WO2016014345A2 - Dispositifs électroniques à deux bornes et leurs procédés de fabrication - Google Patents

Dispositifs électroniques à deux bornes et leurs procédés de fabrication Download PDF

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WO2016014345A2
WO2016014345A2 PCT/US2015/040815 US2015040815W WO2016014345A2 WO 2016014345 A2 WO2016014345 A2 WO 2016014345A2 US 2015040815 W US2015040815 W US 2015040815W WO 2016014345 A2 WO2016014345 A2 WO 2016014345A2
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layer
semiconductor
electrode
metal
terminal device
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PCT/US2015/040815
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English (en)
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WO2016014345A3 (fr
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Gang Yu
Chan-Tong SHIEH
Zhao Chen
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Cbrite Inc.
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Priority claimed from US14/339,210 external-priority patent/US9741901B2/en
Application filed by Cbrite Inc. filed Critical Cbrite Inc.
Publication of WO2016014345A2 publication Critical patent/WO2016014345A2/fr
Publication of WO2016014345A3 publication Critical patent/WO2016014345A3/fr

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    • 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
    • H10K30/353—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 blocking layers, e.g. exciton blocking layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/1365—Active matrix addressed cells in which the switching element is a two-electrode device
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/20—Organic diodes
    • H10K10/29—Diodes comprising organic-inorganic heterojunctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • H10K39/36—Devices specially adapted for detecting X-ray radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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 invention relates to two-terminal electronic devices, such as photodetectors, photovoltaic devices, electroluminescent devices and methods of their fabrication.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • PVD and CVD apparatuses are expensive and their use increases the costs of electronic device fabrication.
  • stress that is developed during deposition process and/or patterning process is often significant and leads to low manufacturing yield.
  • Examples of such conventionally manufactured devices include photosensing elements in digital X-ray imager made from p-i-n photodiodes based on amorphous silicon (a-Si).
  • Plasma-enhanced chemical vapor deposition (PECVD) process used for deposition of a thick amorphous silicon layer in such device often leads to peeling that is encountered after the pixel in the device is patterned.
  • PECVD Plasma-enhanced chemical vapor deposition
  • patterning of a thin film stack having multiple layers using lithographic technique often results in an "undercut" phenomenon due to different etching rates of different layers.
  • undercut makes pixel connection in the following processing steps very difficult. Accordingly, there is a need for electronic devices that can be fabricated with minimal patterning, with low internal stress among different layers and with reduced costs.
  • imaging elements in display and thin film sensor arrays with improved mechanical stability.
  • Two-terminal electronic devices such as two-terminal photodetectors, photovoltaic devices, electroluminescent devices and high density arrays comprising two-terminal devices that can be fabricated with minimal or no photoresist-dependent patterning, are provided.
  • the structure of the devices and the materials used in the device layers are selected such as to allow for less expensive processing than in traditional fabrication methods. Such structure can also significantly improve device mechanical properties, device storage time and stability in operation.
  • a two terminal device e.g., a photodetector, an electroluminescent device, or a photovoltaic device
  • the device includes a first electrode residing on a substrate, wherein the first electrode comprises a layer of metal or metal alloy; an I-layer comprising an inorganic insulating or broad band semiconducting material residing on top of the first electrode, and aligned with the first electrode, wherein the inorganic insulating or broad band semiconducting material is a compound of the metal or metal alloy of the first electrode; a semiconductor layer residing over the I-layer; and a second electrode residing over the semiconductor layer, the electrode comprising a layer of a conductive material.
  • a two terminal device in a second aspect, wherein the device includes a first electrode residing on a substrate, wherein the first electrode comprises a layer of conductive material (e.g., a metal, metal alloy, a conductive oxide); an I-layer comprising an inorganic insulating or broad band semiconducting material residing on top of the first electrode (e.g., a metal oxide, metal nitride, metal— C-H-0 self-aligned with the first electrode or shared by a plurality of first electrodes in an array); a semiconductor layer residing over the I-layer, wherein the semiconductor layer may include a stack (e.g., a first semiconductor sub-layer and a second semiconductor sub- layer comprising a p-type semiconductor); and a second electrode residing over the semiconductor layer, wherein the second electrode comprises a layer of a conductive material, and wherein at least one of the first and second electrodes is transparent.
  • a layer of conductive material e.g., a metal, metal
  • the semiconductor layer of the two-terminal device comprises an organic and/or an organometallic material. In some embodiments, the semiconductor layer of the two-terminal device comprises an inorganic p-type semiconductor material. In some embodiments the two terminal device is a photovoltaic device and/or a photodetector, and the semiconductor layer is capable of absorbing electromagnetic radiation in at least one spectral wavelength band selected from the group consisting of near-ultraviolet, visible, infrared and combinations thereof. In some embodiments the two-terminal device is an X-ray detector.
  • the semiconductor layer of the two-terminal device preferably comprises at least two sub-layers.
  • the device is a photodetector or an electroluminescent device, which includes a first semiconductor sub-layer in contact with the I-layer, that is configured to generate charge upon irradiation with light, or is configured to generate light after being injected with a charge.
  • the device further includes a second semiconductor sub-layer in contact with the second electrode where the second sub-layer includes a p-type semiconductor configured to conduct holes and block electrons.
  • the two terminal device may be an electroluminescent device and the first semiconductor sublayer configured to generate light under charge injection, may include at least one emitter selected from the group consisting of an organic emitter, an inorganic nano-particle emitter and combinations thereof.
  • the first semiconductor sub-layer is a stack of sub-layers, each of which is configured to emit light at different wavelengths corresponding to different colors.
  • the device is a two terminal electroluminescent device, wherein the first semiconductor sub-layer comprises inorganic semiconductor nanoparticles or quantum dots.
  • the two terminal device may include a stack of photodetecting or electroluminescent devices.
  • the semiconductor layer in the two-terminal device comprises an organic semiconductor and further comprises an inorganic semiconductor as a blend with the organic semiconductor or as a separate sublayer in contact with the organic semiconductor sublayer.
  • the semiconductor in the semiconductor layer has a smaller band gap than the material of the I-layer.
  • the second electrode has a work function that is at least 0.3 eV greater than the work function of the first electrode, referring to absolute values.
  • the first electrode of a two terminal device is a metal or metal alloy selected from the group consisting of Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Ta, Al, Ga, In, Nb, Hf, Zn, Zr, Mo, Ni, Cu, Sn, Y and a metal alloy comprising any of these metals.
  • the I-layer in some embodiments includes one or more of a metal oxide, a metal nitride, a metal fluoride, and a metal sulfide (or other chalcogenide). In some embodiments, the I-layer includes an oxide, nitride, fluoride, or sulfide of the same metal or metals that are present in the first electrode.
  • the second electrode of the two-terminal device is substantially optically transparent.
  • the device may be a top-sensing photodetector (or a photovoltaic device) or a top-emitting electroluminescent device.
  • the transparent second electrode may include a material selected from the group consisting of a transparent conductive oxide (TCO), a transparent conductive organic layer, and a transparent thin metal layer.
  • the first electrode of the two-terminal device is substantially optically transparent.
  • the device may be a bottom-sensing photodetector (or a photovoltaic device) or a bottom-emitting electroluminescent device.
  • the transparent bottom electrode may include a material selected from the group consisting of a (TCO), a transparent conductive organic layer, and a transparent thin metal layer.
  • TCO transparent conductive organic layer
  • transparent thin metal layer transparent thin metal layer
  • the semiconductor layer of the two-terminal device comprises an organic semiconductor selected from the group consisting of PPV, MEH- PPV, P3HT, PTB7, PCPDTBT, PDDTT, PTZBTTT-BDT PC 50 BM, PC 70 BM, TPD, NPB and combinations thereof, wherein PPV is poly(p-phenylene-vinylene), MEH- PPV is Poly[2-methoxy-5-(2-ethylhexyloxy)-l,4-phenylenevinylene], P3HT is Poly(3- hexylthiophene-2,5-diyl), PTB7 is Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[l,2-b:4,5- b'] dithiophene-2,6-diyl] [3 -fluoro-2- [(2-ethylhexyl)carbonyl]thieno [3 ,4- bjthiophened
  • the semiconductor layer of the two-terminal device comprises an inorganic semiconductor selected from the group consisting of MoO, NiO, SiC, CuO, PbS, CuInSe, CuInS, CuInGaSe, CdSe, PbSe, and selenium.
  • the two-terminal device is an X-ray or high energy radiation detector
  • the semiconductor layer comprises: (i) a first sublayer in contact with the I-layer, the first sub-layer comprising a material selected from the group consisting of an amorphous selenium, PbO, Cdl, CdTe and Hgl; and (ii) a second sublayer comprising a p-type semiconductor over the first sublayer.
  • the two-terminal device is a visible light and/or I detector or a photovoltaic device
  • the first electrode comprises a metal selected from the group consisting of Ti, Ta, Zn, In, Sn, Ga and a metal alloy comprising any of these metals
  • the I layer comprises an oxide of the metal or of the metals of the alloy of the first electrode
  • the semiconductor layer comprises two sublayers wherein the first sublayer is in contact with the I-layer and comprises a material selected from the group consisting of PPV, MEHPPV, P3HT, PTB7, PCPDTBT, PTZBTTT-BDT, PDDTT, PCBM, CuO, PbS, CuInSe, CuInS, CuInGaSe, selenium, nanoparticles comprising PbS, PbSe, CdSe, CdS, and a blend comprising them; and the second sublayer comprises a p-type semiconductor configured for conducting holes and blocking electrons, and the second electrode is transparent and comprises a
  • PCBM and/or inorganic nanoparticles are blended into the p-type semiconductor, wherein PCBM is [6,6] -Phenyl Cei butyric acid methyl ester
  • the two-terminal device is a top-emitting electroluminescent device having a semiconductor layer comprising a first semiconductor sub-layer comprising quantum dots light emitter, and a second semiconductor sub-layer comprising a p-type semiconductor, wherein the first semiconductor sub-layer is in contact with an I-layer, and the second semiconductor sub-layer is in contact with the second electrode, wherein the second electrode is transparent.
  • the two-terminal device is a transparent electroluminescent device having a semiconductor layer comprising a first semiconductor sub-layer comprising a light emitter, and a second semiconductor sublayer comprising a p-type semiconductor, wherein the first semiconductor sub-layer is in contact with an I-layer, and the second semiconductor sub-layer is in contact with the second electrode, wherein both the first and second electrodes are transparent.
  • each device comprises: a first electrode residing on a substrate and patterned to define the size of each device, wherein the first electrode comprises a layer of metal or metal alloy; an I-layer comprising an inorganic insulating or broad band semiconducting material residing on top of the first electrode, and aligned with the first electrode, wherein the inorganic insulating or broad band semiconducting material is a compound of the metal or metal alloy of the first electrode; a semiconductor layer residing over the I-layer; and an optically transparent second electrode residing over the semiconductor layer, wherein the I-layer is not shared by the individual devices of the array, and the semiconductor layer and the second electrodes are shared by the individual devices of the array.
  • the semiconductor layer comprises at least two sub-layers, wherein the first semiconductor sub-layer is in contact with the I-layer, and is configured to generate charge under light illumination, or to generate light upon being injected with a charge, and wherein the second semiconductor sub-layer is in contact with the second electrode and comprises p-type semiconductor configured to conduct holes and block electrons.
  • an array of two-terminal photosensing or light emission devices comprising: a first electrode residing on a substrate; an I-layer comprising an inorganic insulating or broad band semiconducting material residing on top of the first electrode; a semiconductor layer residing over the I- layer; and a second electrode residing over the semiconductor layer, wherein the I- layer, the semiconductor layer and the second electrode are shared by the individual devices of the array, and wherein at least one of the first and second electrodes is transparent.
  • the semiconductor layer comprises at least two sublayers, and wherein the first semiconductor sublayer is in contact with the I-layer, and is configured to generate charge under light illumination, or to generate light upon being injected with a charge, wherein the second semiconductor sublayer is in contact with the second electrode and comprises p-type semiconductor configured to conduct holes and block electrons.
  • the semiconductor layer comprises at least two sublayers, and wherein the first semiconductor sublayer is in contact with the I-layer, and is configured to generate charge under light illumination, or to generate light upon being injected with a charge, wherein the second semiconductor sublayer is in contact with the second electrode and comprises p-type semiconductor configured to conduct holes and block electrons.
  • a method of forming a two terminal device on a substrate may include in some embodiments: (a) forming a first electrode on a substrate, wherein the first electrode comprises a layer of metal or metal alloy; (b) oxidizing the layer of metal to form a self-aligned layer of a metal compound on the metal layer; (c) forming a layer of semiconductor or a stack of semiconductor layers over the layer of metal compound; and (d) forming a second electrode over the semiconductor layer or the stack.
  • a method of forming a two terminal device on a substrate includes: (a) forming a first electrode on a substrate, wherein the first electrode comprises a layer of conductive material; (b) forming a sacrificial metal-containing layer (e.g., a metal salt and/or an organometallic compound) over the layer of metal; (c) treating the sacrificial layer to convert it to a layer comprising a metal compound (e.g., metal oxide, metal nitride, metal-C-H-O, and the like) suitable for an I-layer; (d) forming a layer of semiconductor or a stack of semiconductor layers over the layer of metal compound; and (e) forming a second electrode over the semiconductor layer or the stack.
  • a metal compound e.g., metal oxide, metal nitride, metal-C-H-O, and the like
  • the metal of the first electrode and the metal of the I-layer may be the same or different metals.
  • a method of forming an array of photosensing or light emitting devices on a substrate includes in some embodiments: (a) forming a patterned first electrode on a substrate which defines individual elements of the array; (b) forming an I-layer comprising an inorganic insulating or a broad band semiconducting material over the first electrode; (c) forming a semiconductor layer or a stack of semiconductor layers over the I-layer such that the semiconductor layer or the stack is shared between the individual devices in an array; and (d) forming a second electrode over the semiconductor layer, wherein the second electrodes are connected between neighboring pixel elements, wherein at least one of the first and second electrodes is transparent.
  • the amount of patterning during fabrication can be substantially reduced by using the methods and device structures provided herein.
  • Figure 1A presents a cross-sectional view of an electronic device in accordance with some embodiments of the present invention.
  • Figure IB presents a cross-sectional view of an electronic device in accordance with some embodiments of the present invention.
  • Figure 2A presents a schematic cross-sectional view of an array of electronic devices in accordance with an embodiment of the present invention.
  • Figure 2B presents a schematic cross-sectional view of an array of electronic devices in accordance with an embodiment of the present invention.
  • Figure 3 is a process flow diagram for a process of fabricating an electronic device in accordance with some embodiments of the present invention.
  • Figure 4 is a process flow diagram for a process of fabricating an electronic device in accordance with some embodiments of the present invention.
  • Figure 5 is an energy diagram for one of the configurations of an electronic device in accordance with an embodiment presented herein.
  • Figure 6A is an experimental plot illustrating external quantum efficiency (EQE) dependence on a wavelength for a top-sensing image array, according to an embodiment presented herein.
  • Figure 6B is an experimental plot illustrating I-V characteristics upon illumination with light of different wavelengths and in the dark, for a top-sensing image array, according to an embodiment presented herein
  • Figure 6C is an experimental plot illustrating I-V characteristics for a top- sensing image array and for a bottom-sensing image array.
  • oxidation refers generally to an increase in the oxidation state (e.g., from 0 to +4), and is not limited to reactions with oxygen, but also includes other oxidation reactions, such as formation of nitrides, sulfides, selenides, and fluorides from metals.
  • Some embodiments of the invention employ liquid-phase processing at relatively low temperature as an alternative to costly and laborious deposition operations and photolithographic patterning at least for some of the components in the device structure, and particularly for the top electrode layer.
  • Some embodiments of the invention employ a layer of a semiconductor material spanning several electronic devices in an array. The use of such blanket semiconductor layer allows one to reduce the number of patterning steps in device fabrication. Further, some embodiments of the invention employ a top electrode layer that is unpatterned and that spans several devices in an array.
  • Several types of electronic devices can be fabricated using methods provided herein. These include photodetectors, photovoltaic devices and electroluminescent devices.
  • Photodetectors are sensors that produce an electrical output signal after they are irradiated. Irradiation is not limited to visible part of the spectrum and also includes X- ray irradiation, ultraviolet (UV) irradiation, infrared (IR) irradiation. X-ray, UV, Vis, and IR photodetectors are provided herein. Photoconductors and photodiodes are examples of photodetectors.
  • Photovoltaic devices produce an electrical output signal upon irradiation that can be used to power other appliances.
  • Electroluminescent devices emit light in response to an electrical signal and are also referred herein to as light emitting devices (LEDs). UV, Vis, and IR LEDs can be formed using provided methods.
  • the electronic devices provided herein in some embodiments include at least four layers: (a) a first electrode (functioning as a cathode) residing on a substrate, wherein the first electrode comprises a layer of metal (wherein the term "metal” includes pure metals and metal alloys); (b) an I-layer comprising an inorganic insulating or broad band semiconducting material residing on top of the first electrode, and aligned with the first electrode, wherein the inorganic insulating or broad band semiconducting material is a compound of the metal of the first electrode; (c) a semiconductor layer residing over the I-layer and comprising an organic semiconductor, an inorganic semiconductor or an organic/inorganic blend, wherein the semiconductor layer is preferably p-type; and (d) a second electrode (functioning as an anode) residing over the semiconductor layer, the second electrode comprising a layer of a conductive material.
  • a first electrode functioning as a cathode
  • the first electrode comprises a layer of metal (
  • the semiconductor layer may include two sub-layers, a first sublayer configured for light emission or photodetection, and a second sublayer comprising a p-type semiconductor material.
  • the term "over" when used to describe relative position of the layers means that one layer at least partially overlies another layer, but the two layers need not necessarily be in direct contact (e.g., there may be a another layer inserted between them).
  • the I-layer need not necessarily be self-aligned with the bottom electrode and need not be made from the same metal as the bottom electrode.
  • the I-layer may be a layer of metal oxide, metal nitride, metal oxynitride, metal-O-C-H and the like, wherein the layer is continuous and may be shared by a plurality of devices (e.g., corresponding to individual pixels) in an array.
  • Such layers may be prepared by coating the substrate containing patterned bottom electrodes with a precursor containing a metal (e.g., a metal salt or an organometalhc compound), followed by treatment to form the I-layer material, e.g., by annealing in a suitable environment.
  • a metal e.g., a metal salt or an organometalhc compound
  • the semiconductor layer can be organic (the term also including organometalhc), inorganic or be in the form of an organic/inorganic blend or stack of individual organic and inorganic layers.
  • the organic semiconductor may include one or more organic semiconductor molecules in a blend or in a stack of individual layers.
  • the inorganic semiconductor may similarly include several inorganic molecules in a blend or in a stack of individual layers.
  • the semiconductor layer includes organometalhc compounds or inorganic nanoparticles. Materials are selected for the electronic devices such as to provide the necessary function.
  • the materials of the first and second electrodes are selected such that the difference between work functions of the two materials is greater than 0.3 eV, e.g., the anode has a work function that is at least 0.3 eV greater than the work function of the cathode in absolute value.
  • the difference in the work function is 0.7eV in absolute value.
  • the materials are selected such that the work function difference between the anode and the cathode is preferably at least about 1 eV, e.g., between about 2-2.5 eV.
  • tantalum, tantalum-aluminum, or tantalum- zirconium alloy can be used as a cathode in an LED, while a conducting polymer having high work function such as PEDOT (work function in a range of about 5.1- 5.3eV) can be used as an anode.
  • PEDOT work function in a range of about 5.1- 5.3eV
  • the described electronic devices are characterized by asymmetrical current-voltage (I-V) curve.
  • a substantially higher current is observed in a forward bias (higher potential applied to anode) than in a reverse bias in their I-V curves.
  • the materials of the electrode need to have the required difference in the work function, but only the materials that directly participate in charge transfer are relevant for this purpose.
  • a titanium- coated ITO electrode where titanium is in contact with the titanium oxide I-layer will be characterized by the work function of titanium rather than ITO. Therefore, for the bottom and top electrodes, the materials that are in direct contact with the I-layer and the semiconductor layer define the work functions of electrodes.
  • the work function of certain materials, e.g., ITO can be tuned in a relatively broad range by changing, e.g., oxygen content, thereby allowing tuning of the required work function difference between the electrodes.
  • the material for the I-layer is selected such that its band gap is at least about 2.5 eV.
  • examples of such materials include metal oxides, metal sulfides, metal fluorides, etc.
  • the band gap of the semiconductor layer overlying the I-layer is preferably smaller than the band gap of the underlying I-layer material.
  • the second (top) electrode is substantially optically transparent.
  • Optical transparency is determined by the type of radiation that the device is designed to sense or emit. For example, if the device is a UV-detector the top electrode is preferably substantially transparent to UV radiation. If the device is designed to sense certain visible light wavelengths, the top electrode is substantially transparent to these wavelengths.
  • optically transparent electrodes include transparent oxides, such as indium-tin-oxide (ITO), indium-zinc-oxide (IZO), and aluminum-zinc-oxide (AZO) and thin layers of conductive polymers such as PEDOT (Poly(3,4-ethylenedioxythiophene))-based, PANI (polyaniline) - based and) PPY (polypyrrole) - based polymers.
  • PEDOT Poly(3,4-ethylenedioxythiophene)
  • PANI polyaniline
  • PPY polypyrrole
  • thin layers containing metals are used.
  • thin Ag/AgO electrode can be used as an optically transparent anode.
  • liquid-phase processing refers to formation of material from a liquid-containing phase material, such as a solution, a suspension, a sol-gel, or a melt.
  • the liquid phase may contain either the material to be deposited or its precursor.
  • the deposition of material by liquid phase processing typically involves delivering the liquid-phase material containing the material or its precursor to an underlying layer or a substrate of the device structure.
  • the liquid phase material is delivered selectively to the final positions where it is to be located in the electronic devices. In other embodiments, it is delivered more broadly over a wider area of the underlying substrate and then selectively removed by a patterning process or other process.
  • the deposited liquid phase material may be modified (e.g., cooled, heated, reacted, etc.) to produce a conductive layer or insulating/semiconducting layer for an electronic device.
  • the liquid phase material can be delivered by a variety of methods known by those of skill in the art. These include immersion, coating, droplet based printing (e.g., ink jet printing), gravure printing, silkscreen printing, thermal transfer printing, offset printing etc. Coating methods include spin-coating, spray-coating, bar-coating, dip- coating, slot coating and the like.
  • the liquid phase material may be delivered in a patterned manner (e.g., printing a pattern), so that no additional patterning is required after material is deposited. Such deposition reduces the necessity of costly and laborious photolithographic patterning.
  • the material can be formed in a number of ways. These include solvent evaporation, cooling or heating of the liquid phase, chemically or electrochemically treating a precursor in the liquid phase, treating a material or its precursor in a liquid by irradiation or high temperature to cause material precipitation. Specific examples include, evaporation of solvent from a printed solution of an ink, electroplating a metal, depositing a metal by electroless deposition, depositing material by cooling a melt, etc.
  • liquid-phase deposition for the deposition of the top electrode of the electronic device (i.e., the electrode further removed from the underlying substrate), while the bottom electrode may be formed by conventional methods.
  • liquid-phase deposition is used to deposit a semiconductor layer over an I-layer.
  • certain embodiments fabricate at least one of the liquid phase layers by a printing/coating process.
  • FIG. 1A An example of a two-terminal electronic device structure, according to one embodiment of the present invention is shown in Figure 1A.
  • the electronic device is a four-layer device, with an I-layer and a semiconductor layer residing between two layers of conductive materials. It is understood, that in other embodiments electronic devices may include additional layers, or any of the three layers may comprise two or more sub-layers forming a stack.
  • a cross-sectional view of an electronic device e.g., a photodetector or a photovoltaic device
  • Electroluminescent devices have similar structures and also typically include an additional layer of electroluminescent material disposed over the I-layer, also referred to here as the first semiconductor sub-layer.
  • the device 101 resides on a substrate 103 and includes a first electrode layer 105, an I-layer 107, a semiconductor layer 109 and a second electrode layer 111. Electrical contacts (not shown) connect the electrodes 105 and 111 to external circuit, or other components above or below.
  • the bottom electrode 105 is connected to a readout circuit underneath through a via-hole in a planarization/passivation insulator layer.
  • the two terminals of the device are connected to a low impedance load such as a lamp.
  • the device is operating with its internal potential created by the p-i-n structure and flows current through the external load.
  • operation can be conducted at a nearly zero bias similarly to a photovoltaic cell, or at a reverse bias (connecting the anode (electrode at the p-layer side) to a voltage bias with low potential and n-layer side (cathode) with a higher potential).
  • the photocurrent can be probed with a current meter in the loop or a voltage drop can be read on a resistive load connected in the loop.
  • the anode is biased with a positive voltage (higher potential to anode).
  • the external biasing voltage is higher than the internal potential created by the P-I-N structure in the LED, a current flows through as in a non-symmetric switch diode.
  • the sizes of devices can vary depending on application and can range from about a few microns in high pixel density image or display array to a few centimeters in photovoltaic devices.
  • macroscopic photodetectors or light emitting diodes are provided as single structures or are incorporated into an array.
  • arrays of small electronic devices with pixel elements sizes of between about a few microns to a few millimeters are provided.
  • the substrate 101 is typically made of an insulating material that does not allow shorting of multiple electronic devices residing on such substrate (e.g., as a matrix of electronic devices).
  • the substrate may include a conductive material (e.g., a metal), but in such cases a protective insulating coating is typically employed to prevent shorting between neighboring elements or circuits.
  • Suitable substrate materials include glasses, crystalline wafers, polymeric materials (e.g., plastic sheets) and stainless steel foils.
  • PET polyethyleneterephthalate
  • Substrates can be either rigid or flexible.
  • substrates have a melting point or glass transition point (Tg) lower than about 300 C or even about 200 °C.
  • device 101 is constructed on top of other circuits underneath. That is, device 101 is stacked on top of another circuit layer on top of substrate 103.
  • the first electrode 105 is also sometimes called the "bottom" electrode to indicate that the electrode is closest to an underlying substrate.
  • the first electrode functions as a cathode in the provided electronic devices. Typically, though not necessarily, it is formed directly on the underlying substrate. In some cases, another circuit can be inserted between the substrate 103 and the first electrode 105.
  • the first electrode may include any suitable conductive metal (wherein the term "metal” includes metal alloys).
  • metals can be used as first electrode layers.
  • metals such as Ti, Ta, Al, Ga, In, Nb, Hf, Sn, Zn, Zr, Cu, Sm, Cd, Mn, Fe, Cr, Ni and Y can be employed. Alloys of these metals with each other, such as TaAl, TaZr, TiZr and TiAl, or with other metals are also suitable conducting materials for the first electrode.
  • alkaline-earth metals such as Ca, Ba, Sr and Mg can be used.
  • Rare earth metals such as Sm and other lanthanides are also suitable.
  • the metal of the first electrode includes one or more of Ti, Ta, Zn, In, Sn, Ga, Hf, Zr, Cd, V, and Nb.
  • Ti, Ta, Zn, In, Sn, and Ga are preferred in some embodiments.
  • the first electrode functions as a cathode, metals with a relatively low work function are typically selected. In some embodiments the work function of the first electrode is less than about 4.5 eV (for a photodetector or a photovoltaic device) or less than about 3.5 eV (for an electroluminescent device).
  • the first electrode 105 may be a single layer of material or may be formed of several layers forming a stack.
  • the thickness of the first electrode is not critical and can be from hundreds of Angstroms to hundreds of microns or thicker.
  • transmission to radiation wavelength is desirable for bottom electrode, for example, in a visible-infrared photodetector array with light incidence from the bottom substrate side or for a light emitting diode arrays with light emission from bottom substrate side.
  • electrode 105 can be made with a thin metal layer, or a thin metal on top of a conducting metal oxide (such as In 2 C>3, Sn0 2 , or In-Sn-O) layer, that is transparent to the desired radiation.
  • the bottom substrate may also be transparent to the desired radiation.
  • the I-layer 107 in the electronic devices of this invention includes an inorganic component which preferably has a band gap of at least about 2.5 eV. In many cases, the I-layer is entirely inorganic, with no organic component. In other embodiments, an inorganic/organic blend or an organometallic compound can be used in the I-layer.
  • the I-layer material is also referred to as an insulator or a broad band semiconductor, and includes, in some embodiments, stoichiometric and non-stoichiometric oxides, nitrides, chalcogenides (e.g., sulfides) and halides of metals. In some embodiments, the I-layer includes a compound of the same metal that is used in the first electrode.
  • the I-layer may be made of tantalum oxide, tantalum nitride, tantalum sulfide, tantalum selenide and the like.
  • Composite oxides and inorganic ceramic nanocomposites comprising single or multiple metal anions, such as Ta-Al-O, Ta-Zr-O, Sr-Ta-O, Sr-Ti-O, Zr-Ti-O, Ca-Ti-O, Mg-Ti-O, Y x Ba y O z (e.g., YBa0 3 ) and Sm x Sn y O z (e.g., Sm 2 Sn 2 0 7 ) are also suitable.
  • the I-layer includes a compound of Ti, Ta, Al, Ga, In, Nb, Hf, Sn, Zn, Zr, W, Sr, Cu, Sm, Cd, Mn, Fe, Cr, Ni, Nb or Y or their combinations
  • Compounds of alkaline-earth metals, such as Ca, Sr, Ba, and Mg are used in some embodiments.
  • the I-layer is formed by converting a portion of an underlying electrode layer 105 into a desired metal compound (e.g., oxide, nitride, chalcogenide, or halide).
  • a desired metal compound e.g., oxide, nitride, chalcogenide, or halide.
  • the I-layer is formed in a self-aligned manner on top of the first electrode thereby eliminating the need of additional patterning.
  • convertion processes includes anodization, surface oxidation at an elevated temperature under oxygen and/or water vapor environment, plasma treatment in oxygen presence, surface treatment in H 2 S vapor environment and their combinations. Similar processes have been disclosed in US Patent No. 8,222,077 which is herein incorporated by reference in its entirety.
  • a sacrificial layer of an organometallic compound or any metal-containing precursor is formed on top of the first electrode and is then converted to an I-layer, e.g. at an elevated temperature under desired environment, such as in proper N 2 , Ar, 0 2 , or H 2 0 ambient.
  • desired environment such as in proper N 2 , Ar, 0 2 , or H 2 0 ambient.
  • I-layer an important parameter that may influence the performance of the electronic device. The thicknesses may range depending on specific applications. For UV, visible and infrared photodetectors and light emitters, the thickness of the I-layer is typically in the 10-10 2 nm range.
  • I-layer thicknesses of greater than 10 2 nm can be used.
  • the actual thickness depends in part on the type of material employed as the I-layer and, especially on its dielectric constant or carrier density generated by mixed-valences of metals that are involved and oxygen vacancies that exist.
  • larger photodetectors, photovoltaic devices, and LEDs with I-layers having thicknesses of greater than 100 nm may be desirable.
  • the I-layer material further serves as a diffusion barrier between the electrode and the organic layer.
  • materials having good barrier properties such as metal nitrides (e.g., tantalum nitride and titanium nitride) are particularly preferred.
  • Semiconductor layer e.g., tantalum nitride and titanium nitride
  • a semiconductor layer 109 resides over the I-layer 107, and in the embodiment depicted in Figure 1A is in direct contact with the I-layer. In other embodiment one or more additional layers of material may be inserted between the I-layer and the semiconductor layer.
  • the semiconductor layer 107 typically includes a semiconductor material that has a band gap that is smaller than the band gap of the I-layer material. Although not limited, p-type semiconductors are preferred in devices with hetero junction structure.
  • the semiconductor layer in some embodiments, comprises a p-type inorganic semiconductor.
  • Examples include Mo-O, Ni-O, V-O, Si-C, Cu-O, Zn-O-N, Cu-In-O, Cu-In-Ga-O, Pb-S, Pb-Se, Cu-In-Se, Cu-In-S, Cu-In-Ga-Se, Cu-In-Ga-S, Cd-S, Cd-Se, Cd-Te, Pb-S, Pb-Se, Pb-Te, Pb-Ta-O.
  • the p-layer can be a single compound film, a blend film comprising multiple compounds or a stack of films with made with different compositions.
  • the semiconductor layer 109 can also be an organic semiconductor or a blend/composite film comprising an organic semiconductor binder with an inorganic or an organometallic molecule(s)/nanoparticle(s).
  • the inorganic nanoparticles and/or molecules in the blend and/or composite can be the same compounds listed above in single phase, or they can be presented in multiple layers in core-shell structures.
  • Examples of specific organic semiconductors as layer 109 or as binder component in blend film 109 include polyacetylene (PA) and its derivatives, polythiophene (PT) and its derivatives, such as poly(3-hexylthiophene) (P3HT), PTB7, PCPDTBT, PDDTT, poly(p-phenyl vinylene) (PPV) and its derivatives, such as poly[2- methoxy-5 -(2 ' -ethylhexyloxy)- 1 ,4-phenylenevinylene] (MEH-PPV), polypyrrole, ("PPY”), and its derivatives; poly(2,5-thienylenevinylene), (“PTV”), and its derivatives; poly(p-phenylene), (“PPP”), and its derivatives; polyflourene, ("PFO”), and its derivatives; polycarbazole and its derivatives; poly(l,6-heptadiyne); polyquinolene and semiconducting poly
  • leucoemeraldine and/or the emeraldine base form include anthracene, tetracene, pentacene, tris- (8-hydroxyquinoline)aluminum (Alq3), and other metal-ligand complexes and organometallic compounds. Of these materials, those which exhibit solubility in organic or aqueous solvents are preferred because of their processing advantages.
  • Examples of PPV derivatives which are soluble to common organic solvents include MEH-PPV (F. Wudl, P. -M. Allemand, G. Srdanov, Z. Ni and D. McBranch, in Materials for Nonlinear Optics: Chemical Perspectives, edited by S. R. Marder, J. E. Sohn and G. D. Stucky (The American Chemical Society, Washington D.C., 1991), p. 683.), poly(2-butyl-5-(2-ethyl-hexyl)-l,4-phenylenevinylene), (“BuEH-PPV”) (M. A. Andersson, G. Yu, A. J. Heeger, Synth.
  • MEH-PPV F. Wudl, P. -M. Allemand, G. Srdanov, Z. Ni and D. McBranch, in Materials for Nonlinear Optics: Chemical Perspectives, edited by S. R. Marder, J. E. Sohn and G. D. Stucky (
  • soluble PTs include poly(3-alkylthiophenes), (P3AT), wherein the alkyl side chains contain more than 4 carbons, such as from 5 to 30 carbons.
  • the semiconductor layer 109 can also be fabricated using donor/acceptor polyblends. These polyblends can be blends of semiconducting polymer/polymer, or blends of semiconducting polymer with suitable organic molecules, organometallic molecules, and/or inorganic molecules or inorganic nanoparticles.
  • Examples for the donor of the donor/acceptor polyblends include but are not limited to the conjugated polymers (e.g., PPV, PT, PTV, and poly(p-phenylene)), and their soluble derivatives.
  • Examples for the acceptors of the donor/acceptor polyblends include but are not limited to poly(cyanaophenylenevinylene) ("CN-PPV"), fullerene molecules such as C 6 o and its functional derivatives, carbon nanotubes (CNT), graphenes and organic semiconductor molecules and organometallic molecules used heretofore in the art for photoreceptors or electron transport layers.
  • CN-PPV poly(cyanaophenylenevinylene)
  • CNT carbon nanotubes
  • organometallic molecules used heretofore in the art for photoreceptors or electron transport layers.
  • charge transfer compounds may be included in the semiconductor layer 109 (either alone or in a mixture with other semiconductor materials described above).
  • Such charge transfer compounds include but are not limited to charge transport molecules comprising oxadiazole groups, such as 2-(4-biphenyl)-5-(4-tert- butylphenyl)-l ,3,4-oxadiazole (PBD), and charge transport molecules comprising arylamine groups, such as 4,4'-bis[N-(l-naphthyl)-7V-phenylamino]biphenyl (NPB), and 4,4'-bis[N-(3-methylphenyl)-N-phenylamino]biphenyl (TPB). Soluble derivatives and oligomers comprising such molecular unit can also be used.
  • the semiconductor layer 109 may comprise an organic semiconductor, an inorganic semiconductor, or a blend or composite.
  • the semiconductor layer 109 comprises a plurality of sub-layers, where different sub-layers may include different semiconductors.
  • sub-layers of organic and inorganic semiconductors may be stacked.
  • several organic semiconductor molecules are blended in one layer 109.
  • distinct sub-layers of different organic semiconductor molecules may be formed in a stack.
  • several inorganic semiconductor molecules are blended in one layer 109.
  • distinct sub-layers of different inorganic semiconductor molecules may be formed in a stack.
  • Electro-optic sometimes also called electroluminescent
  • Opto-electric effect refers to electrons and holes being generated under radiation with photon energy above energy gap of the I- and/or semiconductor layer that can be collected in external circuit connecting the bottom and top electrodes.
  • the thickness of the semiconductor layer can range from about 0.1 to about 1 ⁇ .
  • the thickness of the semiconductor layer can be in a range of about 20-200 nm.
  • the semiconductor layer can be deposited by any suitable method, including thermal deposition, sputter, eBeam, CVD, and atomic layer deposition. Liquid-phase processing (e.g., spin coating, slot/slit coating, screen printing) can be used as well.
  • a non-patterned continuous film can be used for the semiconductor layer 109.
  • the thin film semiconductors disclosed in some embodiments of this invention are either purely amorphous, or polycrystalline with crystal grain size substantially smaller than the film thickness.
  • the process adopted and the materials selected in the provided embodiments enables one to make photosensors and photovoltaic cells with sensing layer that is substantially thinner than the sensing layers used in crystalline wafers. Accordingly, even in high pixel count array devices the sensing layer does not need to be patterned in the provided embodiments (although patterning can be used if desired). These methods substantially save process costs and improve process yields.
  • conventional photodetectors and photovoltaic cells that are made using inorganic covalent semiconductor wafers and films have relatively narrow sensing bandwidth that is typically smaller than 800nm.
  • the sensing wavelength range in conventional photodiodes and photovoltaic cells made using single crystal silicon, polycrystalline silicon, amorphous silicon, GaAs and InGaAs are 0.2-1 mm, 0.3-0.8 mm, 0.3-0.7 ⁇ , 0.2-0.9 ⁇ and 0.8-1.7 ⁇ respectively.
  • organic semiconductors typically possess broader absorption band due to ⁇ 0.2eV energy splitting and shift related to electron-lattice interaction.
  • solution-based processes that can be used in the embodiments provided herein enable forming blend films with multiple components having different absorption and photosensing profiles.
  • photodetectors and photovoltaic cells in some embodiments can have broad range of photoresponse, such as greater than 1 ⁇ .
  • photodetectors with photoresponse from 0.3 ⁇ to 2 ⁇ and even greater was demonstrated. The detection range was thus greater thanl .7 ⁇ .
  • photodetectors and photovoltaic cells with broad photoresponse range can also be made by using several sublayers of materials with different energy structure.
  • second electrode 111 can employ any conductive material that has a work function that is greater than the work function of the first electrode material.
  • the work function of the second electrode material is at least 0.3 eV greater in absolute value than the work function of the first electrode material.
  • the material of the second electrode 111 is substantially optically transparent.
  • optically transparent electrode materials include thin films of conductive polymers and transparent conductive metal oxides, such as indium- oxide, tin-oxide, aluminum-zinc-oxide, indium-zinc-oxide and indium-tin-oxide.
  • organic conductive materials such as conductive polymers and oligomers are found to be particularly suitable.
  • Conductive polythiophene direvatives such as poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrroles (PPY), polyanilines (PANI), and co-polymers thereof can be used.
  • Conducting nanotubes, doped fullerene molecules, graphene molecules can also be used.
  • blends of neutral conjugated polyfluorenes (PFs), PPVs and polythiophenes (PTs) and charge-transporting polythiophenes (e.g., doped polythiophenes), polyanilines and polypyrroles can be used in a top electrode 111.
  • Organic conductive materials often include dopants that increase their conductivity. These dopants may be organic or inorganic (e.g., such as those described above). Preferred organic dopants include charged polymers, such as poly(styrenesulphonate) (PSS), which is commonly used in PEDOT:PSS and PA I:PSS combinations. Other suitable inorganic dopants include certain metal oxides (e.g., Ti0 2 ), dimethylsulfoxide (DMSO), and carbon black, which are commonly used in, for example, PPY:Ti0 2 , and PPY:Carbon black and PEDOT:DMSO combinations. In some embodiments metal nanoparticles, such as silver and gold nanoparticles are used in the second electrode. These materials can be deposited by a liquid-phase processing method such as inkjet printing, screen printing, or slit coating.
  • precursor materials used for the second electrode layer are soluble in a polar or a non-polar solvent.
  • Polar or non-polar organic solvents such as alcohols (e.g., methanol), acetone or hydrocarbon solvents may be used to deliver the above mentioned materials using liquid-phase processing.
  • Materials that are water-soluble or that are soluble in organic/aqueous solutions, such as aqueous alcohols are also used in some embodiments.
  • Such liquid media may be used, in some embodiments, to form the first electrode and/or the I-layer when a liquid phase deposition process is employed.
  • the thickness of the second electrode similarly to the thickness of the first electrode is not critical and can be from hundreds of Angstroms to hundreds of microns or thicker. For the applications requiring transparent top electrode, the thickness is often in 10 nm-1000 nm range. For the applications requiring high conductivity over large device size, for example in a module of photovoltaic cell array with bottom illumination, an opaque top electrode can be used with a thickness in 1-100 ⁇ range.
  • the structure of the device shown in Figure 1A is modified and additional layers are included to tune the electronic performance of the device and/or to include a light-emitting layer.
  • a structure containing 5 layers is shown in Figure IB.
  • the structure shown in Figure IB includes the same types of layers as described with reference to Figure 1A, with the following difference.
  • the semiconductor layer is split into two sub-layers: sub-layer 110 is an inorganic semiconductor layer, and sub-layer 109 is an organic semiconductor layer.
  • an electroluminescent device can have a structure as shown in Figure IB, wherein layer 109 is an emission layer (also referred to as the first semiconductor sub-layer), and layer 110 is a p-type (hole-transport) semiconductor layer (also referred to as the second semiconductor sub-layer).
  • the p-type semiconductor layer 110 may be organic, inorganic or a hybrid organic/inorganic material and may include multiple sub-layers or be in a composite form.
  • suitable emission layer materials for layer 109 include small molecules (such as tris(8- hydroxy-quinolinato)aluminium (Alq3), bis(2-methyl-8-quinolinolate)-4-
  • Luminescent dopants can be added into emission layer 109 to improve emission efficiency and/or to tune emission profile and color.
  • Examples of dopant for emission layer 109 include, BCM, 3-(2-benzothiazolyl)-7- (diethylamino)coumarin (Coumarin 6), 2,3,6,7-tetrahydro-l,l,7,7,-tetramethyl-lH, 5H,l lH-10-(2-benzothiazolyl) (LT-E502) quinolizino[9,9a,lg/z]coumarin (C545T), Tris(2-phenylpyridine)iridium(III), Ir(ppy) 3 , Bis(2- phenylpyridine)(acetylacetonate)iridium(III), Ir(ppy)2(acac), bis(l- phenylisoquinoline)(acetylacetonate)iridium(III), Ir(piq)2(acac), bis(3
  • Layer 109 can be made by thermal deposition, or by coating or printing methods. Emission layer 109 can also be made with inorganic semiconductor nanoparticles dispersed in an organic semiconductor binder (e.g., materials listed above) or with the inorganic nanoparticles passivated with a surfactant molecules/oligomers/polymers comprising a hole-transport group (such as para-methyl triphenylamine) and polar and/or anchor group (such as pentafluorophenole) that processable in a suspension and/or a solution form.
  • a surfactant molecules/oligomers/polymers comprising a hole-transport group (such as para-methyl triphenylamine) and polar and/or anchor group (such as pentafluorophenole) that processable in a suspension and/or a solution form.
  • Examples of such inorganic nanoparticles including CdSe, CdTe, CdS, ZnS, Cdi_ x Zn x S, InP, Cu 2 0, Cui_ x Zn x O, CuS, Ci_ x Zn x S and their combinations in core-shell form or in blend form.
  • a thick non-doped or low- doped semiconductor layer (first semiconductor sub-layer 109) containing elements with large atomic weight can be inserted between the I-layer 107 and the p-type semiconductor layer 110.
  • the materials suitable for such thick semiconductor layer include amorphous selenium, PbO, Cdl and Hgl.
  • Selenium layer may be in an amorphous form, while the PbO, Cdl and Hgl compound materials may be in crystalline form.
  • Thickness of such thick semiconductor layer is often in 10-10 2 micron range and high thickness is needed to optimize the carrier generation and collection efficiency.
  • Such detectors are biased in some embodiments in 30-300 V range to achieve optimized carrier collection efficiency and special imaging resolution.
  • the I-layer materials such as ZnO, Ti0 2 , Ta 2 Os can be used for these applications with thickness of -lOOnm, while MoO, NPB and PPV can be used for the p-type semiconductor layer (second semiconductor sub-layer) for collecting holes and blocking electrons.
  • arrays of electronic devices are provided on a substrate.
  • individual devices in an array correspond to individual pixels, although in other embodiments groups of individual devices in an array may correspond to a single pixel.
  • An embodiment illustrated in Figure 2A illustrates a schematic presentation of such an array 201, where a plurality of electronic devices (e.g., photodetectors, photovoltaic devices or LEDs) is disposed on a substrate 203.
  • the first electrode layer 205 is patterned to define the individual devices.
  • the I-layer 207 is formed in a self-aligned manner with the underlying first electrode layer 205, and therefore does not require additional patterning.
  • the semiconductor layer 207 can be deposited without patterning over the plurality of devices. Organic and inorganic semiconductors, preferably of p-type, as described above can be used for this layer.
  • the second electrode layer 211 is also deposited without patterning and spans a plurality of devices.
  • the thickness of the semiconductor layer is smaller than the space between neighboring electrodes 205. Therefore the carrier conduction along y- direction is substantially greater than in an x-direction.
  • Typical thickness of the semiconductor layer is 30-300 nm in LED devices, 100-1000 nm in photovoltaic and photodetector array devices.
  • the ratio between the thickness of semiconductor layer and the space between neighboring bottom (first) electrodes is typically smaller than 0.5, preferably smaller than 0.35.
  • transparent and/or semitransparent conductive film is selected for electrode 205, wherein the transparency refers to transparency to the wavelength of interest.
  • the top electrode 211 does not need to be transparent.
  • transparent and/or semitransparent conductive film is selected for the electrode 211, where transparency refers to the wavelength of interest.
  • the concept is extended by stacking such two devices together for additional integration of function. For example, by stacking a blue LED array on top of yellow LED array, one could form a light emitting array with emission covering entire visible spectrum, from 400nm to 700nm. By stacking an infrared sensor detector array on top of an LED array, one could convert the incident infrared image into a visible light image.
  • the electrode layer shared by the two arrays is thin enough (typically 0.001-0.1 times of the space between two neighboring bottom electrodes 205), such stacked device arrays with multiple functions can be made with only the bottom electrode 205 being patterned. Such array devices can thus be made with simple manufacturing process and high yield.
  • FIG. 2B illustrates another embodiment of an array of devices on a substrate.
  • the difference from the structure illustrated by Figure 2A is that the I-layer 207 is not patterned and is shared by several devices.
  • the only layer that is patterned is the first electrode layer 205.
  • the continuous I-layer as shown in Figure 2B can be used, for example, in a device that is prepared as follows.
  • the first electrode 203 is deposited and patterned; then a sacrificial metal-containing precursor layer is deposited, e.g., by spin coating or bar coating over a plurality of first electrodes.
  • the sacrificial layer is treated to produce an I-layer 207 (e.g., to produce a metal oxide, nitride, carbide, oxynitride, metal-C-H-O, etc.) that does not need to be patterned.
  • An unpatterned semiconductor layer 209 is deposited over the unpatterned I-layer, followed by deposition of an unpatterned second electrode 211.
  • the I-layer may be patterned after deposition (if it is deposited from a sacrificial layer) to be aligned with each two-terminal device.
  • FIG. 3 One example of a fabrication method of a two-terminal electronic device in accordance with certain embodiments of the invention is illustrated in Figure 3.
  • This example refers to an electronic device that has an I-layer formed by modification of an underlying layer.
  • the top portion of the first electrode may be modified to thereby form a metal/metal oxide, metal/metal nitride, metal/metal sulfide, metal/metal selenide or a metal/metal fluoride interface.
  • Such sequence is superior to other methods since it minimizes the amount of laborious patterning steps conventionally required for electronic device fabrication.
  • only the bottom electrode layer may need to be patterned, while the I-layer is formed conformally over the patterned bottom layer, and the semiconductor layer, and the top electrode layer is deposited as a blanket layer over several electronic devices, thereby remaining unpatterned.
  • the electronic device disclosed in provided embodiments with a pinhole-free I- layer between the bottom electrode and the semiconductor layer also has an advantage of eliminating leaking or shorting in the electronic device due to a robust coverage by the I-layer. This feature makes the devices unique over conventional devices especially for array devices comprising a large number of sensor or display elements.
  • a layer of a first conductive material is deposited onto a substrate in the first operation 301.
  • a variety of deposition methods can be used. These include PVD methods, such as sputtering, evaporation (including thermal evaporation, electron beam evaporation, sputter and the like), and photo-organic deposition methods (PODM).
  • PVD methods such as sputtering, evaporation (including thermal evaporation, electron beam evaporation, sputter and the like), and photo-organic deposition methods (PODM).
  • electroplating and electroless deposition methods can be used, where appropriate.
  • printing can be used.
  • metals such as Ti, Ta, Al etc.
  • certain metals, such as Ni can be electroplated or electrolessly deposited; while some metals, such as Ni can be printed on a substrate.
  • the conductive layer deposited on a substrate is patterned using conventional patterning methods (e.g., lithography techniques), and an I-layer is formed over at least a portion of the first conductive layer in the following operation 303, where a portion of metal is oxidized.
  • oxidation methods can be used to form the I-layer material, such as metal oxide, metal nitride, metal sulfide, metal-selenite, metal chalcogenide or metal halide.
  • a portion of the first electrode can be modified to form an insulator layer by, for example, chemical (thermal), plasma or electrochemical oxidative treatment.
  • an upper portion of the first electrode metal layer can be anodized to form metal oxide.
  • Anodization is a particularly suitable technique, since it conformally covers the first electrode metal layer with a thin layer of metal oxide, typically in a self-limiting fashion.
  • the anodization operation is typically performed by immersing a partially fabricated device structure into an anodizing solution, wherein the conductive layer of first electrode is connected to an anodizing potential source.
  • the anodizing solution typically includes an aqueous solution of an acid, such as phosphoric acid, boric acid, or citric acid. It was discovered that a salt (such as a tartrate, a citrate or a phosphate) when used instead of an acid leads to improved anodization.
  • anodizing solution may also contain ionic surfactants. According to some examples, after an anodizing potential has been applied for about an hour, a thin, pinhole-free layer of metal oxide is formed on the surface of the substrate.
  • anodization When anodization is performed on a patterned metal layer which has electrically isolated portions of metal, in order to form metal oxide over these electrically isolated portions, they need to be electrically connected.
  • a temporary removable conducting material such as silver paste is applied to the patterned metal layer of the first electrode before anodization is performed, and is removed after anodization is complete by washing the silver with a solvent, such as propyl acetate.
  • Anodization typically results in formation of metal oxide over the entire surface of the patterned metal layer, unless it was intentionally protected.
  • intentional protection of a portion of bottom electrode metal layer may be used to form a via.
  • Such a via may be used for connecting bottom electrode to a circuit.
  • Certain polymers can be used as the protection pattern during anodization and then be stripped off to form the via hole through the oxide layer. Such via holes may be used for contact pads or connection to the bottom metal electrodes when needed. Chemical oxidation
  • I-layer by oxidizing the upper portion of first electrode may be used.
  • chemical modification or modification by a plasma treatment can be used.
  • metal oxides, sulfides, oxide- nitrides or nitrides may be formed by treating the underlying metal layer with an appropriate chemical, e.g. 0 2 , H 2 S, N 2 0, N 2 or NH 3 .
  • thermal 0 2 oxidation or oxide formation by a chemical vapor treatment may be used.
  • a portion of a titanium layer can be thermally oxidized in 0 2 atmosphere to form dense, pinhole-free titanium oxide.
  • H 2 0 vapor may be used as an oxidant to form an oxide.
  • Chemical treatment in some cases may be performed by a mild solution- based process and does not necessarily involve high-temperature treatment.
  • the partially fabricated substrate can be immersed into a solution saturated with H 2 S or CS 2 used to form metal sulfides.
  • the metal may be treated with a solution of hydrogen peroxide to form a layer of oxide.
  • formation of metal nitrides such as tantalum or titanium nitrides is preferred because these materials can function as diffusion barriers between the bottom metal electrode 301 and the semiconductor layer 305 above.
  • oxidation of metal involves formation of metal halide layer from an underlying metal layer by a reaction with a halogen source.
  • metal fluoride layers can be formed by treating the metal with CF 4 or SF 6 , as a fluoride source.
  • a transparent electrode such as conductive In-O, Sn-O, In-Sn-O, Al-Zn-O
  • a thin metal layer for example, Ti, Ta, Hf, Zr
  • Ti, Ta, Hf, Zr is then formed on top and then can be oxidized completely to form the metal compound layer 303.
  • the chemical oxidation reaction may be plasma assisted.
  • metal oxides can be formed by exposing metal to a plasma with an oxygen source, e.g. 0 2 .
  • an oxygen source e.g. 0 2 .
  • tantalium/aluminum alloy oxide I-layer was prepared by exposing aluminum bottom electrode layer to an 0 2 plasma.
  • Metal nitrides can be formed by exposing the metal to a nitrogen source (e.g., N 2 0, N 2 or NH 3 ) in a plasma.
  • Metal halides can be prepared by treating the metal surface with a halide source in a plasma.
  • the resulting device When an I-layer is formed by oxidizing a portion of an underlying layer of the device by, e.g., anodization or some types of chemical treatment, the resulting device typically has an entire bottom electrode fully encapsulated in a chemically inert wide band semiconductor material. This is an advantageous feature of this method because such encapsulation prevents shorting between top and bottom electrodes of the device structure, which might otherwise occur around the edges of the bottom electrode layer.
  • the I-layer can be optionally annealed before operation305, by, for example, thermal treatment under oxygen or nitrogen ambient.
  • metal oxides formed by anodization are annealed by exposing the partially fabricated device to a temperature of about 60 - 300 °C for about 0.25 - 3 hours. Deposition of a semiconductor layer
  • a semiconductor layer is deposited over it in the operation 305.
  • the semiconductor layer is deposited by a liquid-phase method such as spin-coating, slot-coating, spray- coating, screen printing, laser transfer printing, or gravure printing. These methods are preferred when the semiconductor layer comprises organic oligomers, polymers (for example, MEH-PPV, polyalkylthiophene), composite semiconductors with an organic binder, and liquid precursors of inorganic semiconductors.
  • the semiconductor layer can also be formed by one of vacuum deposition methods including thermal vapor deposition, sputter, CVD, PECVD, atomic layer deposition and the like.
  • Organic semiconductors single molecules, dimers and trimers with molecular weight of preferably below 5xl0 4
  • Some inorganic semiconductor compounds can also be formed by thermal deposition in vacuum or with oxygen. Examples include Mo-O, and V-O.
  • Inorganic semiconductor compounds can be formed by sputtering (e.g., Cu-In-O, Cu 2 0), by CVD/PECVD or by atomic layer deposition (e.g, Cu-In-Ga-Se, Cu-In-S, Cu-In-Se).
  • amorphous selenium can be deposited by thermal deposition at low substrate temperature.
  • Hgl, PbO can be deposited by sputtering or by one of coating methods using a precursor solution. Saturation condensation can also be used when a high crystalline film is desired.
  • a second electrode layer is deposited in the operation 307.
  • the conducting material of a top electrode is deposited by a liquid-phase processing method.
  • liquid-phase processing methods include printing, coating, electroplating, electroless deposition etc.
  • Material of top electrode can be applied from a solution, a suspension, a sol-gel, or a melt.
  • the material is deposited in a patterned manner.
  • a blanket layer spanning several electronic devices in an array is formed.
  • Suitable liquid dispensing techniques include immersion, coating, droplet based printing (e.g., ink jet printing), gravure printing, silkscreen printing, thermal transfer printing, offset printing etc.
  • Coating methods include spin-coating, spray-coating, bar- coating, dip-coating, slot coating and the like.
  • the material can be formed from the liquid phase by solvent evaporation, cooling or heating of the liquid phase, chemically or electrochemically treating a precursor in the liquid phase, treating a material or its precursor in a liquid by irradiation or high temperature to cause material precipitation.
  • Specific examples include, evaporation of solvent from a printed solution of an ink, electroplating a metal, depositing a metal by electroless deposition, depositing material by cooling down a melt, etc.
  • solvents may be used to provide a liquid phase, including polar solvent such as water, alcohols, chloroform, etc., and nonpolar solvents such as toluene, xylene, etc.
  • Liquid-phase deposition may be performed in a patterned manner (e.g., printing a pattern) or conductive material can be blanket deposited.
  • the top electrode operation 307 can also be formed by one of vacuum deposition methods such as thermal deposition (e.g., for Al, Ag, Au, Mo, etc.), sputter (e.g., for Ni, Cr., Au, In-Sn-O, Sn-O, In-Zn-O) and the like.
  • thermal deposition e.g., for Al, Ag, Au, Mo, etc.
  • sputter e.g., for Ni, Cr., Au, In-Sn-O, Sn-O, In-Zn-O
  • the formation of an electronic device is complete.
  • the device may be used for a variety of purposes, e.g., as a photodetector, a photovoltaic device, or a LED.
  • the described fabrication method reduces the number of steps that require photolithographic patterning and vacuum processing as well as other steps associated with high costs in electronic diode production.
  • methods of this invention provide better control over electrical characteristics of the electronic device and expand the range of materials that can be used for fabrication.
  • FIG. 4 An alternative fabrication method is shown in the process diagram of Figure 4.
  • the process starts in 401 by forming a first electrode on a substrate, wherein the first electrode includes a layer of metal.
  • a sacrificial organometallic layer is deposited onto the first electrode in operation 403, and is then converted to the I-layer material in operation 405.
  • TiS 2 I-layer can be formed by depositing a thin sacrificial layer of Ti(OPr 1 ) 4 onto the first electrode layer, followed by converting the sacrificial layer to TiS 2 by exposing the partially fabricated device to H2S or CS2.
  • the sacrificial layer is converted to a metal oxide or partially to an M-O-C-H containing film by annealing the organometallic layer.
  • a semiconductor layer is deposited over the I-layer, followed by deposition of the second electrode layer in the operation 409, as it was previously described with reference to Figure 3.
  • the sacrificial layer can be any suitable metal- containing layer, including a metal salt, or pure metal, that is converted to an I-layer material upon treatment.
  • the diagram refers to energy levels of a device containing a cathode, an I-layer in contact with the cathode, a first semiconductor sub-layer in contact with the I-layer, a second semiconductor sub-layer in contact with the first semiconductor sub-layer, and an anode in contact with the second semiconductor sublayer.
  • the energy level of the cathode 501 (typically a bottom electrode) is higher than the energy level of the anode 509.
  • the I-layer has a wide band gap illustrated as 503.
  • the I-layer is configured for transporting electrons and blocking holes.
  • the band gap of the first semiconductor sublayer 505, that is used for photosensing or light emission is the smallest of the band gaps of the semiconductors in the device.
  • the band gap 507 of the second semiconductor sub-layer (a p-type semiconductor) is larger than the band gap 505 of the first semiconductor sub-layer.
  • the second semiconductor sub-layer is configured for transporting holes and for blocking electrons.
  • the device When the device is a light-emitting diode, higher potential is applied to the anode than to the cathode. Holes are injected into the second semiconductor sub-layer, and then to the first semiconductor sub-layer. Electrons are injected into the I-layer, and are then transferred to the first sub-layer. Recombination of holes and electrons occurs in the first sub-layer and results in light emission.
  • the blocking capacity of the I-layer and of the second semiconductor sub-layer confines the charges (holes and electrons) to the first sub-layer and leads to improved light emission efficiency.
  • no external potential is applied to the electrodes.
  • the device When the device is operated as a photodetector or photodiode, either no external potential is applied to the electrods or the potential is negative, that is higher potential is applied to the cathode than to the anode. In this instance, absorbed light generates electrons and holes in the first semiconductor sub-layer 505. Holes that are generated in the first sublayer 505 are transported to the second sublayer 507 and are collected at the anode 509. Electrons that are generated in the first semiconductor sublayer 505 are transported to the I-layer 503 and are then collected at the cathode 501.
  • the blocking capacity of the I-layer and of the second semiconductor layer prevent the charges (electrons and holes) from moving in an incorrect direction, especially at low bias.
  • the wider gap of the I-layer 503 and of the second semiconductor sub-layer 507 further also reduces dark current. It is noted that photovoltaic cells may function with a single semiconductor layer, while it is preferable to use a bi-layer semiconductor layer for the photodetectors since this configuration is particularly efficient for reducing dark current (current observed in the absence of photosignal) and improving detection of small photosignals.
  • the first electrode layer includes a layer of metal
  • the I-layer includes a layer of a metal compound made of the same metal
  • the first electrode is any conductive material (e.g., an ITO, InZnO, AlZnO or other conductive oxide)
  • the I-layer is a metal compound or an organic/inorganic blend prepared from a sacrificial layer.
  • the first electrode is a first metal
  • the I-layer is a compound of a second, different metal, prepared e.g., by complete oxidation (e.g., formation of second metal oxide, nitride, chalcogenide, or halide) of a sacrificial metal layer, deposited on a first metal layer.
  • a UV detector which has the following structure: M/MO/p-type semiconductor/TCO.
  • the metal, M is Ti, Ta, Zn, In, Sn, or Ga.
  • the I-layer is a metal oxide layer, where the oxide is formed in a self-aligned manner from the top portion of the first electrode by oxidation which can be achieved by annealing the metal in 0 2 environment, by treating the metal with 0 2 plasma, by anodization of the metal, or by heating the metal and contacting it with H 2 0 2 , or by a combination of the processes listed above In those cases where metal oxide is formed by a dry process (e.g., 0 2 plasma, heating in 0 2 - contained environment) or by a wet process (e.g., by anodization, or hydrogen peroxide treatment), the surface of the oxide may be cleaned, e.g., with a water rinse and is then dried.
  • a dry process e.g., 0 2 plasma, heating in 0 2
  • a p-type organic or inorganic layer or both in stack or in a blend form is then deposited on the clean dry surface of metal oxide.
  • organic semiconductors that can be used include TPD, NPB (e.g., deposited by thermal deposition), PFO or polymers comprising TPD or NPB group (e.g., deposited by spin-coating or slot coating).
  • inorganic p-type semiconductors that can be used include MoO, NiO, NiN and SiC which can be deposited by thermal deposition, sputter or MOCVD/PECVD.
  • TCO top-conducting-oxide
  • the onset of the photoresponse is determined by the absorption edge of the metal oxide and the semiconductor layer (also referred to as a hole transport layer, HTL). For example, when Ti0 2 is used in the I- layer and NPB is used in the semiconductor layer the response starts at approximately 400nm. When SnO is used for the I-layer and NPB is used in the semiconductor layer, the onset of response starts at ⁇ 320nm and therefore a solar-blind UV detection can be achieved.
  • the onset of photoresponse ties with the onset of interband transition or absorption edge. At this wavelength, the electron on top of the valence band is excited into the bottom of conduction band in either I-layer, or the broadband p-type semiconductor layer or both which can be extracted at the contact electrodes above and below.
  • Example UV-A a glass substrate (Corning Eagle 2000) of l"xl" was used.
  • lOOnm Ta metal layer was deposited by DC sputtering using 100 W power level at a pressure of 10 mtorr in argon environment. It was patterned by photolithography and by dry etching to form an array of patterned bottom electrodes lOmmx 1.8mm in size and separated by 0.2 mm.
  • a protection photoresist (PR) coating was then formed on the contact areas of Ta electrodes and the structure was baked at 130 °C for 10 minutes.
  • PR protection photoresist
  • Ta 2 Os_ x I-layer The surface of Ta was then oxidized by anodization to form Ta 2 Os_ x I-layer (similarly to the process used to form two terminal M-I-M switch devices described in Example 1 of US Patent No. 8,222,077 which is herein incorporated by reference in its entirety.
  • the protection PR coating was then removed with a stripper solution, and the sample was then rinsed in deionized water and was blow-dried.
  • the sample was then sent into a vacuum chamber, where a 200 nm thick Mo-0 layer was thermally deposited as the p-type semiconductor layer, and then a transparent, conductive In-Sn-0 top electrode ( ⁇ 100nm thick) was sputter deposited by a direct current (DC) source at room temperature and under argon pressure of ⁇ 10 mtorr.
  • DC direct current
  • the tantalum oxide layer is self-aligned with the bottom electrodes, and is therefore not shared by neighboring devices, while the MoO layer, and the top electrode are continuous and are shared by a plurality of devices.
  • photocurrent was observed under light illumination from top (through the ITO layer) for wavelengths shorter than 400nm with external quantum efficiency in a range of 20-50 % el/ph.
  • Example UV-B the bottom tantalum electrode was deposited, and the tantalum oxide I-layer was formed as described for the Sample UV- A but the semiconductor layer was 100 nm thick PFO layer that was spin coated at 2000 rpm, as a continuous layer spanning a plurality of devices. The PFO coating was then baked at 150 °C for 30 minute to remove solvent. The sample was then coated with a PEDOT:PSS solution with a bar-coater such that it does not contact the bottom electrode contacts. Another baking at 150 °C for 30 minutes was carried out to remove the solvent in PEDOT:PSS, where PEDOT:PSS served as the top electrode. Photosensitivity in the UV region was observed to be similar to the UV-A sample described above.
  • the substrate was a quartz plate and the bottom electrode was In-Sn-0 formed by DC sputter at lOOmW power level at room temperature.
  • a Zn-O-C-H containing film was formed in N2 environment from a precursor solution containing zinc acetate dihydrate monoethanolamine (0.5 M) and 2- methoxyethanol.
  • the solution was coated as a continuous layer shared by a plurality of devices and was then baked at 150 °C for 30 minutes in air or under N 2 environment to form a continuous layer of Zn-O-C-H.
  • a MoO semiconductor layer (a continuous layer spanning a plurality of devices) and a top ITO electrode was deposited identically to deposition of these layers in Sample UV-A.
  • a transparent UV detector was achieved with response in 200-400nm range. UV detection was achieved from both top and bottom illumination. The detector is transparent over the entire visible range.
  • Such transparent UV detector can be used as a UV index meter and can be integrated into a variety of portable electronics, such as a smart watch or a mobile phone.
  • Example 2 Broadband NIR/visible light photodetectors and photovoltaic cells When narrow energy gap semiconductor is used in the semiconductor layer, absorption is shifted to longer wavelengths. I and/or visible light photodetectors can be built. These devices can also be used as photovoltaic devices.
  • the bottom electrode layer is a metal layer.
  • the metal is Ti, Ta, Zn, In, Sn, or Ga.
  • the I-layer is a metal oxide layer, where the metal is the same metal as used for the first electrode.
  • the semiconductor layer can be organic or inorganic p-type semiconductor, or an organic/inorganic blend, or a stack. Examples of suitable materials include PPV, MEHPPV, P3HT, PCPDTBT, PDDTT, CuO, PbS, CuInSe, CuInS, CuInGaSe. Such devices can be used as single detectors but are especially suitable for detector arrays due to simplicity of their manufacturing process and high process yield.
  • the sensor pixel can be defined by the bottom metal pattern, the remaining layers can be deposited in blanket form over entire detector array, while the I-layer is formed over the patterned bottom electrode layer in self-aligned manner without lithographic process.
  • the I-layer passivates the bottom pixel electrodes from all directions (i.e., covers the top portion and side portions of a bottom electrode)
  • borosilicate glass (Corning Eagle 2000) was used as the transparent substrate.
  • 200nm thick Ta was DC sputter deposited at room temperature.
  • the Ta layer was then patterned into same patterns as in the UV-A example.
  • the tantalum oxide I-layer was then formed by anodization in the same way as described in the UV-A example. Thickness of the I- layer was chosen in this experiment to be 20 nm.
  • the semiconductor layer was then deposited either by spin-coating or thermal deposition for organic semiconductors or by RF sputter for the inorganic compounds either directly or by depositing corresponding metal oxides and converting them to sulfides and selenides.
  • Samples containing PPV, MEHPPV, P3HT, PCPDTBT, PDDTT, CuO, PbS, CuInSe, CuInS, and CuInGaSe were prepared.
  • the top electrode was then deposited.
  • the top electrode was AZO (aluminum-zinc-oxide) formed by thermal deposition in vacuum.
  • the top electrode was ITO formed by sputter deposition under argon Ar.
  • Post annealing was performed for devices with spin-coated organic semiconductors at 150 °C for 30 minutes and for devices with sputtered films at 250 °C for 60 minutes.
  • the short wavelength cut-off of the photoresponse for obtained devices is ⁇ 400nm for devices with the AZO top electrode and -300 nm for devices with the ITO top electrodes.
  • the thickness of Ta-0 layer was varied in the 10-50 nm range. Similar photoresponses as with 20 nm Ta-0 were observed. Lower dark current was observed in a device with thicker Ta-O. This fact confirms that one can tune the thickness of the I-layer to optimize overall device performance.
  • Ti-0 was used as the I-layer in similar structures. Higher forward current was observed in Ti-0 - containing device with the same I-layer thickness.
  • Example 3 Visible/near-infrared (NIR) detector array with an unpatterned semiconductor layer
  • the bottom electrode was made with a 100 nm thick ITO or a
  • Titanium oxide I-layer was formed by DC sputtering of titanium metal layer with nominal thickness of 10 or 50 Anstrong, and then the unpatterned Ti layer was oxidized to T1O 2 by thermal oxidation at 200 °C.
  • a blend polymer semiconductor comprising either PTB7:PC 70 BM or PCPDTBT:PC 70 BM (1 :2 weight ratio, purchased from 1 -Materials, Dorval, Quebec, Canada) was coated from a blend solution at room temperature over the I-layer and was then dried at 150 °C for 30 minutes to remove residual solvent. Toluene and chlorobenzene were used for as solvent for this study.
  • this layer (referred to as a sensing layer or the first semiconductor sub-layer) was approximately 200nm. It is an organic semiconductor with bulk p-n junctions in nanoscale, in which photoinduced holes transport in PCPDTBT and photoinducted electrons transport in PCBM (Gang Yu et al, SCIENCE ⁇ Vol. 270, p. 1789 (1995)). The samples were then sent into a vacuum chamber and the pressure was reduced to 5x10 ⁇ 7 torr. A MoO layer (a second semiconductor sub-layer) was then thermally deposited on top of the semiconductor polymer layer (the first semiconductor sub-layer) with thicknesses of 20, 40 and 80 nm for different samples. The formed MoO layer is a p-type semiconductor and is amorphous. It transports holes to and blocks electrons from reaching the anode on top of the device. No substrate heating was performed during MoO deposition.
  • a lOOnm Ag layer was then thermally deposited on top of the MoO as the top anode with optical reflection.
  • a cover glass sheet was glued over the array area as the final passivation step.
  • Top sensing image array was also made with a transparent top electrode.
  • a thin Ag layer (10-15nm) or a Ag/MoO blend coating layer (1 :1 ratio, 10-20nm) were used as the transparent anode.
  • a 200 nm SiOx was then thermally-deposited on top of whole active area as a thin film passivation layer.
  • Figures 6A-6B show performance data for the top sensing image array made with PCPDTBT:PC 7 oBM first semiconductor sub-layer as described above.
  • Figure 6A shows the spectral response, covering from 300nm to over lOOOnm.
  • the external quantum efficiency (EQE) is over 30% el/ph in most regions.
  • Figure 6B shows the current- voltage dependence in the dark and under light illumination.
  • the Iph-V curves were taken under 22 ⁇ W/cm 2 at 530 nm and 16 ⁇ ⁇ / ⁇ 2 at 950nm.
  • the dark current is below 0.2nA/cm 2 for bias within +/-0.3V and is below lnA in -IV to 0V range.
  • the photocurrents are 3-4 orders of magnitude higher than the dark current.
  • the corresponding peak photosensitivity was 0.18 AAV and the peak EQE was >30% el/ph.
  • the corresponding detectivity D* is ⁇ 10 13 Jones.
  • the EQE can be further improved to 60-80% el/ph.
  • Curve (a) illustrates data for a top-sensing image array.
  • Curve (b) illustrates data for a bottom-sensing image array.
  • solution processed Ti-0 or Zn-0 were used to form an unpattemed I-layer.
  • the Zn-containing precursor was prepared by dissolving zinc acetate dihydrate (Zn(CH 3 COO)22H 2 0, Aldrich, 99.9%, 1 g) and ethanolamine (NH 2 CH 2 CH 2 OH, Aldrich, 99.5%, 0.28 g) in 2- methoxyethanol (CH 3 OCH 2 CH 2 OH, Aldrich, 99.8%, 10 mL) under vigorous stirring for 12 h.
  • the Ti-contained precursor was prepared using a similar procedure, but the zinc salt was substituted for a titanium salt.
  • the Ti-containing or Zn-containing precursor solution was spin-cast onto pre-cleaned ITO for a transparent image array or onto patterned Ag layer for a top-sensing image array.
  • the sample was then annealed at 200 °C for 1 hour in air to convert the precursor into an unpattemed TiO or ZnO I-layer.
  • the semiconductor layer and the top electrode were deposited as described above for Experiment 3.
  • a readout circuit Texas Instrument, DDC264.
  • all of the layers above I-layer were covering the entire array area without pixel patterning. Accordingly, a novel image array with pixel pitch defined by bottom pixel contact pads is disclosed.
  • the only patterned layer in the device is the bottom electrode.
  • Example 4 Infrared photodetector array with onset response in short-wave infrared (SWIR) range.
  • SWIR short-wave infrared
  • the photodetector array was formed as described in the Example 3 but the un-patterned blend semiconductor layer (first semiconductor sublayer) was made with PCPDTBT as a binder with added nano particle PbSe (PbSe:NP) as a photosensitizer.
  • Linear array was prepared following a procedure that is similar to the one described in Example 3. Onset of photoresponse at 2200 nm was observed.
  • Table 2 lists arrays of photodetectors (their structure and properties) prepared as described in Example 3 and Example 4. Table 2. Photodetector arrays prepared by the methods described in Examples 3 and 4.
  • Two dimensional sensor array can be manufactured by integrating the photodiode arrays on top of a read out integrated circuit (ROIC) made on Si wafer. It can also be built with readout circuit made with thin film transistor (TFT) on a glass or a plastic substrate.
  • the channel material of the TFT array can be low temperature polysilicon, metal-oxide semiconductor film, II-VI compound semiconductor film such as CdSe, a-Si film or an organic semiconductor film.
  • a 220x220 image array of photosensors was prepared.
  • the photodetectors had the structure shown in Table 2 for the sample, in which PDDTT:PCBM polymer blend was used as the semiconductor sensing layer (first semiconductor sub-layer).
  • An image readout circuit was constructed with metal-oxide TFT (MOTFT) on glass substrate.
  • MOTFT metal-oxide TFT
  • the photoresponse of the array was in a range of 300 to 1400nm.
  • the array was built with a pixel pitch of 50 ⁇ and had an active area of 11mm x 11mm. Only the bottom electrodes were patterned to each pixel pitch and defined the size of the sensing element.
  • the aperture ratio (the area of the sensing element to total pixel pitch area) was ⁇ 80%.
  • the semiconductor sensing layer (first semiconductor sub-layer), the MoO hole transport layer (second semiconductor sublayer) and the top electrode layer were all formed continuously over entire array area.
  • the image readout follows conventional line-scan operation row by row.
  • a commercial gate driver chip was used as the scan driver and two pieces of commercial ROIC (readout integration circuit) chips (Flir 9717) were used as data readout chip.
  • the digital image signals were sent to an image processor and showed over a computer monitor. High quality images with 50 ⁇ special resolution, and with dynamic range over 214 was observed.
  • Image arrays were also made with the same 220x220 image readout array and with the sensing layer (first semiconductor sub-layer) replaced with PCPDTBT:PCBM, and with CuInSe .
  • Example 6 X-ray detector
  • X-ray photodetector array Large size X-ray photodetector array was prepared by placing a commercially available X-ray scintillator sheet on top of the top-sensing two dimensional visible image array.
  • a 4" diagonal MOTFT pixel readout array was designed in 320x240 format with pixel pitch of 255 ⁇ .
  • CdS:I was used as the X-ray phosphor. Its emission profile extends in 400-620 nm range, matching well with the spectral response of PTB7:PCBM and P3HT:PCBM.
  • the top metal layer used for MOTFT source/drain electrode Mo/Al/Mo stack was used directly for the bottom electrode material.
  • the I-layer was formed by spin-coating a Zn-containing precursor solution over the patterned pixel electrodes (cathodes).
  • the dried zinc precursor film was converted into ZnO layer after annealing at 200 °C for 1 hour.
  • the polymer blend layer (first semiconductor sub-layer) was then coated over the ZnO I- layer and was heated to 1 0 °C for 1 hour to remove solvent.
  • Inorganic hole transport layer (HTL) MoO was used as p-type semiconductor layer (second semiconductor sub- layer) and finally, transparent AlZnO or ITO was sputter deposited over the array as the top common anode electrode. 200 nm thick MoO was then deposited as a thin-film passivation layer over the top anode.
  • the CdS:I X-ray phorsphor sheet was then placed over the sensing array.
  • X-ray beam contacts the free surface (top) of the CdS:I
  • visible light emission occurs with emission intensity proportional to the incident X-ray photon density.
  • the visible image is detected by the visible image arrays located underneath the X-ray phosphor.
  • Photocurrent corresponding to emission intensity from CdS:I sheet is read out row by row and the analog current signal is converted into digital signal and transferred into image frame buffer in the image processor and displayed over the computer monitor.
  • Direct X-ray photosensor can also be made. In this case, the photosensor layer
  • first semiconductor sub-layer is replaced with either 300 ⁇ thick amorphous selenium formed by thermal deposition, or a 300 ⁇ thick PS:HgI (1 :9 weight ratio) blend layer.
  • PS:HgI 1 :9 weight ratio
  • This example includes a series of experiments listed below.
  • ITO was used as the transparent bottom electrode.
  • a thin ZnO layer was used as the I-layer and was formed over ITO by coating a zinc oxide nanoparticle film that was baked at 90 °C for 1 hour.
  • the I-layer serves as an electron injection and transport layer in the light emitting device.
  • an organic layer which functioned as carrier transporting and light emission layer was thermally deposited in a vacuum chamber.
  • the thin emission layer (first semiconductor sublayer) contained a blend of mCP:FIrpic (93:7 weight ratio) with thickness of 10-30 nm.
  • a p-type inorganic semiconductor MoO layer (20-8 Onm) was then thermally deposited over the emission layer and served as a hole transport and electron blocking layer (second semiconductor sub-layer).
  • a lOOnm thick Ag or Al metal layer was thermally deposited over the MoO layer as the top electrode (anode).
  • a high efficiency, bottom emission, blue phosphorescent OLED was achieved.
  • the inorganic p-type MoO layer was replaced with an organic NPB layer with thickness in range of 20-80nm. Similar performance was observed.
  • zinc oxide I-layer was formed by means of oxygen plasma reaction or direct heating in O2 atmosphere at 200 °C over the zinc bottom electrode.
  • a transparent top electrode (Ag:MoO with 1 :1 ratio, 20nm) was used in this example and thereby a top-emission OLED was achieved.
  • Other deposited layers (first and second semiconductor sub-layers) were the same as in the bottom emission OLED described above.
  • alumina precursor was deposited on patterned ITO surface by spin-coating and was converted to AI2O 3 after heating at 200 °C in air.
  • Al-containing precursors that are suitable for such deposition are described in J. Mater. Chem. C, 2014, 2, 864, which is herein incorporated by reference in its entirety
  • This alumina layer functions as the I-layer.
  • Semiconductor layer 1 which functions as light emission layer included organic molecule Alq (20nm) or molecular blend CBP:Irppy3 ( ⁇ 20nm). These were deposited by thermal deposition in vacuum with base pressure below 3x10 ⁇ 7 torr. The following layers were the same as that used in experiment 1. Both fluorescent and phosphorescent OLED devices were fabricated.
  • the I-layer was replaced with a thin Ta-Al or Zr-Al alloy ( ⁇ 5nm) which was deposited by co-sputter with the corresponding metal targets, and was then thermally oxidized to Ta 2 05-x-Al 2 03_y or Zr0 2 - X -Al 2 03_ y layer by annealing at temperature above 200 °C. Green emission was observed when biasing such devices in forward bias over 3V.
  • the Alq emission molecule was replaced with Balq.
  • the other layers were not changed. Blue light emission was observed under forward bias larger than 3V.
  • ITO was used as the bottom electrode.
  • Zirconia was used as the I-layer and was formed by spin-coating a zirconium -containing precursor solution followed by heating under oxygen ambient at 250 °C.
  • the ZrO I-layer serves as electron injection/transport layer as well as hole blocking layer.
  • PFO-based blue, green or red emission polymers were then spin-coated from their chlorobenzene solutions.
  • the PFO-based layer served as the first semiconductor sublayer.
  • MoO or NPB were used as the p-type second semiconductor sublayer.
  • lOOnm Ag was used as the top electrode.
  • Bottom emission organic light emitting devices were formed with emission color in red, green and blue colors in visible spectral range
  • a top emission device was also fabricated with a ZrAl metal alloy layer used as the bottom electrode. The surface was oxidized by oxygen plasma followed by baking at 200 °C. In this case, transparent top electrode was made with 20nm Ag:MoO blend layer with (1 :1) weight ratio. A 80nm MoO layer were deposited on top of second electrode as thin film passivation. Other layers were the same as described above.
  • ZnO was used as the I-layer and was formed from Zn- containing precursor solution. Red, green and blue LEDs were achieved with CdSe quantum dots (QD) layer as the first semiconductor sublayer. It was formed by slot- coating or dip-coating of the QD solution, followed by a soft baking at 120 °C to remove solvents. MoO or NPB was used as the second semiconductor sublayer and served as hole transport and electron blocker. It was observed that the ZnO I-layer provided sufficient electron injection, and light emission occurs at forward voltage right above the corresponding optical photon energies.
  • QD CdSe quantum dots
  • the bottom electrode and the I-layer were replaced with Ti/TiO or Ta/TaO formed with surface oxidation and used as the first electrode/I-layer.
  • the two semiconductor layers were kept without change.
  • 20nm Ag:MoO (1 :1 weight ratio) was used as a transparent top electrode.
  • Top emission LEDs were achieved with similar operation voltage and emission efficiency.
  • mCP isl,3-Di(9H-carbazol-9-yl)benzene, 9,9'-(l,3-Phenylene)bis-9H-carbazole, ⁇ , ⁇ '- Dicarbazolyl-3, 5 -benzene
  • FIrpic is Bis[2-(4,6-difluorophenyl)pyridinato-C2,N](picolinato)iridium(III)
  • Alq isTris-(8-hydroxyquinoline)aluminum
  • BAlq is Bis(2-methyl-8-quinolinolato-N 1 ,08)-(l , 1 '-Biphenyl-4-olato)aluminum
  • CBP is 4,4'-Bis(N-carbazolyl)-l,l'-biphenyl
  • Irppy3 is Tris[2-phenylpyridinato-C2,N]iridium(III)
  • oxides, sulfides and other chalcogenides mentioned in this application need not necessarily be interpreted as stoichiometric.
  • MoO, MoOx and M0O 3 may refer to the same compound.
  • High pixel density emissive displays can be made with the bottom cathode light emitters shown in this example. It is noted that such bottom cathode light emitting devices are particularly suitable for active matrix displays with n-type metal-oxide TFT. Similarly to that in image array devices, only the bottom electrode needs to be patterned to pixel level, while the other layers can be formed with coating over the entire display area.

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Electroluminescent Light Sources (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Light Receiving Elements (AREA)

Abstract

La présente invention concerne des dispositifs électroniques à deux bornes, tels que des photodétecteurs, des dispositifs photovoltaïques et des dispositifs électroluminescents. Les dispositifs comportent : une première électrode placée sur un substrat, la première électrode comprenant une couche de métal; une couche I comprenant un matériau isolant non organique ou semi-conducteur large bande placé au sommet de la première électrode et aligné avec la première électrode, le matériau isolant non organique ou semi-conducteur large bande étant un composant du métal de la première électrode; une couche semi-conductrice, comprenant de préférence un semi-conducteur de type P, placé sur la couche I; et une seconde électrode placée sur la couche semi-conductrice, l'électrode comprenant une couche d'un matériau conducteur. La bande interdite du matériau de la couche semi-conductrice est de préférence plus petite que la bande interdite du matériau de la couche I. La bande interdite du matériau de la couche I est de préférence supérieure à 2,5 eV.
PCT/US2015/040815 2014-07-23 2015-07-16 Dispositifs électroniques à deux bornes et leurs procédés de fabrication WO2016014345A2 (fr)

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WO2018234878A1 (fr) * 2017-06-23 2018-12-27 King Abdullah University Of Science And Technology Couches de blocage de trous pour dispositifs électroniques et procédé de production d'un dispositif électronique ayant une couche de blocage de trous
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Publication number Priority date Publication date Assignee Title
US9741901B2 (en) 2006-11-07 2017-08-22 Cbrite Inc. Two-terminal electronic devices and their methods of fabrication
EP3389103A1 (fr) * 2017-04-10 2018-10-17 Panasonic Intellectual Property Management Co., Ltd. Dispositif d'imagerie
CN108695356A (zh) * 2017-04-10 2018-10-23 松下知识产权经营株式会社 摄像装置
JP2018182314A (ja) * 2017-04-10 2018-11-15 パナソニックＩｐマネジメント株式会社 撮像装置
US10461130B2 (en) 2017-04-10 2019-10-29 Panasonic Intellectual Property Management Co., Ltd. Image device including photoelectric conversion layer
US10707272B2 (en) 2017-04-10 2020-07-07 Panasonic Intellectual Property Management Co., Ltd. Imaging device including photoelectric conversion layer
US11081528B2 (en) 2017-04-10 2021-08-03 Panasonic Intellectual Property Management Co., Ltd. Imaging device including photoelectric conversion layer
JP7249548B2 (ja) 2017-04-10 2023-03-31 パナソニックＩｐマネジメント株式会社 撮像装置
CN110770910A (zh) * 2017-04-20 2020-02-07 爱色乐居 包括有机光电二极管的辐射检测装置
WO2018234878A1 (fr) * 2017-06-23 2018-12-27 King Abdullah University Of Science And Technology Couches de blocage de trous pour dispositifs électroniques et procédé de production d'un dispositif électronique ayant une couche de blocage de trous
CN111490176A (zh) * 2019-01-28 2020-08-04 武汉华星光电半导体显示技术有限公司 一种显示面板及其制备方法、电子装置
CN111490176B (zh) * 2019-01-28 2022-08-02 武汉华星光电半导体显示技术有限公司 一种显示面板及其制备方法、电子装置

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