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WO2016015077A1 - Capteur infrarouge optoélectronique - Google Patents

Capteur infrarouge optoélectronique Download PDF

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Publication number
WO2016015077A1
WO2016015077A1 PCT/AT2015/050182 AT2015050182W WO2016015077A1 WO 2016015077 A1 WO2016015077 A1 WO 2016015077A1 AT 2015050182 W AT2015050182 W AT 2015050182W WO 2016015077 A1 WO2016015077 A1 WO 2016015077A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
silicon
organic semiconductor
infrared sensor
semiconductor layer
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.)
Ceased
Application number
PCT/AT2015/050182
Other languages
German (de)
English (en)
Inventor
Niyazi Serdar Sariciftci
Vedran DEREK
Eric Daniel GLOWACKI
Mile IVANDA
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.)
Universitaet Linz
Original Assignee
Universitaet Linz
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Filing date
Publication date
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Publication of WO2016015077A1 publication Critical patent/WO2016015077A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
    • H10F77/148—Shapes of potential barriers
    • 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
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • H10K30/352—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles the inorganic nanostructures being nanotubes or nanowires, e.g. CdTe nanotubes in P3HT polymer
    • 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 an optoelectronic infrared sensor with two each connected to an electrode, a heterojunction forming semiconductor layers, namely a silicon layer and an organic semiconductor layer on the silicon layer.
  • Infrared sensors are major components in many optoelectronic devices used in telecommunications, sensor technology and image technology. Near-infrared sensors are commonly fabricated using low-band-gap semiconductors, with indium gallium arsenide prevalent in most applications, although the toxicity of the starting materials and integration into silicon-based microelectronics leads to difficulties. Silicon-based near-infrared sensors would therefore represent an advantageous alternative to infrared indium gallium arsenide sensors. Many attempts have therefore been made to provide near-infrared sensors based on silicon, but the known infrared sensors of this type could not compete with the sensors based on indium gallium arsenide due to various disadvantages.
  • 09/023881 A1 which have an inorganic semiconductor layer forming a heterojunction with an organic semiconductor layer, wherein the inorganic semiconductor layer preferably consists of a p-doped silicon layer which, with a semiconductor layer based on a fullerene, forms the heterojunction forms.
  • a disadvantage of these known infrared sensors is that the two semiconductor layers must be cooled. With increasing cooling, the photocurrent based on absorption of the infrared radiation increases and can be used to detect infrared radiation. Infrared sensors for the near infrared range have also been proposed (Mateusz Bednorz, Gebhard J. Matt, Eric D. Glowacki, Thomas Fromherz, Christoph J. Brabec, Markus C.
  • the achievable increase in performance depends in particular on the structure of the nanowire field and the upper contact points between the nanowire field and the organic semiconductor layer and is attributed on the one hand to the scattered by the wire structure light scattering and thereby improved light absorption and on the other hand to the new contact points.
  • low charge carrier mobility and thus overall poor electrical properties result.
  • the invention is thus based on the object, an optoelectronic infrared sensor with a heterojunction between a silicon layer and an organic semiconductor layer in such a way that a high sensitivity for a caused by a near infrared radiation photocurrent can be ensured without having to make a cooling of the semiconductor layers.
  • the invention achieves the stated object in that the organic semiconductor layer is provided on a nanostructured and / or microstructured surface layer of the silicon layer and covers it over its entire area.
  • the heterojunction resulting boundary layer between the inorganic and organic semiconductor layers is increased by the nano- and / or microstructure of the silicon layer accommodating the organic semiconductor layer, this interfacial increase can be compared to the detectable increase in the sensitivity of an infrared sensor according to the invention by ten to five hundred times to known infrared sensors with a un-structured interface between the inorganic and organic semiconductor layers and the functionality of the infrared sensors according to the invention also at room temperature do not explain, especially since these effects are not observed in an n-doped silicon layer.
  • the organic semiconductor layer is the structured surface of the silicon layer while maintaining a largely constant
  • Suitable organic semiconductor layers are molecular or polymeric organic semiconductors, the polarity of their majority charge carriers having to be negative.
  • Preferred semiconductor materials are organic molecules which have good stability due to hydrogen bonds. Due to the chemical and operational stability of such organic semiconductors given by the hydrogen bonds, the prerequisite for many different applications is created.
  • R 1, R 2 is H, an alkyl, alkoxyl, aryl or an aryloxyl group
  • R 3 , R 4 is a halogen, an alkyl or alkoxy group or an aromatic
  • R 5 indicates an alkyl or alkoxy group or an aromatic group such as phenyl or thienyl substituent.
  • a p-doped, momokristallines, but also polycrystalline silicon can be used for the silicon layer.
  • the nanostructure of the surface layer of the silicon layer can be produced by a chemical or electrochemical etching process in a manner known per se. Microstructures can be obtained by expanding the pores of a nanostructure by a subsequent chemical etching step or the formation of micropyramids by means of anisotropic etching. Particularly favorable conditions for structuring can be achieved when using a silicon having a ⁇ 100> or a ⁇ 1 1 1> orientation, because the etching processes are carried out using appropriate etching methods ⁇ 1 1 1> crystal facets of silicon are selectively released to form a pyramidal pattern.
  • Fig. 1 an optoelectronic infrared sensor according to the invention in one
  • FIG. 2 shows the silicon layer with a nanostructured surface layer receiving the organic semiconductor layer
  • the optoelectronic infrared sensor forms a photodiode, which is composed of an inorganic semiconductor layer formed by a p-doped silicon layer 1 and an organic semiconductor layer 2 applied to this silicon layer 1 to form a heterojunction the silicon layer 1 and the organic semiconductor layer 2 are each connected to an electrode 3, 4, for example of vapor-deposited aluminum.
  • the exposure of the photodiode with a near infrared radiation 5 takes place from the side of the silicon layer 1.
  • the silicon layer 1 acts as a filter for the exciting radiation, so that due to the size of the band gap of the silicon, the radiation range only up to about 1, 1 eV can be used.
  • the detectable radiation is limited by the electronic structure formed by the boundary layer between the silicon layer 1 and the organic semiconductor layer 2 used in each case.
  • the silicon layer 1 is provided with a nano- and / or microstructured surface layer 6, as indicated in FIG.
  • Such a pore structure can be achieved for example by an electrochemical etching of the monocrystalline silicon layer by known methods.
  • other known methods for surface structuring can also be used, as the following examples show.
  • a p-doped, monocrystalline, ⁇ 100> -oriented silicon with a carrier density in the range of 10 13 to 10 15 cm "3 is used as a substrate, wherein an electrode preferably made of aluminum on one side of the silicon substrate is applied so that The silicon substrate is provided with a nanostructured surface layer in the form of pores formed by electrochemical anodization in 48% hydrofluoric acid
  • the silicon substrate was vacuum heated to 580 ° C. by flashlamp annealing and then cooled to 70 ° C.
  • An organic semiconductor layer of 6,6'-dibromindigo in a thickness of 20 to 40 nm was applied to the silicon substrate prefabricated in this manner a hot wall epitaxial process to form a conformal coating of the structure to reach the silicon layer.
  • An electrode made of aluminum, the size of which determines the active area of the infrared sensor, is then deposited on the organic semiconductor layer. The responsiveness of such an infrared sensor begins at 2700 ⁇ .
  • FIG. 3 shows the current density profile versus an infrared sensor with a comparable heterojunction, but without nanostructuring Surface of the silicon layer clearly.
  • the voltage in V and on the ordinate the current density in mA / cm 2 is plotted on a logarithmic scale.
  • the current density profile 7 of the infrared sensor according to Example 1 is shown with a full thicker line compared to the current density profile 8 of the unstructured comparative example.
  • the infrared radiation was in each case with 40 mW / cm 2 at a wavelength of 1, 48 ⁇ .
  • the p-doped silicon substrate with a ⁇ 100> crystal orientation is not subjected to an electrochemical anodization in hydrofluoric acid, but to anisotropic etching using a KOH-isopropanol-water mixture, to give micropyramides with a high content at the surface to produce facing ⁇ 1 1 1> facets.
  • the silicon substrate is vacuum heated to 580 ° C by flash-annealing and then cooled to 70 ° C before the substrate of Example 1 with an organic semiconductor layer of 6,6'-dibromoindigo in thickness between 20 and 40 nm is coated.
  • the infrared sensor manufactured in this way has a response sensitivity beginning at 2700 ⁇ with a peak sensitivity in the range of 1.5 ⁇ . 4, in turn, the course 9 of the current density of the infrared sensor according to Example 2 is compared with the current density curve 10 of a comparison sensor without a structured surface layer of silicon, wherein the irradiation conditions were selected according to Example 1.
  • Example 3 A silicon substrate according to Examples 1 and 2 is subjected to electrochemical anodization in an electrolyte consisting of 0.25M tetrabutylammonium perchlorate in 2M HF acetonitrile to form a porous surface layer. After drying and cleaning according to known methods, the silicon substrate is heated to 580 ° C. in vacuo by flash-lamp annealing and then cooled to 70 ° C. before the substrate has reacted in the same way. In previous examples, an organic semiconductor layer of 6,6'-dibromindigo is coated to a thickness between 20 and 40 nm. The manufactured infrared sensor has a responsiveness beginning at 2700 ⁇ .
  • Example 4 A silicon substrate according to Examples 1 and 2 is subjected to electrochemical anodization in an electrolyte consisting of 0.25M tetrabutylammonium perchlorate in 2M HF acetonitrile to form a porous surface layer. After drying and cleaning according to known methods,
  • a p-doped, ⁇ 100> -oriented silicon with a charge carrier density in the range from 10 17 to 10 20 cm -3 is coated with an organic semiconductor layer according to Example 1.
  • the structuring of the surface layer of the silicon substrate takes place by an anisotropic etching method according to Example 2.
  • the current density profile 1 1 of an infrared sensor fabricated on the basis of this example is shown by dash-dotted lines.
  • the p-doped, monocrystalline, ⁇ 100> -oriented silicon substrate with a charge carrier density in the range between 10 17 to 10 20 cm -3 is provided with a structured surface layer according to Example 1.
  • an organic semiconductor layer an N, N ' Dimethyl-3,4,9,10-perylenetetracarboxylic diimide used as an organic semiconductor layer.
  • a polycrystalline silicon is deposited on a substrate, preferably quartz glass or a glass of high optical quality, by a chemical vapor deposition method or by a method other than silicon.
  • the desired p-type doping is initiated and an ohmic metal contact is applied.
  • the porous surface layer of the silicon layer is provided by means of electrochemical or chemical processes in a region which determines the active range of the infrared sensor. According to a standardized cleaning method, an organic semiconductor layer of 6,6'-dibromoindigo is applied before the semiconductor layer is provided with a metal contact.
  • Example 7 A polycrystalline silicon is used as the active layer of a substrate according to Example 6. After the porous surface layer is formed, an existing pore-expanding method is used to enlarge the pores so that the incident light can be better utilized at the desired near-wavelength wavelength.
  • Example 8 A p-doped, ⁇ 100> oriented silicon with a carrier density in the range of 10 17 to 10 20 cm -3 is provided with an electrode of vapor-deposited aluminum, a metal-supported etch using metallic nanoparticles, preferably silver , which are physically or chemically deposited on the silicon surface to be subsequently exposed to a solution of hydrogen peroxide and fluorine ions, this method results in nanowire-like column surface morphology After this nanostructuring of the surface layer, the substrate becomes again after drying and cleaning a vacuum heating by flash lapping to 580 ° C and subsequent cooling to 70 ° C exposed before an organic semiconductor layer of N, N'-dimethyl-3,4,9,10 perylenetetracarboxylic diimide is applied in a thickness between 20 and 200 nm An infrared sensor manufactured in this way r has a high sensitivity in the range of 1, 5 ⁇ .
  • the dashed line current density curve 12 of an infrared sensor fabricated on the basis of this example can be taken.
  • Example 8 It is provided as in Example 8, a nanowire structure of the silicon substrate. However, a monocrystalline, ⁇ 1 1 1> -oriented silicon is used.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Light Receiving Elements (AREA)
  • Photometry And Measurement Of Optical Pulse Characteristics (AREA)

Abstract

L'invention concerne un capteur infrarouge optoélectronique comportant deux couches à semi-conducteur formant une hétérojonction, connectées chacune à une électrode (3, 4), à savoir une couche de silicium dopée p (1) et une couche à semi-conducteur organique (2) sur la couche de silicium (1). Afin de créer des conditions de construction avantageuses, selon l'invention la couche à semi-conducteur organique (2) est disposée sur une couche de surface nanostructurée et/ou microstructurée (6) de la couche de silicium (1) et elle la recouvre sur toute sa surface.
PCT/AT2015/050182 2014-07-29 2015-07-28 Capteur infrarouge optoélectronique Ceased WO2016015077A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA50534/2014 2014-07-29
ATA50534/2014A AT516109A1 (de) 2014-07-29 2014-07-29 Optoelektronischer Infrarotsensor

Publications (1)

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WO2016015077A1 true WO2016015077A1 (fr) 2016-02-04

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020027670A1 (fr) 2018-07-31 2020-02-06 Fibrain Spółka Z Ograniczoną.Odpowiedzialnoscią. Détecteur proche infrarouge

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT519193A1 (de) * 2016-09-01 2018-04-15 Univ Linz Optoelektronischer Infrarotsensor

Citations (3)

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Publication number Priority date Publication date Assignee Title
US20060263922A1 (en) * 2005-04-25 2006-11-23 Levitsky Igor A Hybrid solar cells based on nanostructured semiconductors and organic materials
WO2006138671A2 (fr) * 2005-06-17 2006-12-28 Illuminex Corporation Fil photovoltaique
WO2009023881A1 (fr) 2007-08-23 2009-02-26 Universität Linz Dispositif de conversion de rayonnement infrarouge en courant électrique

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CN1139997C (zh) * 1997-03-21 2004-02-25 三洋电机株式会社 光电器件及其制造方法
CN102263204B (zh) * 2011-07-20 2013-02-27 苏州大学 一种有机-无机杂化太阳能电池及其制备方法

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US20060263922A1 (en) * 2005-04-25 2006-11-23 Levitsky Igor A Hybrid solar cells based on nanostructured semiconductors and organic materials
WO2006138671A2 (fr) * 2005-06-17 2006-12-28 Illuminex Corporation Fil photovoltaique
WO2009023881A1 (fr) 2007-08-23 2009-02-26 Universität Linz Dispositif de conversion de rayonnement infrarouge en courant électrique

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BEDNORZ MATEUSZ ET AL: "Silicon/organic hybrid heterojunction infrared photodetector operating in the telecom regime", ORGANIC ELECTRONICS, ELSEVIER, AMSTERDAM, NL, vol. 14, no. 5, 14 March 2013 (2013-03-14), pages 1344 - 1350, XP028579696, ISSN: 1566-1199, DOI: 10.1016/J.ORGEL.2013.02.009 *
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020027670A1 (fr) 2018-07-31 2020-02-06 Fibrain Spółka Z Ograniczoną.Odpowiedzialnoscią. Détecteur proche infrarouge

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