WO2012050543A1 - Procédé de formation d'un matériau nanostructuré flexible pour panneaux photovoltaïques et appareil servant à réaliser le procédé - Google Patents

Procédé de formation d'un matériau nanostructuré flexible pour panneaux photovoltaïques et appareil servant à réaliser le procédé Download PDF

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WO2012050543A1
WO2012050543A1 PCT/US2010/002728 US2010002728W WO2012050543A1 WO 2012050543 A1 WO2012050543 A1 WO 2012050543A1 US 2010002728 W US2010002728 W US 2010002728W WO 2012050543 A1 WO2012050543 A1 WO 2012050543A1
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liquid medium
rotating body
nanoparticles
source
flexible substrate
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PCT/US2010/002728
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English (en)
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Boris Gilman
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Boris Gilman
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Priority to PCT/US2010/002728 priority Critical patent/WO2012050543A1/fr
Publication of WO2012050543A1 publication Critical patent/WO2012050543A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/12—Applying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/222—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of pipes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/30—Devices controlled by radiation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention generally relates to flexible nanostructured materials, in particular to highly efficient and low-cost flexible materials for photovoltaic (PV) and optoelectronic (OE) applications. More specifically, the invention relates to a method and apparatus for
  • the method and apparatus apply to the forming of high-efficient and low-cost PV solar panels of large surface area.
  • Nanoparticles of various semiconductors can be synthesized by means of a well known colloidal organic process (see “Efficient solution-processed infrared photovoltaic cells,” Applied Physics Letters, 90, 183113) by deposition from a gas phase or by sputtering.
  • the typical size of a nanoparticle ranges from 2 to 8 run.
  • Nanoparticles may have different shapes, such as quantum dots, wires, rods, crystals, etc.
  • Nanoparticles suitable for photovoltaic (PV) application are exemplified by Si, Ge, CdTe, CdSe, CdS, InP, TiOx, InAs, PbS, PbSe, HgTe, CuInSe 2 , CuInGaSe 2 , etc. (see “Advanced inorganic materials for photovoltaics,” MRS Bulletin, Vol. 32, pp. 211 to 214).
  • a nanoparticle-containing solution is deposited onto a precoated transparent substrate (e.g., glass) and consequently is converted into a very thin film (30 to 200 nm) of a selected type by the spin-casting procedure.
  • Nanoparticles also can be embedded in some photoactive organic films (e.g., polymers) to form a "hybrid" hetero-junction PV device or a bilayer structure to form a bulk hetero-junction (see “Semiconductor- nanocrystal/conjugated polymer thin films," U.S. Patent Application Publication, US2005/0133087, inventor Alivisatos, A. Paul, et al, which discloses manufacture of thin films comprising inorganic semiconductor nanocrystals dispersed in semiconducting polymers in high loading amounts).
  • Such films possess some unique material properties highly desirable for PV applications. Such properties relate to better ability of nanoparticles to use incoming radiation energy, particularly in the IR portion of the spectrum, as compared with bulk and TF counterparts.
  • nanoparticle "patterning” typically relates to device layout formation along the active surface of a device (i.e., horizontal patterning) rather than cross-section patterning across active nanoparticle layers (i.e., vertical patterning).
  • Other types of nanoparticle-based films can be formed in the complimentary layer that has a junction interface with the first layer, e.g., as in the reference “Air-stable all-inorganic nanocrystal solar cells processed from solution," Science, Vol. 310, pp. 462 to 465.
  • nanocomposite films by depositing and processing nanoparticle-based layers are fundamentally limited in producing predefined nanoparticle spatial arrangements of size or type of material. Consequently, PV devices made of such nanocomposite films typically exhibit low carrier transport and collection efficiency (i.e., internal quantum efficiency), incomplete spectral coverage, limited Voc, etc.
  • Some advanced nanocomposite structures for PV applications are described in "Nanostructured Organic-inorganic Hybrid Solar Cells," MRS Bulletin, Vol. 34, pp. 95 to 100. It should be noted, however, that none of the proposed structures present a nanostructured film that comprises a sequence of nanoparticle layers arranged in the order of their size or type of material.
  • U.S. Patent No. 6,368,406 issued in 2002 to S. Deevi, et al discloses a method of forming intermetallic nanoparticles by subjecting a starting material to laser energy so as to form a vapor and condensing the vapor so as to form intermetallic nanoparticles.
  • the starting material can be a mixture of pure elements or an alloy of two or more elements.
  • the nanoparticles can be provided with a narrow size distribution, with an average particle size of 2 to 100 nm, preferably 2 to 9 nm.
  • the nanoparticles can be formed in a vacuum chamber wherein a temperature gradient is provided.
  • the atmosphere in the chamber can be an inert atmosphere, such as argon, or a reactive atmosphere, such as isobutene or oxygen.
  • An electric field can be used to form filaments of the nanoparticles.
  • U.S. Patent No. 5,770,126 issued in 1998 to J. Singh, et al discloses a process and apparatus for producing nanoscale particles using the interaction between a laser beam and a liquid precursor solution.
  • a solid substrate is used during laser-liquid interaction.
  • the laser beam is directed at the solid substrate, which is immersed in the liquid precursor solution, and rotates.
  • the present invention provides a novel and efficient method of depositing multilayer
  • the proposed method of depositing multilayer nanostructured film also provides a predefined sequence of layers in accordance with the size of nanoparticles in the layer. Nanoparticles are assumed to have a round shape of a given radius (quantum dots). The type of material (e.g., InAs, CdSe, etc.). from which the nanoparticle is made defines the density of a nanoparticle.
  • the method of this invention provides depositing nanostructured films on various types of substrates, preferably on flexible substrates of a large area and preferably precoated with conductive and barrier layers.
  • the multilayer nanostructured film can be deposited in a form of an all-inorganic (i.e., consisting of nanoparticles only) structure on the surface of a substrate or, according to another aspect of the invention, in the form of nanoparticle layers embedded into a polymer-based film which was preliminarily applied onto the substrate surface.
  • the aforementioned bulk heteroj unction structure is achieved in the deposited film, thus making it possible to ensure PV-energy conversion.
  • the method can be used to form a novel type of flexible nanostructured material suitable for highly efficient and low-cost PV applications, as well as for optoelectronic, microelectronic, and other applications.
  • the method of depositing multilayer nanostructured films is based on the principles of nanoparticle motion (flight) through a gaseous medium.
  • this process of flying particles is referred to as “FP process” and the term “flying particles” is abbreviated "FP.”
  • the concept and the physical model of the FP process are described below.
  • the essence of the method, according to this invention is to create conditions for nanoparticles of a different size and/or type of material to fly from a properly prepared nanoparticle-containing solution toward a preplaced flexible substrate and through the selected gaseous medium, thus experiencing ambient resistance forces.
  • the nanoparticle-containing solution has a predefined mixture of nanoparticles of different sizes or densities, or both.
  • resistance force experienced by a given nanoparticle moving through a gaseous medium depends on ambient resistance (dynamic viscosity) and on the velocity, size, and density of the nanoparticle.
  • equal initial velocity is provided for all nanoparticles contained in the solution.
  • the resistance force experienced by an FP depends on its instantaneous velocity, size, and density (i.e., type of material). It should be noted that FP motion through the gaseous medium is considered to be identical to the motion of a regular solid mass through the same medium and consequently following the same mechanical laws.
  • the proposed method will create a sequence of nanoparticle layers with well controlled thickness of each layer following each other in order of size or type of material, or both, throughout the film, thus forming a desired multilayer nanostructured film.
  • the FP process described above is realized in an apparatus that comprises the following: (1) sealable cylindrical chamber filled with gas of a required pressure; (2) initial flexible substrate made of an insulating film and precoated with a proper conductive coating (e.g., in the form of a metal conductive film with a carrier- blocking layer on top of the film that covers the inner wall of the chamber; (3) colloidal nanoparticle-containing solution supplied to the recess of a rotating body, such as a rotating crucible located in the interior of the chamber; (4) means for driving the aforementioned crucible into rotation and means for moving the aforementioned crucible in the vertical direction of the chamber; (5) power laser capable of interaction with the contents of the crucible by irradiating a predetermined part of the crucible surface; (6) other auxiliary components of the chamber required for the process, such as the source of vacuum, the colloidal solution source, the source of electric supply, etc.
  • a proper conductive coating e.g., in the form of a metal conductive film with a
  • the nanoparticle-containing solution comprises a predefined mixture of nanoparticles of different sizes and/or type of material dissolved, e.g., in a solution.
  • Conditions are created in the deposition process for nanoparticle-containing solutions to rotate together with the crucible, to move radially outward under the effect of centrifugal forces, and to partially evaporate during the deposition process under the effect of laser irradiation. While the solution evaporates, the nanoparticles remain intact and fly out of the solution in the tangential direction of the rotating crucible.
  • each FP experiences a resistance force that depends on the size and density (i.e., type of material) of the particle. Therefore, the time-to-target will be
  • nanoparticle size and/or type of material corresponding to nanoparticle size and/or type of material.
  • the nanoparticles are made, e.g., from Si, Ge, CdTe, CdSe, CdS, InP, TiOx, InAs, PbS, PbSe, HgTe, CuInSe 2 , CuInGaSe 2 , etc., and if the substrate coating is made from an electron-collecting thin metal film combined with hole-blocking layers such as C 60 , then the obtained flexible nanostructured material is suitable for use as a high-efficient low-cost solar panel.
  • the present invention also provides a novel and efficient apparatus for carrying out the aforementioned method by depositing multilayer nanostructured films on a substrate to ensure a predefined sequence of nanoparticle layers, each layer having nanoparticles of the same size or type of material, or both, in order of size of nanoparticles in the layers throughout the film.
  • the apparatus that comprises the following: (1) sealable cylindrical chamber filled with gas of a required pressure; (2) initial flexible substrate made of an insulating film and precoated with a proper conductive coating (e.g., in the form of a metal conductive film with a carrier-blocking layer on top of the film that covers the inner wall of the chamber; (3) colloidal nanoparticle-containing solution supplied to the recess of a rotating body, such as a rotating crucible located in the interior of the chamber; (4) means for driving the aforementioned crucible into rotation and means for moving the aforementioned crucible in the vertical direction of the chamber; (5) power laser capable of interaction with the contents of the crucible by irradiating a predetermined part of the crucible surface; (6) other auxiliary components of the chamber required for the process, such as the source of vacuum, the source of the colloidal solution supply, the source of electric supply, etc.
  • a proper conductive coating e.g., in the form of a metal conductive film with a carrier-blocking layer
  • Fig. 1 is a schematic elevational sectional view of the apparatus for realization of the method, the components being shown in static.
  • Fig. 2 is a partial view of the apparatus in Fig. 1 , showing the apparatus in action.
  • Fig. 3 is a view that details the essential parts of the apparatus of Figs. 1 and 2 on a larger scale.
  • Fig. 4 is a sectional view along line IV -IV of Fig. 2, some details being omitted for simplicity of explanation.
  • Fig. 5 is a sectional view that shows the structure of the flexible nanostructured material of the invention during its formation.
  • Fig. 6A is a graph that shows effects of nanoparticle size on time-to-target for various gas pressures in the chamber, the distance to target being equal to 2 cm.
  • Fig. 6B is graph that shows effects of nanoparticle size on velocity at the target for various gas pressures in the chamber, the distance to target being equal to 2 cm.
  • Fig. 6C is a graph that shows effects of nanoparticle size on time-to-target for various gas pressures in the chamber, the distance to target being equal to 10 cm.
  • Fig. 6D is graph that shows effects of nanoparticle size on velocity at the target for various gas pressures in the chamber, the distance to target being equal to 10 cm.
  • Fig. 7 is a view that shows a fragment of the flexible nanostructured item of the invention removed from the apparatus after nanoparticles are deposited onto the substrate.
  • Fig. 8 is a cross-sectional view of a solar panel based on use of the flexible nanostructured item of the invention.
  • the term "flexible nanostructured material” means the combination of a flexible substrate that includes preliminarily applied conductive and other suitable layers and a multilayer nanostructured film formed on the surface of the top conductive layer.
  • nanostructured film means a film that comprises a sequence of nanoparticle layers arranged in order of size and type of material.
  • the method and apparatus for depositing a multilayer nanostructured film onto a flexible substrate are based on the motion of a nanoparticle through a gaseous medium (i.e., the FP process as defined above).
  • a gaseous medium i.e., the FP process as defined above.
  • nrdV/dt - 6 ⁇ ⁇ V /Cp ( 1 )
  • m nanoparticle mass
  • ⁇ gas dynamic viscosity
  • r nanoparticle radius
  • V instantaneous velocity of FP
  • Cp slip factor
  • Equation 2 above shows that for each specific value of the factor K, the values of V and dV/dt (which is FP acceleration) strongly depend on both nanoparticle size (radius, r) and density, p.
  • time-to-target depends on nanoparticle radius and density, thus providing consecutive deposition of nanoparticle layers in order of size and type of material.
  • Equation 2 above can be easily solved, and the resulting plots are shown and described below (see Figs. 6A to 6D).
  • the electric field can be applied to the space through which FPs fly.
  • motion equations 1 and 2 can be slightly modified to include potential impact from the electric field without significantly changing the dependence of FP motion parameters on size and density of the FP.
  • Fig. 1 is a schematic elevational sectional view of the apparatus for realization of the method of the invention, the components being shown in static;
  • Fig. 2 similar to Fig. 1 , shows the apparatus in action;
  • Fig. 3 shows the details of the essential parts of the apparatus in Figs. 1 and 2 on a larger scale;
  • Fig. 4 is a top view of the apparatus shown in Fig. 2, with some details omitted for simplicity of explanation.
  • FIG.1 is general schematics of the apparatus of the invention which as a whole is designated by reference numeral 100.
  • the apparatus 100 shown in this drawing comprises a sealable cylindrical chamber 200 that has an inner wall 220 and is filled with a gaseous medium (e.g., nitrogen) maintained at a required pressure that, depending on specific operational conditions, may vary in the range of 0.1 mTorr to 100 mTorr.
  • Reference numeral 225 designates the cover of the chamber 200 with an optical window 410 for an energy source, as mentioned below.
  • a flexible substrate 221 Placed onto the inner wall 220 of the chamber 200 is a flexible substrate 221 that consists, e.g., of an insulating layer, e.g., a vinyl layer 222, which is precoated with a proper multilayer conductive coating 223 that comprises, e.g., a conductive film, such as a metal film 224 made, e.g., of Al, Cr, Ti, or the alloys thereof, and a carrier-blocking layer, e.g., a hole-blocking layer 226 on the top of a metal film 224.
  • the flexible substrate After placement onto the inner wall 220 of the chamber 200, the flexible substrate is turned into a cylindrical body.
  • the layers used for precoating the vinyl layer 222 may comprise a conductive polymer film (not shown) in a soft, semiliquid state.
  • the chamber 200 contains in its interior a rotating body, hereinafter referred to as "crucible 300" which is rotationally supported by a shaft 310 driven, e.g., by an electric motor 314.
  • the crucible can perform linear motion in the vertical direction, shown by arrow 312.
  • the apparatus 100 is provided with a linear stepper motor 315, and a guide key 311 is provided on the shaft 310 for guiding the crucible along the shaft.
  • the cylindrical body of the flexible substrate 221 has a longitudinal axis Z-Z and surrounds the crucible 300 so that a space 299 is provided between the crucible and the flexible substrate.
  • the crucible On its upper side, the crucible has a recess 306 intended for receiving a liquid medium, i.e., the nanoparticle-containing solution 302 that is supplied to the recess 306 from a supply container 307 located outside the chamber 200 and by means of a mass-flow controller 308 to the recess 306 of the crucible 300.
  • a liquid medium i.e., the nanoparticle-containing solution 302 that is supplied to the recess 306 from a supply container 307 located outside the chamber 200 and by means of a mass-flow controller 308 to the recess 306 of the crucible 300.
  • the nanoparticle-containing solution may contain nanoparticles, the materials of which are selected from the group of materials belonging to groups IV, II- VI, and III-V of elements, metals, and metal oxides, said nanoparticles having sizes ranging from 2 nm to 10 nm.
  • these materials are the following: Si, Ge, CdTe, CdSe, CdS, InP, TiOx, InAs, PbS, PbSe, HgTe, CuInSe 2 , CuInGaSe 2 , etc.
  • the path of the nanoparticle-containing solution contains a tube that passes through the wall 220 of the container and terminates in the flexible tube 320.
  • the outlet end of the flexible tube 320 is maintained at a constant and predetermined distance from the surface of the recess 306 by means of a tube holder 330 that rests on the upper surface of the recess and is supported by frictionless members, such as balls.
  • a tube holder 330 that rests on the upper surface of the recess and is supported by frictionless members, such as balls.
  • frictionless members such as balls.
  • Point contact of the holder with the crucible surface does not present an obstacle for movement of the nanoparticle-containing solution in the radial outward direction.
  • the upper side of the crucible recess 306 is smooth, e.g., polished for imparting to it antifriction properties, and has a surface 301 flattened toward the edges of the rotating body.
  • An essential component of the apparatus of Fig. 1 is the energy source, e.g., a power laser 400, capable of interacting with the nanoparticle-containing solution 302 located in the crucible 300 by irradiating a predetermined part of the crucible surface, i.e., a substantially flat peripheral surface 301 on which the solution forms a thin, easily vaporizable layer.
  • the power laser 400 should have radiation energy sufficient for evaporating the liquid medium and should be capable of generating an annular-shaped beam (not shown in Fig. 1) for creating an annular light spot on the aforementioned peripheral surface.
  • Such power lasers are known in the art, and the power laser 400 can be operated, e.g., on the principle of the power laser source described in U.S. Patent 7585751 issued in 2009 to Naotoshi Kirihara and others.
  • the apparatus 100 is provided with means for moving the laser 400 in synchronism with the crucible.
  • these means comprise a stepper motor 420 connected to the laser 400 and guides 421 for guiding the laser 400 in the vertical direction.
  • the stepper motors 315 and 420, the rotor motor 314, and the mass-flow controller 308 are connected to a control unit, such as a central processing unit (CPU), which controls operation of the mechanisms and synchronizes their motions.
  • a control unit such as a central processing unit (CPU)
  • CPU central processing unit
  • reference numeral 423 designates the source of inert gas, e.g., nitrogen
  • 425 designates a nitrogen gas pump for the supply of gaseous nitrogen to the chamber through a pipe 431 and by means of a pressure-controlling valve 427 installed in the pipe 431
  • reference numeral 429 designates a pump-motor driver through which the pump motor is connected to the CPU.
  • Fig. 2 is a partial view of the apparatus of Fig. 1 that shows the apparatus in action, some details of the apparatus being not shown.
  • the process begins with raising the crucible 300 in the direction of the arrow 312 to the vertical position in which the upper surface 301 of the crucible is aligned with the position on the flexible substrate 221 from which deposition begins.
  • the pump 425 activates and begins to supply gaseous nitrogen to the chamber 200 through the pipe 431 by means of the valve 427.
  • the stepper motor 420 activates and moves the laser 400 in the guides 421 to a position in which the beam generated by the laser is focused onto the aforementioned flat peripheral surface 301 of the crucible 300.
  • the supply of the nanoparticle- containing solution 302 begins and proceeds to the recess 306 of the crucible 300 from the container 307 by means of the mass-flow controller 308 and through the flexible tube 320.
  • the CPU also sends a command to start the motor 314, the crucible 300 is brought into rotation by means of the shaft 310 with such frequency of rotation that causes movement of the nanoparticle-containing solution 302 under the effect of the centrifugal force in the radial outward direction along the curved surface of the recess 306 to the flat peripheral surface 301 of the crucible 300.
  • a layer 303 of the nanoparticle-containing solution is formed on the surface 301.
  • the power laser 400 is activated, and an annular laser beam 405 is directed through the optical window 410 of the cover 225 (Figs. 1 and 2) onto the aforementioned flat peripheral surface 301 on which the beam is focused.
  • a liquid component of the solution 302 evaporates instantaneously (i.e., in a very short time as compared to the FP time-to-target), which is conventionally shown by arrows 304 in Figs. 2 and 3, which is a fragmental view of the crucible shown in operation on a larger scale (for simplicity, the tube holder 330 is not shown in the drawings).
  • arrows 304 in Figs. 2 and 3
  • the nanoparticles which are solid and are designated by reference numerals 500, 10, 520, etc., remain and fly out from the edge of the circular crucible in the tangential direction. This is shown in Fig.
  • Reference numeral 600 designates the multilayer nanostructured film deposited onto layer 226 of the flexible substrate 221 (Fig. 1).
  • reference numeral 710 designates a slit that is formed between the edges of the rectangular flexible substrate 221 when the latter is formed into a cylinder and is inserted into the space formed by the inner walls 220 of the chamber 200.
  • instantaneous velocity V of each FP and FP acceleration dV/dt strongly depend on both nanoparticle size (radius, r) and density, p.
  • time it takes for a given FP to reach the target positioned at a given distance from the starting point depends on nanoparticle radius and density, thus providing consecutive deposition of nanoparticle layers in the order of their size and/or type of material.
  • nanoparticles that form the multilayer nanostructured film are sorted by their dimensions and or/densities in the thickness direction of the film.
  • Fig. 5 is a cross section through multilayer nanostructured film 600 in the film thickness direction.
  • reference numeral 221 designates the flexible substrate.
  • a first layer 610 which is nearest the substrate 221, is formed from the largest nanoparticles of those present in the solution 302.
  • the next layer 620 which deposited on the layer 610, is formed from particles that are smaller in size, and so on.
  • the uppermost layer 650 of the obtained multilayer nanostructured film 600 is formed from the smallest nanoparticles of the nanoparticle-containing solution.
  • an item 602 of the flexible nanostructured material is obtained and comprises the flexible substrate 221 with the multilayer nanostructured film 600.
  • Some of the aforementioned layers, e.g., the layer 615 may consist of nanoparticles made from material different from that of other layers. In Fig. 4 this is shown by different colors of the particles that form the layer 615.
  • the multilayer nanostructured film of the invention suitable for efficient use in the manufacture of solar panels and in various optoelectronic devices. It is also understood that the spherical nanoparticles will not be ideally packed in the multiplayer structure 600 formed on the surface of the flexible substrate 221, but from the practical point of view the structure of the nanoparticle layers shown in Fig. 5 will be sufficient for providing an essential improvement in the PV- conversion efficiency.
  • an electric voltage source 350 may be electrically connected between the conductive (metal) layer 224 and the crucible 300.
  • the purpose of the source 350 is to produce an electric field in the space intersected by FPs on their way to the substrate so that on FP arrival at the surface of the flexible substrate 221, an attractive electric force is applied to the particles.
  • Figs. 6A through 6D show that the time-to-target and FP velocity at the target depend on the size of the nanoparticles.
  • Fig.6A is a graph that shows effects of nanoparticle size on the time-to-target for various gas pressures in the chamber, the distance to target being equal to 2 cm.
  • Fig. 6B shows the effects of nanoparticle size on the velocity at target (arrival velocity) for various gas pressures in the chamber, the distance to target being equal to 2 cm.
  • Fig. 6C is a graph that shows the effects of nanoparticle size on time-to-target for various gas pressures in the chamber, the distance to target being equal to 10 cm.
  • Fig. 6A is a graph that shows effects of nanoparticle size on the time-to-target for various gas pressures in the chamber, the distance to target being equal to 2 cm.
  • 6D is a graph that shows the effects of nanoparticle size on the velocity at target for various gas pressures in the chamber, the distance to target being equal to 10 cm. All four drawings are shown for the specific materials of nanoparticles such as InAs or HgTe. Depending on the working gas pressure in the chamber, the respective curves are shown by solid lines, broken lines, dotted lines, or dash-and-dot lines.
  • the chamber 200 Upon completion of FP process, the chamber 200 is depressurized, the cover 225 is opened, and an item 700 of the flexible nanostructered material 602 is removed from the apparatus.
  • Fig.7 shows item 700 removed from the apparatus after nanoparticles are deposited onto the substrate. It is understood that the item 700 is unfolded into a flat plate-like piece (not shown) before solar panel assembly.
  • Fig. 8 is a cross-sectional view of a solar panel 800 based on the use of the flexible
  • the solar panel 800 is manufactured as follows.
  • a hole-conductive / electron-blocking layer 655 e.g. a TPD layer
  • an n-type layer (not shown) made, e.g., of amorphous silicon or conductive polymer, is applied onto the layer 655.
  • the next layer 660 which is an indispensable transparent conductive oxide (TCO) made, e.g. of indium tin oxide (ITO), is placed onto the aforementioned n-type layer or directly onto the layer 660.
  • TCO transparent conductive oxide
  • ITO indium tin oxide
  • the subsequent layers which are inherent to any solar panel, may comprise metal electrodes (only one of which, i.e., the metal electrode 670, is designated in the drawing), an antireflective coating 665, and a protective layer 680.
  • Inner radius cylindrical chamber (of wall 220 of Fig.1): 14 cm;
  • Rotational frequency of crucible during FP deposition 9600 rpm (providing initial FP velocity is 100 m/s);
  • Pulse energy of laser 400 0.01 to 0.1 J/cm 2 ;
  • Laser pulse duration 10 to 100 ns
  • Pulse frequency during process e.g., 500 Hz; 6.
  • Vertical speed of crucible 300 0.5 to 1.0 cm/s.
  • the nanoparticle material is InAs or HgTe.
  • the nanoparticle-containing solution 302 is prepared according to a colloidal-solution-processing technique described, e.g., in "Efficient solution- processed infrared photovoltaic cells," Applied Physics Letters, 90,183113.
  • the nanoparticle mix in the solution consists of nanoparticles having radii of 2, 3, 4, 5, and 6 nm, with concentration in the range of 5 x 10 n - 2 x 10 13 cm " (smaller particles have a higher concentration than larger particles).
  • nanoparticles are in a solution, they are present in the form of quantum dots with attached organic ligands; these ligands either disappear during the evaporation cycle or remain with an FP during flight and deposition on the flexible substrate.
  • Time-to-target for all FPs will range from 1.2 to 2.0 ms.
  • the nanostructured film 600 (Figs. 2, 4, and 5) is formed when nanoparticles with the above- described parameters are deposited onto the flexible substrate 221 (Fig. 1) in the apparatus of the above-described application example and under conditions of the process described.
  • This multilayer nanostructured film comprises a sequential nanoparticle layer structure with the thickness of each nanoparticle layer ranging from 8 to 15 nm.
  • the size of the nanoparticles in an individual layer varies from 6 nm in the first deposited layer 610 to 2 nm in the uppermost layer 650 (Fig. 5).
  • vertical motion of the crucible can start at the lowest position and proceed in the upward direction.
  • the laser that produces an annular spot can be replaced by a regular IR-laser in combination with beam-deflecting and beam-guiding optics.
  • the solution-evaporation area is not necessarily limited by the peripheral portion of the crucible, and, if necessary, a larger part of the solution surface can be irradiated by the laser beam.
  • the structure of the flexible substrate is not limited by the example described and illustrated in the present specification and may include additional layers for more efficient electron collection and transport that follows photovoltaic conversion in PV-active nanostructured film.
  • the nanostructure produced by the method of the invention is characterized by gradual increase in nanoparticle size in the direction from the substrate to the crucible, it is understood that the method allows arrangement of sizes and types of material in a variety of desired orders and thicknesses.
  • the use of flexible nanostructured material produced by the method and apparatus of the invention is not limited by application only to photovoltaic panels and this flexible nanostructured material may be used, e.g., in energy storage devices, or the like.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un procédé efficace et économique et un servant à former un matériau nanostructuré flexible pouvant être utilisé comme un élément actif d'un panneau photovoltaïque. Le procédé consiste à évaporer une solution colloïdale, qui contient des nanoparticules de diverses tailles et/ou masses, depuis une surface plate d'un corps tournant sur lequel la solution forme une couche mince et facilement vaporisable, et à libérer simultanément les nanoparticules de la solution pour leur migration libre à travers un milieu gazeux vers le substrat flexible. Par conséquent, les particules de différentes tailles et/ou types de matériau sont déposées sur le substrat flexible dans un ordre prédéfini qui correspond à l'importance de la résistance subie par les nanoparticules pendant leur migration libre.
PCT/US2010/002728 2010-10-12 2010-10-12 Procédé de formation d'un matériau nanostructuré flexible pour panneaux photovoltaïques et appareil servant à réaliser le procédé WO2012050543A1 (fr)

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CN108672942A (zh) * 2018-05-16 2018-10-19 汪玉洁 一种薄膜太阳能电池板激光刻膜机

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014032874A1 (fr) * 2012-09-03 2014-03-06 Siemens Aktiengesellschaft Détecteur de rayonnement et son procédé de production
CN108672942A (zh) * 2018-05-16 2018-10-19 汪玉洁 一种薄膜太阳能电池板激光刻膜机

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