EP2115788A2 - Structure de dispositif à semi-conducteurs - Google Patents

Structure de dispositif à semi-conducteurs

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Publication number
EP2115788A2
EP2115788A2 EP08715844A EP08715844A EP2115788A2 EP 2115788 A2 EP2115788 A2 EP 2115788A2 EP 08715844 A EP08715844 A EP 08715844A EP 08715844 A EP08715844 A EP 08715844A EP 2115788 A2 EP2115788 A2 EP 2115788A2
Authority
EP
European Patent Office
Prior art keywords
layer
device structure
charge
structure according
charge transport
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08715844A
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German (de)
English (en)
Inventor
Michael Graetzel
Henry James Snaith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ETeCH AG
Original Assignee
ETeCH AG
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Filing date
Publication date
Application filed by ETeCH AG filed Critical ETeCH AG
Publication of EP2115788A2 publication Critical patent/EP2115788A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/112—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor
    • H01L31/1127—Devices with PN heterojunction gate
    • H01L31/1129—Devices with PN heterojunction gate the device being a field-effect phototransistor

Definitions

  • the invention relates to a novel detector device structure having an organic device concept, capitalizing on knowledge from both the photovoltaic cell and the field effect transistor.
  • This hybrid "photo gated" detector comprises of an inorganic capacitive layer, a molecular sensitizing layer and an organic charge transport layer, caped with in- plane gold electrodes defining an active channel. Under illumination, the sensitizer injects an electron in the capacitive layer, constituted by a wide band gap inorganic oxide of mesoscopic morphology, while the resulting positive charge is transferred to the hole-transporter.
  • the increased hole density results in vastly enhanced film conductivity and charge carrier mobility.
  • a molecular sensitizer layer as the photoactive material, which is located at the interface between a capacitive "electron reservoir” and a hole transporting material (HTM).
  • HTM hole transporting material
  • the sensitizer Upon light excitation the sensitizer injects an electron in to the capacitive component and is subsequently regenerated with hole transfer to the HTM, both events are completed within nanoseconds.
  • the increased hole density in the hole-transporter results in up to 10 6 enhancement in conductivity at low temperature and 10 4 at room temperature.
  • the device demonstrates a novel organic device concept, capitalizing on knowledge from both the photovoltaic cell and the field effect transistor.
  • This hybrid "photo gated" detector comprises an inorganic capacitive layer, a molecular sensitizing layer and an organic charge transport layer, caped with in-plane gold electrodes defining an active channel. Under illumination, the sensitizer injects an electron in the capacitive layer, constituted by a wide band gap inorganic oxide of mesoscopic morphology, while the resulting positive charge is transferred to the hole-transporter.
  • the increased hole density results in vastly enhanced film conductivity and charge carrier mobility. Strikingly high light/dark current ratios of up to 10 6 at low temperature and 10 4 at room temperature are observed corresponding to mobility enhancements of up to 10 3 . This not only presents a new method for estimating mobility in organic materials but also offers a broad range of sensing and memory applications.
  • Fig. Ia Chemical structure of the sensitizing dye (termed K68) and the molecular hole-transporter.
  • Fig. Ib Schematic illustration of the photo gated detector.
  • Fig. 2a Conductivity of the film versus white light illumination intensity (I) at
  • Fig. 2b Normalized incident-photon to collected electron action spectra for the same PGD as measured in (a) (open circles) and absorption spectrum of a 1 ⁇ m thick film of nanoporous TiO 2 sensitized with "K68" dye (solid- squares).
  • Fig. 2c The calculated charge carrier mobility as a function of illumination intensity (bottom axis) and charge density (top axis).
  • the inset shows the charge recombination rate constant for a diode fabricated with an identical active layer to that of the PGD, measured by a transient open- circuit voltage decay technique.
  • Fig. 2d Transient response of the PGD to a light pulse.
  • Fig. 3 Scheme for the charge generation and "trap-filing" processes occurring at the dye-sensitized heterojunction.
  • Fig. 4 Arrhenius plot of conductivity versus temperature for the photo gated detector over a range of illumination intensity.
  • Fig. 5 A schematic view of a device structure according to an embodiment of the invention.
  • FIG. 6 A schematic view of a device structure according to another embodiment of the invention.
  • the active layer is similar to that in the solid-state dye-sensitized solar cell (SDSC), as disclosed in U. Bach, D. Lupo, P. Comte, et al., Nature 395, 583 (1998).
  • SDSC solid-state dye-sensitized solar cell
  • Such a solid- state DSC is known from US 6,335,480. It comprises of a glass slide coated with a 1 ⁇ m thick mesoporous film of TiO 2 nanoparticles (a capacitive component).
  • This film is coated with dye molecules to act as an optical sensitizer, and infiltrated with a molecular hole transporting material (HTM), 4,4":4"',4""-ter-N,N-diphenyl[4- (methoxymethyl)phenyl] amine (ter-DPMMPA) (Avecia).
  • HTM molecular hole transporting material
  • ter-DPMMPA 4,4":4"',4""-ter-N,N-diphenyl[4- (methoxymethyl)phenyl] amine
  • the TiO 2 acts as a capacitive layer allowing a large charge density to build-up within the HTM.
  • the hole density in the HTM controls the charge mobility.
  • the average TiO 2 particle size is 19 nm and the nanoporous film has a 60 % porosity.
  • Fig. 2a we present data for the film conductivity versus illumination intensity (white light diode source: Lumiled Model LXHL-NWE8 whitestar) at room temperature and at 215 K. We note that the points at an intensity of 0.02 mWcm "2 are taken in the dark and placed at this point to fit on the logarithmic axis). The light was incident from the electrode side (top), though we note that the illumination direction made negligible difference to the measured currents. We observe approximately four orders of magnitude increased conductivity at room temperature over the intensity range studied, demonstrating a highly sensitive response to light.
  • illumination intensity white light diode source: Lumiled Model LXHL-NWE8 whitestar
  • the device has been biased with a 9 V battery and connected in series with a 1 M ⁇ resistor, with the voltage across the resistor recorded on an oscilloscope.
  • a fast silicon diode was exposed to the pulse simultaneously, with the voltage generated also recorded on the oscilloscope.
  • the rise and fall time (time to rise/fall to l/exp(l) of the final/initial value) of the light source is approximately 140 ⁇ s.
  • the rise and fall times for the PGD signal are 230 and 210 ⁇ s respectively.
  • the PGD was exposed to light pulses from a white light diode source.
  • the voltage drop across the resistor was measured on an oscilloscope, from which the current was calculated.
  • the inset shows the response to a series of light pulses.
  • the mechanism which we propose for the device operation is largely based upon the photovoltaic process in the solid-state dye-sensitized solar cell and the current knowledge of charge transport in disordered organic semiconductors.
  • Light is absorbed in the sensitizing molecules with subsequent rapid (femtosecond) electron transfer in to the conduction band (CB) of the TiO 2 nanoparticles.
  • CB conduction band
  • the hole is then transferred to the hole-transporter (on a nanosecond to microsecond timescale). 13
  • the solid-state dye- sensitized solar cell not the PGD
  • following charge generation the hole migrates to and is collected at the cathode and the electron to the anode.
  • Fig. 3 This process is represented diagrammatically in Fig. 3.
  • the energy levels for the materials used are also shown there (from vacuum).
  • the highest occupied molecular orbital (HOMO) energy level of the hole-transporter is approximately -5.0 eV with respect to vacuum (measured by cyclic voltammetry).
  • the density-of states (DOS) in the HOMO level is depicted as a Gaussian, the energetic spread has been exaggerated for clarity.
  • Electrons and holes are represented by filled and empty circles respectively and the dashes in the HOMO level represent available sites for holes.
  • E 1 is the energy region in which charge transport can easily occur due to an abundance of states.
  • the sensitivity of the device will depend strongly upon the nature of the density-of- states (DOS) in the hole-transporter, with a narrower tail to the DOS giving a larger light/dark current ratio.
  • the sensitivity will also be directly related to the charge recombination lifetime, with a larger steady state charge density possible if the recombination is suppressed. This can be envisioned to be achieved by having further capacitive layers in contact with the TiO 2 which are "down hill” in energy for the electrons. A charge “cascade” will then further separate the electrons and holes, reducing recombination in a similar way to that employed in natural photosynthesis. We do note that this will slow down the response of the device, however if the charges are suitably separated such that the device remains "on” for a sufficiently long period of time, then this device concept functions as a light driven short-term memory application.
  • a charge density dependent mobility has been difficult to observe experimentally in space-charge limited diodes due to the filed dependence and the charge density dependence simultaneously increasing with applied bias.
  • Field effect transistors generally operate at much higher charge densities, of greater than 10 18 cm “3 , due to the charges being confined to a thin accumulation layer, making it difficult to study the low charge density regime.
  • Electrochemical doping of materials adds further complications due to the added dopant impurities.
  • the PGD presents a new and "clean" method for estimating charge carrier mobility in hybrid and organic composites, directly applicable to analyzing materials for photovoltaic applications. Our findings clearly demonstrate that a charge density dependent mobility should be considered when analyzing organic materials under photovoltaic operation.
  • this hybrid dye-sensitized photo gated detector can perform as a very sensitive and fast photodetector.
  • the dye-sensitized functionality enables the responsive region of the spectrum to be finely tuned by choosing the desired dye.
  • this PGD can be made sensitive to x-rays by using heavy metal nanoparticles as the sensitizing component.
  • the PDG is therefore useful in applications of low cost large area medical imaging. It can also be used as a memory device, by introducing further capacitive layers to significantly enhance the "on time”. Further to the broad range of applications, this device presents a very "clean" system to study the effects of photo-injected charges upon the charge transport in organic semiconductors, and a novel method for estimating charge carrier mobility in such materials.
  • FIG. 5 The basic structure of an embodiment of the device of the invention is shown in Fig. 5.
  • Such a structure comprises a capacitive layer 15, a charge transport layer 10 and a sensitizer layer 14, the latter being situated at the interface of the two formers.
  • the capacitive layer 15 may be made of an n-type material and the charge transporter of a p- type material, or vice versa, respectively.
  • Incoming photons (not shown) will separate an electron from the sensitizer 14 and eject it to the n-type layer, with a hole being generated simultaneously in the p-type layer.
  • the charge generated in the charge transport layer 10 will modify the conductivity of the same, thus giving rise to the device applications mentioned in the claims.
  • An "in-plane” device structure according to the embodiment shown in Fig. 6 comprises electrodes 11, 12 which inject and collect charge which are symetrically contacting a charge transport layer 10, which is in contact with a sensitizer layer 14 and a capacitive layer 15, said sensitizer layer 14 being located at the interface between the capacitive layer 15 and the charge transport layer 10.
  • Said electrodes 11, 12 can be fabricated from metal, conducting metal oxides, conducting semiconductor or conducting polymers.
  • Such a device having non mesoscopic junctions i.e. planar device structures is illustrated in Fig 6. Therefore said material layers (capacitive, sensitizer and hole- transporter) comprise of flat, planar material layers.
  • the charge transport layer can be an organic charge transport layer 10, especially comprising a molecular, oligomeric or polymeric charge transport material.
  • it comprises an organic hole or electron transporting material.
  • Organic hole or electron transporting materials may be selected from acetylene, benzene, napthaline, indene, fluorene, phenantrene, anthracene, triphenylene, pyrene, pentalene, indene, azulene, heptalene, biphenylene, indacene, phenalene, acenaphtene, fluoranthene, pyridine, pyrimidine, pyridazine, perylene, quinolizidine, quinoline, isoquinoline, quinoxaline, phtalazine, naphthyridine, quinazoline, fullerene, phtalocyanine, cinnoline, pteridine, indolizine, indole, isoin
  • organic charge transport material can generally be used in an n-type or p-type mode depending upon which carrier is injected (see: Chua Nature 2005, Zaumseil Nat Matter 2006).
  • the capacitive layer 10 may comprise an organic, capacitive material.
  • the capacitive layer comprises materials selected from organic electron or hole storing materials (n-layer or p-layer).
  • the capacitive layer comprises materials selected from acetylene, benzol, napthaline, indene, fluorene, phenantrene, anthracene, triphenylene, pyrene, pentalene, indene, azulene, heptalene, biphenylene, indacene, phenalene, phthalocyanine, acenaphtene, fluoranthene, fullerene, pyrimidine, pyridazine, perylene, quinolizidine, quinoline, isoquinoline, quinoxaline, phtalazine, naphthyridine, quinazoline, cinnoline, pteridine, indolizine, indole, isoindole, carbazole,
  • the capacitive layer 10 may comprise an inorganic, capacitive material.
  • the capacitive layer comprises materials selected from inorganic electron storing materials (n-layer), such as Si, TiO 2 , SnO 2 , Fe 2 O 3 , WO 3 , ZnO, Nb 2 O 5 , CdS, CdSe, CdTe, ZnS, PbS, PbSe, Bi 2 S 3 , GaP, InP, GaAs, CuInS 2 , and/or CuInSe 2 or from hole storing materials (p-layer), such as SiC, CdTe, CuI, CuSCN.
  • n-layer inorganic electron storing materials
  • p-layer such as SiC, CdTe, CuI, CuSCN.
  • the capacitive layer 15 is an p-layer, or, when the charge transporting layer 10 is an hole transporting layer (p-layer), the capacitive layer 15 is an n-layer.
  • the charge transporting layer is a p-layer and the capacitive layer is an n-layer.
  • the device according to the invention allows to provide a method for estimating or studying charge carrier mobility in organic semiconducters and in particular hybrid and organic composites. Such a method then comprises the steps of:
  • the device structure according to the invention can also be applied for analyzing materials for photo-voltaic devices, or suitable for light driven short-term memory applications, or having application in low cost large area medical imaging.
  • the device structure according to the invention can have the charge transport layer (i) or the capacitive layer (ii) acting as the sensitizer, said sensitizer thus not being separate from (i) or (ii), but being integrated in one of them.
  • the sensitizer layer 14 is located at the interface between the capacitive layer 15 and the charge transport layer 10, which also may encompass the situation of incorporating one or the other layer as intregal part.
  • Molecular sensitizers can be dyes, metal organic complexes, organic sensitizers, incorporating a surface attachment group such as carboxilic acid, or phosphonic acid, for example.
  • Molecular metal complex sensitizers can be found in US 5,463,057.
  • Polymeric sensitizers comprise sensitizer made of poly phenylene vinylene, poly thiothene, poly fluorene, poly acetylene, poly perylene, and derivatives thereof.
  • Quantum dot sensitizer, for example PbS or CdSe nanoparticles as well as inorganic sensitizers are described in "Solid state heterojunction and solid state sensitized photovoltaic cell" US 2002/017656.
  • a thin layer of a semicondutor for example Si, CuO, CdTe or PbSe capable of injecting one charge carrier in the capacitve charge storage layer and the oppositely charged carrier in the charge transport layer, can also be used as sensitizer as well as ruthenium sensitizers.

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Light Receiving Elements (AREA)
  • Testing Or Measuring Of Semiconductors Or The Like (AREA)

Abstract

L'invention concerne une structure de dispositif à semi-conducteurs qui présente un nouveau concept de dispositif organique, s'appuyant sur les connaissances aussi bien de la cellule photovoltaïque que du transistor à effet de champ. Le détecteur 'photo-porte' hybride comprend une couche capacitive inorganique, une couche sensible moléculaire et une couche de transport de charge organique, coiffées par des électrodes en or dans le plan définissant un canal actif. En éclairage, le sensibilisateur injecte un électron dans la couche capacitive constituée par un oxyde inorganique à large bande interdite de morphologie mésoscopique, tandis que la charge positive résultante est transférée au transporteur de trous. La densité de trous accrue produit une conductivité de film et une mobilité de porteurs de charge largement renforcées. On observe des rapports de courant faible/noir étonnement élevés jusqu'à 106 à basse température et 104 à température ambiante correspondant à des renforcements de mobilité jusqu'à 103. Il s'agit là non seulement d'un nouveau procédé pour estimer la mobilité dans des matériaux organiques, mais aussi d'une large gamme d'applications de détection et de mémoire.
EP08715844A 2007-02-16 2008-02-18 Structure de dispositif à semi-conducteurs Withdrawn EP2115788A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US90174707P 2007-02-16 2007-02-16
PCT/EP2008/001248 WO2008098797A2 (fr) 2007-02-16 2008-02-18 Structure de dispositif à semi-conducteurs

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EP2115788A2 true EP2115788A2 (fr) 2009-11-11

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GB0909818D0 (en) 2009-06-08 2009-07-22 Isis Innovation Device
CN105280817B (zh) 2014-07-16 2017-11-07 财团法人工业技术研究院 太阳能电池与其形成方法
CN105552131B (zh) * 2016-01-27 2018-12-14 东南大学 基于量子点掺杂栅绝缘层的光调制薄膜晶体管
CN105854899B (zh) * 2016-05-31 2019-01-04 枣庄学院 一种Bi2S3/TiO2复合型可见光催化剂及其制备方法
US11164988B2 (en) * 2017-02-07 2021-11-02 The Governing Council Of The University Of Toronto Photovoltage Field-Effect Transistor
CN109742165A (zh) * 2019-01-02 2019-05-10 南京大学 一种基于二维层状材料的雪崩光电探测器及探测系统
CN114242921B (zh) * 2021-12-09 2024-02-20 广东省科学院半导体研究所 一种发光场效应晶体管及其制备方法

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EP1176646A1 (fr) * 2000-07-28 2002-01-30 Ecole Polytechnique Féderale de Lausanne (EPFL) Hétérojonction à l'état solide et cellule photovoltaique sensibilisé à l'état solide
KR100624413B1 (ko) * 2003-10-21 2006-09-18 삼성전자주식회사 수발광 소자 및 그 제조 방법
US7592539B2 (en) * 2003-11-07 2009-09-22 The Trustees Of Princeton University Solid state photosensitive devices which employ isolated photosynthetic complexes
GB2429837A (en) * 2005-07-25 2007-03-07 Kontrakt Technology Ltd Organic photovoltaic device comprising polycrystalline discotic liquid crystal

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WO2008098797A2 (fr) 2008-08-21

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