WO2014055387A1 - Dispositifs optoélectroniques dotés de films nanostructurés colloïdaux totalement inorganiques - Google Patents

Dispositifs optoélectroniques dotés de films nanostructurés colloïdaux totalement inorganiques Download PDF

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WO2014055387A1
WO2014055387A1 PCT/US2013/062541 US2013062541W WO2014055387A1 WO 2014055387 A1 WO2014055387 A1 WO 2014055387A1 US 2013062541 W US2013062541 W US 2013062541W WO 2014055387 A1 WO2014055387 A1 WO 2014055387A1
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film
fused
inorganic
nanostructures
ligands
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PCT/US2013/062541
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Daniel Landry
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Sunpower Technologies Llc
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Priority claimed from US13/755,186 external-priority patent/US8779413B1/en
Application filed by Sunpower Technologies Llc filed Critical Sunpower Technologies Llc
Publication of WO2014055387A1 publication Critical patent/WO2014055387A1/fr
Priority to US14/328,004 priority Critical patent/US20140319525A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
    • H01L31/035218—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
    • H01L27/14696—The active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03925—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIIBVI compound materials, e.g. CdTe, CdS
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate

Definitions

  • the present disclosure relates in general to optical and electronic devices, and more particularly, to fused films of all-inorganic colloidal semiconductor nanometer scale materials ("nanostructures”) including semiconductor nanoparticles and functional inorganic ligands, which may be employed in an optoelectronic device.
  • nanostructures all-inorganic colloidal semiconductor nanometer scale materials
  • semiconductor nanoparticles semiconductor nanoparticles and functional inorganic ligands
  • Image sensors include arrays of pixelated semiconductors and/or active pixel arrays that are optically sensitive to light (or wavelengths of electromagnetic radiation) and convert the incident photons to electrons. These photodetectors are integrated in circuit, and with other electronic circuits to convert optical signals to electronic signals, to store charge accumulated by the pixels, to transfer the charge and/or signals from the array, to convert the analog into digital signals, and to process digital data to form still or video digital images.
  • Examples of image sensors include devices that use silicon for sensing, read-out electronics, and multiplexing functions.
  • optically sensitive silicon photodetectors and electronics are formed on the same single silicon wafer.
  • larger area, flat panel image sensors consist of a large array of pixels as part of an active matrix where each pixel has a thin-film transistor (TFT) that can be externally addressed.
  • TFT thin-film transistor
  • Prior methods for solution-based nanoparticle films include volume losses of 30% or higher which may leave voids, holes, cracks and other defects in the film that negatively affect optoelectronic performance and require post-treatment to repair.
  • All-inorganic colloidal nanostructures including semiconducting nanoparticles can be processed in solution and/or included in inks that can be deposited on a suitable substrate. This solution-processing compatibility allows post-processing atop other integrated circuits.
  • the fabrication of optically active films using all-inorganic colloidal nanostructure inks can be achieved at low temperature to accommodate additional device structures including existing and new TFT and organic substrate, and integrated circuit materials.
  • nanoparticle ligands that are linked to nanoparticles are exchanged for shorter organic or volatile organic or inorganic ligands that are vaporized during a subsequent heating (annealing, sintering) step to provide a film consisting mainly of nanoparticles and being substantially free of ligands.
  • the nanoparticle ligands may be removed by soaking the deposited layers in a solvent that dissolves and thus dissociates the ligands from the nanoparticles.
  • Embodiments of the present disclosure provide methods for manufacturing fused films for optoelectronic devices.
  • the fused film may incorporate an all-inorganic colloidal nanostructured layer.
  • the all-inorganic colloidal nanostructured layer may include semiconductor nanoparticles that may be processed in a solution and formed into inks.
  • Nanocrystals may be synthesized in order to create the ink that may be thermally treated to form the fused film.
  • semiconductor nanoparticles may be produced by known techniques such as batch or continuous flow wet chemistry processes.
  • Semiconductor nanoparticles may include spherical nanometer-scale, crystalline materials and other shaped nanometer- scale, crystalline particles such as oblate and oblique spheroids, rods, wires, the like and combinations thereof.
  • the semiconductor nanoparticles may include metal, semiconductor, oxide, metal-oxides and ferromagnetic compositions.
  • the semiconductor nanoparticles may be subject to ligand exchange where organic ligands may be substituted with pre- selected, functional inorganic ligands.
  • the exchange and extraction of organic ligands may provide a solution or ink of all- inorganic colloidal nanostructures (including functional inorganic ligands and inorganic nanoparticles) that is substantially free of the organic materials.
  • the ligand exchange may involve precipitating the as- synthesized semiconductor nanoparticles from their original solution, washing, and re-dispersing in a liquid or solvent which either is or includes the ligands to be substituted onto the semiconductor nanoparticles and so completely disassociates the original ligands from the outer surfaces of the semiconductor nanoparticles and links the functional inorganic ligands to the semiconductor nanoparticles.
  • the functional inorganic ligands may maintain the stability of semiconductor nanoparticles in the solution and provide preferred ordering and close-packing of the semiconductor nanoparticles, without aggregation or agglomeration, via electrostatic forces.
  • Functional inorganic ligands are inter-particle media, including inorganic complexes, ions, and molecules that eliminate insulating organic ligands, stabilize the semiconductor nanoparticles in solution, facilitate close-packing between semiconductor nanoparticles, and create all-inorganic colloidal nanostructures that may be processed in solution to form all- inorganic films.
  • the ink may be deposited using spin-coating, spray- casting, or inkjet printing techniques on any suitable substrate conducting or insulating, crystalline or amorphous, rigid or flexible.
  • the all-inorganic nanostructured ink may be transformed into a solid, all-inorganic fused film via thermal treatment.
  • the fused film may function as an optically active layer for optoelectronic devices based on the fused all-inorganic colloidal nanostructures incorporated into the fused film.
  • the final material composition, size of the imbedded all-inorganic colloidal nanostructures, and the thickness of the fused film may depend on the light or wavelength region selected for detection.
  • aspects of the present disclosure may include an imaging system, a focal plane array which incorporates a fused film formed that may work as an optically sensitive layer formed on an underlying integrated circuit patterned to measure and relay optical signals, electronic signals, or both, on a pixel-by-pixel basis, where the signal may be indicative of light absorbed in the medium from which the focal plane array is made.
  • the circuit may achieve multiplexing of the values read from individual pixels into row or columns of data, carried by electrodes and stored for digital imaging. Subsequent layers, typically processed from the solution phase, which, with appropriate interfacing, sensitize the underlying focal plane array to become responsive to the wavelengths absorbed by these new layers. Their resultant electronic signals may be registered and relayed using the underlying chip.
  • the present disclosure may provide a range of solution-processed fused films that may lie atop the underlying chip or active array.
  • the present disclosure may provide a method of sensitizing a charge-coupled device (CCD), complementary metal- oxide-semiconductor (CMOS) focal plane array, or thin-film transistor (TFT) active pixel array using all-inorganic fused films.
  • CCD charge-coupled device
  • CMOS complementary metal- oxide-semiconductor
  • TFT thin-film transistor
  • the disclosure may provide efficient, highly sensitive photo detectors based on solution-processed all-inorganic colloidal nanostructured fused films. Additionally, highly sensitive photodetectors based on a combination of two (or more) types of solution- processed all-inorganic colloidal nanostructures, each including a distinct semiconductor material, are provided.
  • Multispectral detection of electromagnetic radiation wavelengths or ranges of wavelengths may be facilitated by incorporating various sizes of all-inorganic colloidal nanostructures within a single, continuous optically active layer within the optoelectronic device, depositing varied respective all-inorganic colloidal nanostructures per pixel and/or incorporating stacked (e.g., vertical) fused film layers having a fused all- inorganic colloidal nanostructures, where each fused film represents an optically active layer in electrical communication with at least two electrodes.
  • the imaging devices may be efficient photoconductive optical detectors active in the x-ray, ultraviolet, visible, short-wavelength infrared, long- wavelength infrared regions of the spectrum, and are based on solution-processed nanocrystalline quantum dots. Some embodiments may have the potential to be used in creating multi- spectral, low-cost, large area, and flexible-substrate imaging systems.
  • a film comprises fused nanostructures substantially devoid of organic material wherein the nanostructures comprise an inorganic nanoparticle fused with a functional inorganic ligand, and wherein charge carriers are mobile between the nanostructures and throughout the film.
  • a device comprises (a) a film comprising a network of fused all-inorganic nanostructures, wherein the nanostructures include an inorganic nanoparticle fused with a functional inorganic ligand, and wherein electrical communication exists between the nanostructures and throughout the film, and the film has substantially no defect states in the regions where the nanostructures are fused; and (b) first and second electrodes in spaced relation and in electrical communication with first and second portions of the network of fused nanostructures.
  • FIG. 1 is a block diagram of fused film manufacturing method, according to an embodiment.
  • FIG. 2 shows fused film having all-inorganic colloidal nanostructures on a substrate, according to an embodiment.
  • FIG. 3 depicts a fused film with an electrode, according to an embodiment.
  • fused film refers to a layer of all-inorganic colloidal semiconductor nanostructures that may be converted into a solid matrix after a thermal treatment, and which may be optically active.
  • Optically active refers to a substance's ability to convert optical to electrical light.
  • semiconductor nanoparticles refers to particles sized between about 1 and about 100 nanometers made of semiconducting materials.
  • the present disclosure relates to optical devices and methods of producing devices from films synthesized from all-inorganic colloidal semiconductor nanostructures.
  • the all- inorganic colloidal semiconductor nanostructures may be fused to form nanocrystalline films ("fused films") that may be optically active and/or photoconductive and may be used in photodiodes, photodetectors, optical sensors, imaging devices, photovoltaic applications, among others.
  • Devices incorporating the fused films may be designed to absorb specific or multiple electromagnetic wavelengths based on the design of the all-inorganic colloidal nanostructures having the fused film.
  • FIG. 1 is a block diagram of a fused film manufacturing method 100.
  • nanocrystal synthesis 102 may first take place.
  • semiconductor nanoparticles may be produced using known techniques such as batch or continuous flow wet chemistry processes.
  • the known synthesis techniques for colloidal nanoparticles may include capping semiconductor nanoparticle precursors in a stabilizing organic material, or organic ligands, which may prevent the agglomeration of the semiconductor nanoparticle during and after nanocrystal synthesis 102.
  • organic ligands are long chains radiating from the surface of the nanoparticle and may assist in the suspension and/or solubility of the nanoparticle in solvents.
  • Semiconductor nanoparticles employed in the present disclosure may be spherical nanometer-scale, crystalline materials, also known as semiconductor nanocrystals or quantum dots. Other shaped nanometer- scale, crystalline particles may be employed including oblate and oblique spheroids, rods, wires, and the like.
  • Semiconductor nanoparticles may include metal, semiconductor, oxide, metal-oxides and ferromagnetic compositions.
  • the nanoparticles may have a diameter ranging between about 1 nm and about 1000 nm, with the preferred range being between about 2 nm and about 10 nm. Due to the small size of the crystals, quantum confinement effects may manifest resulting in size, shape, and compositionally dependent optical and electronic properties, rather than the properties for the same materials in bulk scale.
  • Semiconductor nanoparticles may have a tunable absorption onset that has increasingly large extinction coefficients at shorter wavelengths, multiple observable excitonic peaks in the absorption spectra that correspond to the quantized electron and hole states, and narrowband tunable band-edge emission spectra.
  • Semiconductor nanoparticles may absorb light at wavelengths shorter than the modified absorption onset and emit at the band edge.
  • the semiconductor nanoparticles may be manufactured to be optically sensitive to the ultraviolet, x-ray, visible, and infrared regions of the electromagnetic spectrum by manufacturing nanoparticles in different sizes.
  • Inorganic semiconductor nanoparticles may include II- VI, III-V, and IV- VI binary semiconductors.
  • binary semiconductor materials may include ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe (II- VI materials), PbS, PbSe, PbTe (IV- VI materials), A1N, A1P, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb (III-V materials).
  • the semiconductor nanoparticles may be ternary, quaternary, and quinary semiconductor nanostructures and combinations and mixtures of the materials thereof.
  • the semiconductor nanoparticles may include core-shell type semiconductors in which the shell is one type of semiconductor and the core is another type of semiconductor, metal, oxide, and metal-oxide compounds or core-shell compositions, and mixtures thereof, which may have conductive or semi conductive properties or serve to introduce certain defect states.
  • fused film manufacturing method 100 may involve ligand exchange 104, in which substitution of organic ligands with functional inorganic ligands may be achieved.
  • functional inorganic ligands may be dissolved in a polar solvent, while organic capped semiconductor nanoparticles may be dissolved in an immiscible, generally non-polar, solvent. These two solutions may then be combined and stirred for about 10 minutes, after which a complete transfer of semiconductor nanoparticles from the non-polar solvent to the polar solvent may be observed.
  • Immiscible solvents may facilitate a rapid and complete exchange of organic ligands with functional inorganic ligands.
  • Functional inorganic ligands may be soluble functional reagents that are free from organic functionality, may have a greater affinity to link to the semiconductor nanoparticles than the organic ligands, and therefore, may displace the organic ligands from organic capped semiconductor nanoparticles.
  • Ligand exchange 104 may involve precipitating the organic capped semiconductor nanoparticles from their original solution containing organic ligands, washing, and re-dispersing in a liquid or solvent which either is or includes the functional inorganic ligands. These functional inorganic ligands may disassociate the organic ligands from the outer surfaces of the organic capped semiconductor nanoparticles and may link the functional inorganic ligands to the semiconductor nanoparticles.
  • the functional inorganic ligands may maintain the stability of semiconductor nanoparticles in the solution and may provide preferred ordering and close-packing of the semiconductor nanoparticles without aggregation or agglomeration via electrostatic forces. Functional inorganic ligands may assist in the suspension and/or solubility of the semiconductor nanoparticle in solvents or liquids. Once applied, the functional inorganic ligands may not substantially change the optoelectronic characteristics of the semiconductor nanoparticles originally synthesized with organic ligands.
  • Functional inorganic ligands may include materials that are the same as the coordinated semiconductor nanoparticle or different to design and affect the electronic, optical, magnetic, or other properties for the final fused films.
  • two or more types of semiconductor nanoparticles may be separately manufactured. Each different type of semiconductor nanoparticle may be subject to the exchange of organic ligands for functional inorganic ligands and the extraction of post-exchanged organic ligands. Subsequently, the two types of semiconductor nanoparticles with functional inorganic ligands may be mixed in a solution to create a heterogeneous mixture. A plurality of semiconductor nanoparticle compositions and/or sizes may be included in the all-inorganic nanostructured ink. Functional inorganic ligands fused with semiconductor nanoparticles may have the beneficial effect of making nanostructured surfaces more stable to oxidation and photoxidation and increase material performance and longevity.
  • Functional inorganic ligands may include suitable elements from groups such as polyatomic anions, transition metals, lanthanides, actinides, chalcogenide molecular compounds, Zintl ions, inorganic complexes, metal-free inorganic ligands, and/or a combination including at least one of the foregoing.
  • functional inorganic ligands may be partially volatilized, where some portion of the functional inorganic ligand remains as solid state electronic material within the nanostructured ink.
  • Examples of polar solvents containing functional inorganic ligands may include 1,3- butanediol, acetonitrile, ammonia, benzonitrile, butanol, dimethylacetamide, dimethylamine, dimethylethylenediamine, dimethylformamide, dimethylsulfoxide (DMSO), dioxane, ethanol, ethanolamine, ethylenediamine, ethyleneglycol, formamide (FA), glycerol, methanol, methoxyethanol, methylamine, methylformamide, methylpyrrolidinone, pyridine, tetramethylethylenediamine, triethylamine, trimethylamine, trimethylethylenediamine, water, and mixtures thereof.
  • DMSO dimethylsulfoxide
  • FA formamide
  • glycerol methanol, methoxyethanol, methylamine, methylformamide, methylpyrrolidinone, pyridine, tetramethylethylenediamine, triethylamine,
  • non-polar or organic solvents containing organic ligands may include pentane, pentanes, cyclopentane, hexane, hexanes, cyclohexane, heptane, octane, isooctane, nonane, decane, dodecane, hexadecane, benzene, 2,2,4-trimethylpentane, toluene, petroleum ether, ethyl acetate, diisopropyl ether, diethyl ether, carbon tetrachloride, carbon disulfide, and mixtures thereof; provided that organic solvent is immiscible with polar solvent.
  • Other immiscible solvent systems that are applicable may include aqueous- fluorous, organic- fluorous, and those using ionic liquids.
  • the exchange and extraction of the organic ligands in ligand exchange 104 may provide a solution or ink of all-inorganic colloidal nanostructures that may be substantially free of organic materials.
  • the relative concentration of the organic ligands to the semiconductor nanoparticle in the solution of the functional inorganic ligand may be less than about 10%, 5%, 4%, 3%, 2%, 1%, 0.5% and/or 0.1% of the concentration in a solution of the semiconductor nanoparticle with the organic ligands.
  • Organic materials in organic ligands are known to be less stable and more susceptible to degradation via oxidation and photo-oxidation; therefore, all-inorganic materials may enhance the stability, performance and longevity of the device.
  • organic materials may act as insulating agents that prevent the efficient transport of charge carriers between semiconductor nanoparticles, resulting in decreased device efficiencies.
  • Semiconductor nanoparticles with inorganic functional ligands may differ from core/shell nanoparticles where one nanoparticle has an outer crystalline layer with a different chemical formula.
  • the crystalline layer, or shell generally forms over the entire semiconductor nanoparticle but, as used in the present disclosure, core/shell nanoparticles may refer to those nanoparticles where at least one surface of the semiconductor nanoparticle is coated with a crystalline layer.
  • the functional inorganic ligands may form ordered arrays that may radiate from the surface of a semiconductor nanoparticle, these arrays may differ from a core/shell crystalline layer, as they are not permanently bound to the core semiconductor nanoparticle in the all-inorganic nanostructured ink.
  • the ink may undergo a deposition 106 over a substrate or may be deposited as additional layers to all-inorganic fused films.
  • Deposition 106 techniques may include: blading, growing three- dimensional ordered arrays, spin coating, spray coating, spray pyrolysis, dipping/dip-coating, sputtering, printing, inkjet printing, stamping, the like and combinations thereof.
  • all-inorganic nanostructured ink may be transformed into a solid, all-inorganic fused film via thermal treatment 108.
  • Crystalline films from all-inorganic colloidal nanostructures may be formed by a low temperature thermal treatment 108.
  • thermal treatment 108 of the colloidal material may include heating to a temperature less than about 350, 300, 250, 200, 150, 100 and/or 80°C.
  • Fused film 200 may maintain approximately the same optoelectronic characteristics as the all-inorganic nanostructured ink or solution including the all-inorganic colloidal nanostructures.
  • the fused film substantially maintains the same size and shape of the semiconductor nanoparticles that were deposited from the all-inorganic nanostructured ink.
  • Excessive thermal treatment 108 may create fused films that do not maintain nanostructures and may result in fused films that have optoelectronic characteristics more closely performing to the respective bulk semiconductor material.
  • Deposition 106 of all- inorganic nanostructured inks and film fusing via thermal treatment 108 to create all-inorganic nanostructured films may be performed in repetition to achieve desired film characteristics, including multiple layers, for use in optoelectronic devices.
  • FIG. 2 shows fused film 200.
  • Fused film 200 may be enhanced as an optically active layer for finished optoelectronic devices based on fused all-inorganic colloidal nanostructures 204 integrated into fused film 200.
  • Final material composition, size of imbedded all-inorganic colloidal nanostructures 204, and thickness of fused film 200 may be dependent on light or wavelength region selected for detection. Thickness of fused film 200 may range between about 50 nm and about 3 um, though thinner or thicker fused films 200 may be employed according to the desired functionality of the device.
  • the functional inorganic ligands may effectively bridge the semiconductor nanoparticles to form an electrical network and facilitate efficient electronic transport between all-inorganic colloidal nanostructures 204 within fused film 200.
  • the fused all- inorganic colloidal nanostructures 204, and the juncture between them, may generally not have defect states, so current will flow readily between them.
  • This aspect of fusing all- inorganic colloidal nanostructures 204, including functional inorganic ligands may increase the electronic transport properties between all-inorganic colloidal nanostructures 204 and throughout fused film 200, providing a carrier mobility which may range within about 0.01 cm 2 /Vs and about 80 cm 2 /Vs.
  • Fused film 200 having all-inorganic colloidal nanostructures 204 may also exhibit a relatively low electrical resistance above about 25 k-Ohm/square.
  • Nanostructured ligands remaining in the deposited all-inorganic ink/solution to form fused film 200 may not be removed, either before or as a function of the fusing steps or thermal treatment. Furthermore, inks including all-inorganic colloidal nanostructures 204 may lose less than about 20%, 15%, 10% and/or 5% of their mass upon a thermal treatment up to about 400°C and/or 450°C.
  • FIG. 3 depicts a fused film structure 300.
  • Optical devices may include single image sensor chips having a plurality of pixelated metal oxide semiconductors each of which may include fused film 200 that may be optically active and at least two electrodes 302 in electrical communication with fused film 200. Size of pixels may range from less than about 1 micron square to about 1 micron square.
  • optical devices may be large-area image sensors including active pixel or matrix arrays incorporating thin film transistors (TFTs) which may include fused film 200 that is optically active and at least two electrodes 302 in electrical communication with fused film 200.
  • TFTs thin film transistors
  • Pixel size may be reduced to about 40 microns square or may be sized to accommodate the detected wavelength as required.
  • Electrodes 302 may be related to the amount of light absorbed by fused film 200. Photons absorbed by fused film 200 may generate electron-hole pairs and a current and/or voltage. By determining such current and/or voltage for each pixel, the image across the chip may be reconstructed via digital multiplexing and other integrated circuit components.
  • the responsiveness of the sensor chips to different electromagnetic wavelengths may be made tunable by changing the material systems for the all-inorganic colloidal nanostructures 204 inks and/or changing the size of the all-inorganic colloidal nanostructures 204 within fused film 200 to take advantage of the quantum size effects in all- inorganic colloidal nanostructures 204 included in the ink.
  • Fused film 200 may be deposited and created as a monolithic layer(s) over the image sensor chip, integrated circuit, integrated circuit components, and/or TFT active matrices. Fused film 200 may be solution-deposited onto a substrate 202 or pre- fabricated CCD, CMOS, or TFT electronics.
  • Image sensor chip, integrated circuit, and/or TFT architecture may include one or more semiconducting materials, such as silicon, silicon-on-insulator, silicon-germanium, indium phosphide, indium gallium arsenide, gallium arsenide, or semiconducting polymers (for flexible substrate and non-planar devices).
  • Optical device substrates 202 may also include plastic and glass.
  • flexible substrate 202 devices may include metal foil and organic substrates.
  • Additional layers may be included in the layers atop the structure, including additional depositions of all-inorganic colloidal nanostructures 204 on fused film 200 to enable multispectral detection and subsequent layers of at least partially transparent electrodes.
  • Multiple optically active layers may be layered on the image sensor substrate 202 to provide greater sensitivity for the respective wavelengths, improved imaging for multiple wavelengths, decreased complexity in device architectures (e.g., multilayer, monolithic deposition and without additional color or wavelength filters).
  • additional optically active layers may include additional contact electrodes per layer.
  • Contact electrodes 302 may be at least partially transparent and overlay all-inorganic colloidal nanostructures 204 in fused film 200. Electrode 302 materials may include aluminum, gold, platinum, silver, magnesium, copper, indium tin oxide (ITO), tin oxide, tungsten oxide, layer structures and combinations thereof.
  • ITO indium tin oxide
  • Substrates 202 may include one or more electrodes 302, or electrodes 302 may be deposited in a later step.
  • Optical devices may also be large-area image sensors on plastic or other flexible substrates.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thin Film Transistor (AREA)

Abstract

L'invention concerne des dispositifs optoélectroniques et leurs procédés de production. Des procédés peuvent consister à former un film à partir de nanostructures colloïdales totalement inorganiques fusionnées, les nanostructures pouvant comprendre des nanoparticules inorganiques et des ligands inorganiques fonctionnels, et les nanostructures fusionnées pouvant former un réseau électrique qui est photoconducteur. D'autres procédés peuvent consister à produire un dispositif optoélectronique qui peut comprendre un circuit intégré ou une matrice de transistors à film mince sous forme de grand panneau, un réseau de régions conductrices et un matériau de sensibilité optique sur au moins une portion du circuit intégré et en communication électrique avec au moins une région conductrice du réseau de régions conductrices.
PCT/US2013/062541 2012-10-01 2013-09-30 Dispositifs optoélectroniques dotés de films nanostructurés colloïdaux totalement inorganiques WO2014055387A1 (fr)

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US201261744593P 2012-10-01 2012-10-01
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US13/755,186 US8779413B1 (en) 2012-10-09 2013-01-31 Optoelectronic devices with all-inorganic colloidal nanostructured films
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Cited By (1)

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CN107210329A (zh) * 2015-01-19 2017-09-26 米兰-比可卡大学 无色发光太阳能集光器，具有扩展到近红外区的吸收的无重金属、基于至少三元硫属化合物的半导体纳米晶体

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US20070006914A1 (en) * 2004-06-18 2007-01-11 Lee Howard W Nanostructured materials and photovoltaic devices including nanostructured materials
US20110315959A1 (en) * 2005-01-07 2011-12-29 Invisage Technologies, Inc. Electronic and optoelectronic devices with quantum dot films

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
US20070006914A1 (en) * 2004-06-18 2007-01-11 Lee Howard W Nanostructured materials and photovoltaic devices including nanostructured materials
US20110315959A1 (en) * 2005-01-07 2011-12-29 Invisage Technologies, Inc. Electronic and optoelectronic devices with quantum dot films

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107210329A (zh) * 2015-01-19 2017-09-26 米兰-比可卡大学 无色发光太阳能集光器，具有扩展到近红外区的吸收的无重金属、基于至少三元硫属化合物的半导体纳米晶体

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