spatial calibration pattern and conductor of a conductive atomic force microscope.
    Commonly to carry out electrical conductivity measurements with a c-AFM microscope, the sample to be analyzed is fixed on a metallic disk with conductive material, for example a conductive epoxy resin, silver paint, copper adhesive, and said disk is introduced into the visualization zone of the microscope. Then a tip is selected that is conductive and suitable for measurements in contact mode, for example a common tip that is coated with PtIr and the c-AFM measurement mode is selected on the device. For this type of measurement the electrical contact between the support and the sample, the sample and the tip and the tip and the equipment, is critical, which means an error in the measurement if they cannot be controlled.
    The use of the material of the invention as a spatial calibration pattern and driver of the c-AFM provides not only information on the correct operation of the equipment in conductive mode but also spatial information. Applying a potential difference in the range -10 to 10 V, topography and conductivity images can be taken in real time and simultaneously, observing conductive regions (valleys) separated by non-conductive regions (ridges or peaks).
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    The advantages of the present invention with respect to the material of the invention are therefore:
    - The micro-nano structure of the present invention is characterized by presenting an alternation of conductive and insulating regions which allows simultaneous spatial and conductive calibration
    - The material of the invention is a semiconductor material, selected from a semiconductor polymer, a fullerene, a derivative of a fullerene or a combination thereof, whereby the measurement of electrical current of these organic materials is carried out at moderate voltages, comparable to those needed in inorganic semiconductors.
    The advantages of the present invention with respect to the process of the invention are:
    - In a single step, two-scale structures of micro- and nanometric size are obtained using moderate creeps in the range of tens of mJ / cm2 in contraposition with other techniques such as lithography
    - No special environmental conditions are necessary, such as those in clean rooms or glove boxes necessary for the application of lithographic techniques.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE FIGURES
    FIG. 1st plan view of the micro- and nanostructured surface of the material of the invention.
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    FIG. 1b Plan view and elevation view of the interior of a cell of the material of the invention.
    FIG. 2 Photograph of the polymer pattern in the microscope.
    FIG. 3 Image through optical microscope objective in which several cells with a size of 90 pm x 90 pm are observed.
    FIG. 4 AFM topography image in which the microstructures and nanostructures obtained by laser irradiation are observed.
    FIG. 5 AFM topography image in which the microstructures and nanostructures obtained by laser irradiation are observed.
    FIG. 6 AFM images of topography and conductivity in a sample of P3HT modified by irradiation at 266 nm.
    FIG. 7 AFM images of topography and conductivity in a sample of P3HT modified by irradiation at 532 nm.
    EXAMPLES
    The invention will now be illustrated by tests carried out by the inventors, which show the effectiveness of the product of the invention.
    A P3HT pellet with a thickness of 150 nm and prepared by centrifugal deposition is irradiated with a wavelength of 266 nm in normal incidence with a creep of 13.4 mJ / cm2 and 3600 pulses through a grid with square cells with a size of 90 pm side and 18 pm thick that is placed in contact with the pofimero sample. The samples are characterized by AFM and by c-AFM and it is observed that the valleys are conductive.
    In FIG. 1 shows the plan view of the surface of the material of the invention. FIG. 1a shows the plan view of said surface where 1 is the surface of the semiconductor material of the invention and 2 is a Cell. In FIG. 1b shows the plan view and the elevation view of the interior of the cell of the material of the invention
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    where 2 indicates the Cell, 3 the 1st zone, that is, the Fresnel diffraction zone and 4 the 2nd zone corresponding to the LIPSS structuring zone.
    In FIG. 2 a photo of the polymer pattern is shown on the conductive support being introduced into the microscope.
    In FIG. 3 an image is observed through an optical microscope objective in which several cells are observed with a size of 90 qm x 90 qm resulting from the irradiation of the semiconductor material sheet with a wavelength of 532 nm through a grid with a cell size of 90 qm x 90 qm.
    FIG. 4. Image of topography of AFM in which the micro- and nanostructures obtained by laser irradiation with a wavelength of 266 nm are observed through a grid with a cell size of 90 qm x 90 qm. The microstructures produced by the effect of Fresnel diffraction are observed in the areas near the edge of the cell
    FIG. 5. Image of topography of AFM, magnification of the area of the edge of the image of the previous figure. The microstructures and nanostructures obtained by laser irradiation are observed. The vertical lines correspond to the structuring resulting from the Fresnel diffraction with a decreasing oscillation of 2.5 qm, 1.4 qm, 1 qm, and 0.9 qm as the distance from the edge of the cell increases. A profile corresponding to the line marked on the topography image is shown below the image.
    FIG. 6. AFM images of topography and conductivity in a sample of modified P3HT by irradiation at 266 nm in the central area of the cell. It is observed that the valleys of the nanometric structures with a period of 190 nm have conductivity.
    Additionally a sample of P3HT prepared under the same conditions is irradiated at 532 nm with 3600 pulses at a creep of 26 mJ / cm2.
    FIG. 7. Images of topography and conductivity AFM in a sample of modified P3HT by irradiation at 532 nm in the central area of the cell. It is observed that the valleys of the nanometric structures with a period of 430 nm have conductivity.
    The sample is inserted into the microscope and a conductive tip is used for calibration, in this case silicon coated with PtIr. The mode of conductive measurements in the microscope is selected. A potential difference of -10 V is applied and the current flow through the sample is measured. The sheet of micro- and nanostructured semiconductor material 5 exhibits conductivity in the valleys of structures of the order of 300 pA.
    权利要求:
    Claims (22)
    [1]
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    1. A material characterized in that it is a semiconductor material with a roughness between 0.1 nm and 10 nm capable of absorbing light between 30 nm and 1100 nm, and in that it comprises a surface with at least one cell, where said cell it comprises a representative magnitude of micrometric size, and, within said cell, a first zone and a second zone are located,
    • where said second zone is registered in the first zone,
    • where said first zone has a period of decreasing oscillation, a decreasing amplitude and a distance between two equivalent points within the period of oscillation of the micrometric order, between 0.5 pm and 5 pm,
    • where said second zone has a period of constant oscillation and a distance between two equivalent points within the period of oscillation of the nanometric order, between 20 nm and 1000 nm,
    • and where the valleys of the period of oscillation of said first zone and of said second zone have electrical conductivity between 2 pA and 1 pA when a potential difference between -10 V to 10 V. is applied.
    [2]
    2. The material according to claim 1, wherein the semiconductor material is selected from a polymer, a fullerene, a fullerene derivative or a combination thereof.
    [3]
    3. The material according to any of claims 1 or 2, wherein the material is PC71BM.
    [4]
    4. The material according to any one of claims 1 or 2, wherein the semiconductor material is P3HT.
    [5]
    5. The material according to any one of claims 1 to 4, wherein the semiconductor material is capable of absorbing light between 150 nm and 600 nm and where the second zone of the cell has a period of constant oscillation and a distance between two equivalent points within the period of oscillation between 130 nm and 550 nm.
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    [6]
    6. The material according to any one of claims 1 to 5, wherein the semiconductor material is capable of absorbing light of 266 nm and where the second zone of the cell has a period of constant oscillation and a distance between two equivalent points within the period of 190 nm and 210 nm oscillation.
    [7]
    7. The material according to any one of claims 1 to 5, wherein the semiconductor material is capable of absorbing light of 532 nm and where the second zone has a period of constant oscillation and a distance between two equivalent points within the period of oscillation of 410 nm and 470 nm.
    [8]
    8. The material according to any one of claims 1 to 5, wherein the semiconductor material is capable of absorbing light of 213 nm and where the second zone of the cell has a period of constant oscillation and a distance between two equivalent points within the period of 150 nm and 190 nm oscillation.
    [9]
    9. The material according to any one of claims 1 to 8, characterized in that the cell is a calculation and the first representative magnitude is the diameter of said calculation that varies between 50 pm and 500 pm.
    [10]
    10. The material according to any one of claims 1 to 8, characterized in that the cell comprises a first representative magnitude and a second representative magnitude, where the first representative magnitude and the second magnitude are orthogonal to each other, and where the first representative magnitude and the second representative magnitude are micrometric in size,
    [11]
    11. The material according to claim 10, wherein the cell is a square and the sides of said square measure between 50 pm and 500 pm.
    [12]
    12. The material according to claim 10, wherein the cell is a rectangle and a first side or first representative magnitude measures between 40 pm and 100 pm and the second side or second representative magnitude measures between 100 pm and 500 pm.
    [13]
    13. Material manufacturing process as defined in any one of claims 1 to 12, comprising the following steps:
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    a) preparing a sheet of a rough semiconductor material between 0.1 nm and 10 nm and between 100 nm and 200 nm thick, capable of absorbing light between 30 nm and 1100 nm on a conductive substrate by deposition techniques ,
    b) place a mask parallel to the surface of the sheet obtained in step (a) at a distance between 100 pm and 500 pm,
    c) irradiate the coated sheet with a mask of step (b) perpendicular to the surface of the sheet with a pulsed laser,
    d) peel off the mask from the micro-nano-structured sheet obtained in step (c).
    [14]
    14. The method according to claim 13, wherein the conductive substrate used in step (a) is conductive silicon, pyrolltic graphite oxidium indium and tin, metals such as gold or platinum and metal coatings of gold or platinum.
    [15]
    15. The method according to any of claims 13 or 14, wherein step (a) is carried out by a deposition technique selected from the centrifugal deposition technique and the deposition and evaporation technique.
    [16]
    16. The method according to any of claims 13 to 15, wherein, in step (b), the distance between the mask and the surface is between 100 pm and 120 pm when the mask is between 15 and 20 pm thick. .
    [17]
    17. The method according to any one of claims 13 to 16, wherein step (c) of the procedure is carried out with a pulsed laser, where the pulses of the laser are of the order of nanoseconds, between 4 ns and 15 ns,
    [18]
    18. The method according to claim 17, wherein step (c) is carried out with a pulsed laser operating at a wavelength of 266 nm and at a creep of between 12 mJcm "2 and 15 mJcm" 2.
    [19]
    19. The method according to claim 17, wherein step (c) is carried out with a pulsed laser operating at a wavelength of 532 nm and a creep of between 25 mJcm "2 and 35 mJcm" 2.
    [20]
    20. The method according to claim 17, wherein step (c) is carried out with a pulsed laser operating at a wavelength of 213 nm and a creep of between 10 mJcm "2 and 15 mJcm" 2.
    [21]
    21. Use of the material according to any of claims 1 to 12 as a calibration pattern of a microscope.
    5 22. Use of the material according to claim 21, as a spatial calibration pattern
    of an atomic force microscope.
    [23]
    23. Use according to any of claims 21 or 22, as a spatial calibration pattern and conductor of a conductive atomic force microscope.
    10
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    同族专利:
    公开号 | 公开日
    WO2017187002A1|2017-11-02|
    ES2644586B1|2018-09-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP4644723B2|2008-03-31|2011-03-02|株式会社日立ハイテクノロジーズ|Measuring device with nanotube probe|
    EP2976678B1|2013-03-18|2017-06-14|Eulitha A.G.|Methods and systems for printing periodic patterns|
    CN103364595B|2013-07-17|2015-04-22|中国科学院半导体研究所|Method for representing phase separation degree of polymer solar cell photosensitive layers|
    KR20150029997A|2013-09-11|2015-03-19|삼성디스플레이 주식회사|Halftone mask and method of manufacturing display device using the same|
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    ES201630556A|ES2644586B1|2016-04-29|2016-04-29|MICRO- AND NANO- STRUCTURED SEMICONDUCTOR MATERIAL, PROCEDURE FOR OBTAINING AND USE AS A CALIBRATION PATTERN|ES201630556A| ES2644586B1|2016-04-29|2016-04-29|MICRO- AND NANO- STRUCTURED SEMICONDUCTOR MATERIAL, PROCEDURE FOR OBTAINING AND USE AS A CALIBRATION PATTERN|
    PCT/ES2017/070266| WO2017187002A1|2016-04-29|2017-04-28|Micro-and nano-structured semiconductor material, production method and use as a calibration standard|
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