EP1512184A2 - Electrodes for optoelectronic components and the use thereof - Google Patents
Electrodes for optoelectronic components and the use thereofInfo
- Publication number
- EP1512184A2 EP1512184A2 EP03740075A EP03740075A EP1512184A2 EP 1512184 A2 EP1512184 A2 EP 1512184A2 EP 03740075 A EP03740075 A EP 03740075A EP 03740075 A EP03740075 A EP 03740075A EP 1512184 A2 EP1512184 A2 EP 1512184A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrode
- allotropes
- organic
- electrodes
- nanotubes
- 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.)
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Links
- 230000005693 optoelectronics Effects 0.000 title claims description 8
- 239000004065 semiconductor Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001002 functional polymer Polymers 0.000 claims abstract description 9
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 8
- 239000002071 nanotube Substances 0.000 claims description 33
- 239000002131 composite material Substances 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000002620 silicon nanotube Substances 0.000 abstract description 4
- 229910021430 silicon nanotube Inorganic materials 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 231100000289 photo-effect Toxicity 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- 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
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/221—Carbon nanotubes
-
- 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
-
- 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
Definitions
- the invention relates to electrodes which comprise spherical allotropes, in particular silicon and / or carbon nanotubes, and their use in organic semiconductor technology.
- Electrodes for optoelectronic components based on organic conductors such as PANI, PED0T: PSS (polystyrene sulfonic acid) etc.
- the conductivity, the transparency for light, the electronic work function and / or the surface properties of these electrodes can still be optimized.
- the object of the present invention is therefore to provide a new electrode with improved (opto) electronic properties for organic semiconductor components and optoelectronic components.
- the invention relates to an electrode for optoelectronic and / or organic semiconductor components, which comprises allotropes.
- the invention also combines, for example, allotropes with organic conductors or semiconductors (typically conjugated polymers) to form a semi-transparent or non-transparent electrode.
- the electrodes can comprise the allotropes either in their metallic conductive form or in their semiconducting form.
- metallic-conductive allotropes are, for example, from the literature (ZF Ren, ZP Huang, J.. Xu, DZ Wang, JH Wang, L. Calvet, J. Chen, JF Klemic, and MA Reed, "Large Arrays of Well-Aligned Carbon Nanotubes ", Proceedings of 13th International Winter School on Electronic Properties of Nove Materials, Pages 263-267, (1999).
- Nanotubes have a variety of unique electronic, optical and mechanical properties.
- Single-walled nanotubes have high tensile strength and, depending on the diameter and chirality, can be metallic, semiconducting or insulating.
- chemical derivatization of nanotubes can also make sense, because this can influence their solubility and processability.
- the derivatized and / or soluble nanotubes can be used as part of a phase mixture in organic functional polymers of microelectronics.
- Spherical allotropes such as nanotubes are e.g. in Nature 1991, vol. 354, pages 56 to 58. There are silicon and carbon nanotubes.
- the alltotropes can either be added to conductive organic materials and / or drawn on substrates.
- the electrodes can either be realized purely with metallic allotropes, or by means of composite materials with metallic allotropes and / or with semiconducting allotropes.
- the following allotropes are suitable for positive / negative electrodes, which are formed by prior deposition of a suitable catalyst on substrates such as glass, metal (molybdenum), semiconductors (silicon) or also on foils (PET).
- a combination of at least two elements selected from the group of conductive substrates (conductive oxides (ITO), doped semiconductors (silicon, germanium ...), - of metals such as AL, Ag ... is also suitable for positive / negative electrodes. . or
- non-conductive substrates glass, foils, ...) on which allotropes are applied either in their purest form or in mixtures with conductive or non-conductive binding materials (polymers ).
- organic material or “functional polymer” or “polymer” here encompasses all types of organic, organometallic and / or organo-inorganic plastics (hybrids), in particular those which are described in English e.g. be called “plastics”. These are all types of substances with the exception of the semiconductors that form the classic diodes (germanium, silicon) and the typical metallic conductors. A restriction in the dogmatic sense to organic material as carbon-containing material is therefore not provided, but rather is also due to the widespread use of e.g. Silicones thought.
- polymer in the functional polymer is historical and therefore contains no information about the presence of an actually polymeric compound.
- functional polymer can refer to semiconducting, conducting and / or insulating substances.
- Metallic allotropes or nanotubes grown (formed) on a substrate result in conductive electrodes with a a three-dimensional structure, for example a two-dimensional array with nanotubes on it, which has a large surface area.
- the increase in surface area that is to say the ratio of the substrate surface on which the allotorop is applied, to the usable electrode surface, that is to say the active area, can be increased further by the density of the planting, that is to say the grown allotropes and / or by their length ,
- Composite material for electrodes can e.g. can be produced by embedding metallic allotropes in a matrix of conductive functional polymer. In this mixture of the allotrope with the organic functional polymer, the conductivity and / or the transparency of the electrode can be optimized via the amount of allotrope, its concentration in the matrix. From this composite material e.g. an electrode can be printed as a solution.
- semiconducting allotopes can also be used as the positive electrode (electron acceptor) for heterojunction applications. It has recently been shown that nanotube composites with conjugated polymers show a strong photo effect (SB Lee, T. Karayama, H. Kajii, H. Araki and K. Yoshino, Synth. Met 121 (2001) 1591-1592 ).
- the optical properties of the electrode can be adjusted by changing the length of the allotropes.
- Allotropic or nanotubes of suitable length function like a ⁇ / 4 antenna that is used to absorb electromagnetic radiation.
- allotropes for example, allotropes with a length of 100 to 200 nm are used. The invention is explained in more detail below with the aid of examples:
- Example 1 is the embodiment of the invention as an organic solar cell or organic photodetector, based on a metallic nanotube electrode.
- the nanotubes are either deposited on a conductive substrate, as an alternative, the nanotubes can also be “grown” on a non-conductive substrate, that is, “formed by growing”.
- the nanotube electrode is coated with a conductive (optionally or optionally semitransparent polymer) (eg by means of a printing process from the solution).
- This electrode then comprises these layers - substrate optionally conductive layer, eg. B. Au, ITO, AI ... - nanotube (selectable adjustable length, arrangement) optionally conductive polymer.
- the organic semiconductor (or a mixture of organic p-type and n-type semiconductor) is then deposited on this electrode (for example by a printing process from the solution).
- the component is finished by applying a counter electrode (typically by thermal vapor deposition of a thin metal layer).
- the optical absorption can be increased by a suitable choice of the length of the nanotubes and their arrangement.
- the second example describes an organic solar cell or an organic photodetector based on a semiconducting nanotube electrode.
- the nanotubes are either deposited on a conductive substrate, alternatively the nanotubes can also be grown on a non-conductive substrate.
- the nanotube electrode is coated with a conductive (optionally semi-transparent polymer) (e.g. by printing from the solution).
- a conductive optionally semi-transparent polymer
- the organic semiconductor preferably a p-type semiconductor
- is deposited typically by solution printing process.
- the semiconducting nanotubes of the electrode act as n-type semiconductors, so that a photo effect occurs between the polymeric semiconductor and the nanotubes.
- the component is finished by applying a counter electrode (typically by thermal evaporation of thin metal layers).
- the optical absorption can be increased by a suitable choice of the nanotube length and the arrangement of the nanotubes.
- the third example describes an organic light-emitting diode (or an organic display) based on a nanotube electrode (nanotube electrode array).
- the nanotubes are either deposited on a conductive substrate, as an alternative, the nanotubes can also be grown on a non-conductive substrate, for contacting, the nanotube electrode is coated with a conductive (optionally semitransparent polymer) (e.g. by printing process from the solution).
- the organic semiconductor preferably a p-type semiconductor
- is deposited onto this electrode isting of substrate / (optionally conductive layer, for example Au, ITO, AI ...) / nanotube / (optionally conductive polymer) (typically through printing process from solution).
- the component is completed by applying a counter electrode (typically by thermal evaporation of thin metal layers).
- the semiconductor component is composed as follows: Step 1: Production of the underside: substrate / electrode 1 (metal) / organic semiconductor Step 2: pressing a grown nanotube electrode into the organic semiconductor. By pressing, the carbon nanotubes penetrate into the organic semiconductor and make contact. With this technology, either the electrode 1 or the nanotube electrode can be designed to be semi-transparent.
- the invention relates to electrodes which comprise spherical allotropes, in particular silicon and / or carbon nanotubes, and their use in organic semiconductor technology.
- the electrodes can either comprise only allotropes and / or allotropes which are embedded in an organic functional polymer.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Manufacturing & Machinery (AREA)
- Theoretical Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Photovoltaic Devices (AREA)
- Electrodes Of Semiconductors (AREA)
- Electroluminescent Light Sources (AREA)
- Carbon And Carbon Compounds (AREA)
- Light Receiving Elements (AREA)
Abstract
The invention relates to electrodes, which comprise spherical allotropes, particularly silicon and/or carbon nanotubes, and to the use thereof in organic semiconductor technology. The electrodes can either exclusively contain allotropes and/or contain allotropes that are embedded in an organic functional polymer.
Description
Beschreibungdescription
Elektroden für optoelektronische Bauelemente und deren VerwendungElectrodes for optoelectronic components and their use
Die Erfindung betrifft Elektroden, die sphärische Allotrope, insbesondere Silizium- und/oder Kohlenstoff-Nanoröhren umfassen sowie deren Verwendung in der organischen Halbleitertechnik-The invention relates to electrodes which comprise spherical allotropes, in particular silicon and / or carbon nanotubes, and their use in organic semiconductor technology.
Bekannt sind aus der DE 101 268 59.9 Elektroden für optoelektronische Bauelemente basierend auf organischen Leitern wie PANI, PED0T:PSS(Polystyrolsulfonsäure) etc.Known from DE 101 268 59.9 are electrodes for optoelectronic components based on organic conductors such as PANI, PED0T: PSS (polystyrene sulfonic acid) etc.
Aus der 101 53 316.0 sind derivatisierte Nanoröhren und sphärische Allotrope für den Einsatz in (opto) elektronischen Bauelementen bekannt.Derivatized nanotubes and spherical allotropes for use in (opto) electronic components are known from 101 53 316.0.
Die Leitfähigkeit, die Transparenz für Licht, die elektroni- sehe Arbeitsfunktion und/oder die Oberflächenbeschaffenheit dieser Elektroden können jedoch noch optimiert werden.However, the conductivity, the transparency for light, the electronic work function and / or the surface properties of these electrodes can still be optimized.
Es besteht daher der Bedarf, neue und bessere Elektroden auf organischer Basis zum Einsatz in der sogenannten „Polymer- Elektronik" , also dem Zweig der Elektronik, der abseits von den herkömmlichen Materialien wie Silizium, Germanium etc. Halbleitertechnik realisiert, zu schaffen.There is therefore a need to create new and better electrodes on an organic basis for use in the so-called “polymer electronics”, ie the branch of electronics that realizes semiconductor technology apart from conventional materials such as silicon, germanium etc.
Aufgabe der vorliegenden Erfindung ist es daher, eine neue und in ihren (opto) elektronischen Eigenschaften verbesserte Elektrode für organische Halbleiterbauelemente und optoelektronische Bauelemente zur Verfügung zu stellen.The object of the present invention is therefore to provide a new electrode with improved (opto) electronic properties for organic semiconductor components and optoelectronic components.
Gegenstand der Erfindung ist eine Elektrode für optoelektro- nische- und/oder organische Halbleiterbauelemente, die Allotrope umfasst.
Die Erfindung kombiniert z.B. auch Allotrope mit organischen Leitern oder Halbleitern (typischerweise konjugierten Polymeren) zu einer semitransparenten oder nicht transparenten Elektrode.The invention relates to an electrode for optoelectronic and / or organic semiconductor components, which comprises allotropes. The invention also combines, for example, allotropes with organic conductors or semiconductors (typically conjugated polymers) to form a semi-transparent or non-transparent electrode.
Die Elektroden können die Allotrope entweder in ihrer metallisch-leitfähigen Form oder in ihrer halbleitenden Form umfassen. Beispiele metallisch-leitender Allotrope sind beispielsweise aus der Literatur (Z. F. Ren, Z. P. Huang, J. . Xu, D. Z. Wang, J. H. Wang, L. Calvet, J. Chen, J. F. Klemic, and M. A. Reed, "Large Arrays of Well-Aligned Carbon Nanotubes" , Proceedings of 13th International Winter School on Electronic Properties of Nove Materials, Pages 263 - 267, (1999) bekannt.The electrodes can comprise the allotropes either in their metallic conductive form or in their semiconducting form. Examples of metallic-conductive allotropes are, for example, from the literature (ZF Ren, ZP Huang, J.. Xu, DZ Wang, JH Wang, L. Calvet, J. Chen, JF Klemic, and MA Reed, "Large Arrays of Well-Aligned Carbon Nanotubes ", Proceedings of 13th International Winter School on Electronic Properties of Nove Materials, Pages 263-267, (1999).
Nanoröhren weisen eine Vielzahl einzigartiger elektronischer, optischer und mechanischer Eigenschaften auf. Einwandige Nanoröhren besitzen hohe Dehnungsfestigkeit und können je nach Durchmesser und Chiralität metallisch, halbleitend oder iso- lierend sein. Um diese Eigenschaften für nanotechnologische Anwendungen ausnützen zu können, kann auch eine chemische De- rivatisierung von Nanoröhren sinnvoll sein, weil dadurch deren Löslichkeit und Verarbeitbarkeit beeinflusst werden kann. Insbesondere sind die derivatisierten und/oder löslichen Na- noröhren als Teil eines Phasengemisches in organischen Funktionspolymeren der Mikroelektronik einsetzbar.Nanotubes have a variety of unique electronic, optical and mechanical properties. Single-walled nanotubes have high tensile strength and, depending on the diameter and chirality, can be metallic, semiconducting or insulating. In order to be able to use these properties for nanotechnological applications, chemical derivatization of nanotubes can also make sense, because this can influence their solubility and processability. In particular, the derivatized and / or soluble nanotubes can be used as part of a phase mixture in organic functional polymers of microelectronics.
Sphärische Allotrope wie Nanoröhren sind z.B. in Nature 1991, Vol. 354, Seiten 56 bis 58 beschrieben. Es gibt Silizium und Kohlenstoff-Nanoröhren.Spherical allotropes such as nanotubes are e.g. in Nature 1991, vol. 354, pages 56 to 58. There are silicon and carbon nanotubes.
Die Alltotrope können leitfähigen organischen Materialien entweder zugesetzt werden und/oder auf Substraten gezogen werden. Die Elektroden können entweder rein mit metallischen Allotropen, oder durch Verbundmaterialien mit metallischen Allotropen und/oder mit halbleitenden Allotropen realisiert werden.
Für positive/negative Elektroden eignen sich folgende Allotrope, die durch vorherige Deposition eines geeigneten Katalysators auf Substraten wie Glas, Metall (Molybdän) , Halb- leiter (Silizium) oder auch auf Folien (PET) gebildet werden. Für positive/negative Elektroden eignet sich auch eine Kombination aus zumindest zwei Elementen ausgewählt aus der Gruppe der leitfähigen Substrate (leitfähige Oxide (ITO) , der dotierten Halbeiter (Silizium, Germanium...), - von Metallen wie AL, Ag.... oderThe alltotropes can either be added to conductive organic materials and / or drawn on substrates. The electrodes can either be realized purely with metallic allotropes, or by means of composite materials with metallic allotropes and / or with semiconducting allotropes. The following allotropes are suitable for positive / negative electrodes, which are formed by prior deposition of a suitable catalyst on substrates such as glass, metal (molybdenum), semiconductors (silicon) or also on foils (PET). A combination of at least two elements selected from the group of conductive substrates (conductive oxides (ITO), doped semiconductors (silicon, germanium ...), - of metals such as AL, Ag ... is also suitable for positive / negative electrodes. . or
- von nicht leitfähigen Substraten ( Glas, Folien,...) auf denen Allotrope entweder in Reinstform, oder in Mischungen mit leitfähigen oder nicht-leitfähigen Bindematerialien (Polymere.... ) aufgetragen werden.- of non-conductive substrates (glass, foils, ...) on which allotropes are applied either in their purest form or in mixtures with conductive or non-conductive binding materials (polymers ...).
Der Begriff "organisches Material" oder "Funktionspolymer" oder "Polymer" umfasst hier alle Arten von organischen, metallorganischen und/oder organisch-anorganischen Kunststoffen (Hybride), insbesondere die, die im Englischen z.B. mit "plastics" bezeichnet werden. Es handelt sich um alle Arten von Stoffen mit Ausnahme der Halbleiter, die die klassischen Dioden bilden (Germanium, Silizium) , und der typischen metallischen Leiter. Eine Beschränkung im dogmatischen Sinn auf organisches Material als Kohlenstoff-enthaltendes Material ist demnach nicht vorgesehen, vielmehr ist auch an den breiten Einsatz von z.B. Siliconen gedacht. Weiterhin soll der Term keiner Beschränkung im Hinblick auf die Molekülgröße, insbesondere auf polymere und/oder oligomere Materialien unterliegen, sondern es ist durchaus auch der Einsatz von "small molecules" möglich. Der Wortbestandteil "polymer" im Funktionspolymer ist historisch bedingt und enthält insofern keine Aussage über das Vorliegen einer tatsächlich polymeren Verbindung. Als Funktionspolymer können halbleitende, leitende und/oder isolierende Stoffe gemeint sein.The term "organic material" or "functional polymer" or "polymer" here encompasses all types of organic, organometallic and / or organo-inorganic plastics (hybrids), in particular those which are described in English e.g. be called "plastics". These are all types of substances with the exception of the semiconductors that form the classic diodes (germanium, silicon) and the typical metallic conductors. A restriction in the dogmatic sense to organic material as carbon-containing material is therefore not provided, but rather is also due to the widespread use of e.g. Silicones thought. Furthermore, the term should not be subject to any restriction with regard to the molecular size, in particular to polymeric and / or oligomeric materials, but the use of "small molecules" is also entirely possible. The word component "polymer" in the functional polymer is historical and therefore contains no information about the presence of an actually polymeric compound. The term functional polymer can refer to semiconducting, conducting and / or insulating substances.
Auf einem Substrat aufgewachsene (gebildete) metallische Allotrope oder Nanoröhren ergeben leitfähige Elektroden mit ei-
ner dreidimensionalen Struktur, beispielsweise einen zweidi- mensionalen Array mit darauf stehenden Nanoröhren, die eine große Oberfläche hat. Die Oberflächevergrößerung, also das Verhältnis der Substratoberfläche, auf der das Allotorop auf- gebracht wird, zu der nutzbaren Elektrodenoberfläche, also der aktiven Fläche, lässt sich durch die Dichte der Bepflan- zung, also der gewachsenen Allotrope und/oder durch deren Länge noch steigern.Metallic allotropes or nanotubes grown (formed) on a substrate result in conductive electrodes with a a three-dimensional structure, for example a two-dimensional array with nanotubes on it, which has a large surface area. The increase in surface area, that is to say the ratio of the substrate surface on which the allotorop is applied, to the usable electrode surface, that is to say the active area, can be increased further by the density of the planting, that is to say the grown allotropes and / or by their length ,
Verbundmaterial für Elektroden kann z.B. durch Einbettung von metallischen Allotropen in eine Matrix aus leitendem Funktionspolymer hergestellt werden. In dieser Mischung des Al- lotrops mit dem organischen Funktionspolymer kann über die Menge an Allotrop, dessen Konzentration in der Matrix die Leitfähigkeit und/oder die Transparenz der Elektrode optimiert werden. Aus diesem Verbundmaterial kann z.B. als Lösung eine Elektrode gedruckt werden.Composite material for electrodes can e.g. can be produced by embedding metallic allotropes in a matrix of conductive functional polymer. In this mixture of the allotrope with the organic functional polymer, the conductivity and / or the transparency of the electrode can be optimized via the amount of allotrope, its concentration in the matrix. From this composite material e.g. an electrode can be printed as a solution.
Als positive Elektrode (Elektronenakzeptor) für Heterojuncti- on Anwendungen können insbesondere auch halbleitende Alloto- rope eingesetzt werden. Vor kurzem wurde gezeigt, dass Compo- sites aus Nanoröhren mit konjugierten Polymeren einen starken Photoeffekt zeigen (S. B. Lee, T. Karayama, H. Kajii, H. Ara- ki and K. Yoshino, Synth. Met 121 (2001) 1591-1592) .In particular, semiconducting allotopes can also be used as the positive electrode (electron acceptor) for heterojunction applications. It has recently been shown that nanotube composites with conjugated polymers show a strong photo effect (SB Lee, T. Karayama, H. Kajii, H. Araki and K. Yoshino, Synth. Met 121 (2001) 1591-1592 ).
Für optoelektronische Bauelemente wie beispielsweise organische Leuchtdioden (OLEDs) aber auch organische Solarzellen und Photodetektoren lassen sich die optischen Eigenschaften der Elektrode durch die Veränderung der Länge der Allotrope anpassen. Allotrope oder Nanoröhren geeigneter Länge funktionieren wie eine λ/4 Antenne, die zur Absorption von elektromagnetischer Strahlung dient. Um z.B. mit Allotropen eine Absorption im sichtbaren Lichtwellenbereich zu erreichen (400 nm - 800 nm) , werden Allotrope mit einer Länge von 100 bis 200 nm eingesetzt.
Im folgenden wird die Erfindung noch anhand von Beispielen näher erläutert:For optoelectronic components such as organic light-emitting diodes (OLEDs) but also organic solar cells and photodetectors, the optical properties of the electrode can be adjusted by changing the length of the allotropes. Allotropic or nanotubes of suitable length function like a λ / 4 antenna that is used to absorb electromagnetic radiation. In order to achieve absorption in the visible light wave range (400 nm - 800 nm) with allotropes, for example, allotropes with a length of 100 to 200 nm are used. The invention is explained in more detail below with the aid of examples:
Beispiel 1 ist die Ausführungsform der Erfindung als organi- sehe Solarzelle oder organischer Photodetektor, basierend auf einer metallischen Nanoröhrenelektrode. Zunächst werden die Nanoröhren entweder auf einem leitfähigen Substrat abgeschieden, als Alternative können die Nanoröhren auch auf einem nicht leitfähigen Substrat „gewachsen" das heißt „durch Wach- senlassen gebildet" werden. Zur Kontaktierung wird die Nano- röhren-Elektrode mit einem leitfähigen (gegebenenfalls oder optional semitransparenten Polymer) beschichtet (z. B. durch einen Druckprozess aus der Lösung) . Diese Elektrode umfasst dann diese Schichten - Substrat optional leitfähige Schicht, z. B. Au, ITO, AI... - Nanoröhre (gezielt einstellbare Länge, Anordnung) optional leitfähiges Polymer. Auf diese Elektrode wird dann der organische Halbleiter (oder eine Mischung aus organischem p-Typ und n-Typ Halbleiter) abgeschieden (beispielsweise durch einen Druckprozess aus der Lösung) . Das Bauteil wird durch das Aufbringen einer Gegenelektrode (typischerweise durch thermisches Aufdampfen einer dünnen Metallschicht) fertiggestellt. Durch geeignete Wahl der Länge der Nanoröhren und ihrer Anordnung kann die optische Absorption erhöht werden.Example 1 is the embodiment of the invention as an organic solar cell or organic photodetector, based on a metallic nanotube electrode. First, the nanotubes are either deposited on a conductive substrate, as an alternative, the nanotubes can also be “grown” on a non-conductive substrate, that is, “formed by growing”. For contacting, the nanotube electrode is coated with a conductive (optionally or optionally semitransparent polymer) (eg by means of a printing process from the solution). This electrode then comprises these layers - substrate optionally conductive layer, eg. B. Au, ITO, AI ... - nanotube (selectable adjustable length, arrangement) optionally conductive polymer. The organic semiconductor (or a mixture of organic p-type and n-type semiconductor) is then deposited on this electrode (for example by a printing process from the solution). The component is finished by applying a counter electrode (typically by thermal vapor deposition of a thin metal layer). The optical absorption can be increased by a suitable choice of the length of the nanotubes and their arrangement.
Das zweite Beispiel beschreibt eine organische Solarzelle oder einen organischen Photodetektor, basierend auf einer halbleitenden Nanoröhrenelektrode. Zur Kontaktierung werden die Nanoröhren entweder auf einem leitfähigen Substrat abgeschieden, als Alternative können die Nanoröhren auch auf einem nichtleitfähigem Substrat gewachsen werden. Zur Kontaktierung wird die Nanoröhrenelektrode mit einem leitfähigen (optional semitransparenten Polymer) beschichtet (z. B. durch Druckprozess aus der Lösung) . Auf diese Elektrode (bestehend aus Substrat /(optional leitfähige Schicht, z. BP, Au, ITO,
AI...) / Nanotube / (optional leitfähiges Polymer)) wird der organische Halbleiter (bevorzugt ein p-Typ Halbleiter) abgeschieden (typischerweise durch Druckprozess aus der Lösung) . Die halbleitenden Nanoröhren der Elektrode fungieren als n- Typ Halbleiter, so dass es zwischen dem polymeren Halbleiter und den Nanoröhren zu einem Photoeffekt kommt. Das Bauteil wird durch das Aufbringen einer Gegenelektrode (typischerweise durch thermisches Verdampfen von dünnen Metallschichten) fertiggestellt. Durch geeignete Wahl der Nanoröhrenlänge und der Anordnung der Nanoröhren kann die optische Absorption erhöht werden.The second example describes an organic solar cell or an organic photodetector based on a semiconducting nanotube electrode. For contacting, the nanotubes are either deposited on a conductive substrate, alternatively the nanotubes can also be grown on a non-conductive substrate. For contacting, the nanotube electrode is coated with a conductive (optionally semi-transparent polymer) (e.g. by printing from the solution). On this electrode (consisting of substrate / (optionally conductive layer, e.g. BP, Au, ITO, AI ...) / Nanotube / (optional conductive polymer)) the organic semiconductor (preferably a p-type semiconductor) is deposited (typically by solution printing process). The semiconducting nanotubes of the electrode act as n-type semiconductors, so that a photo effect occurs between the polymeric semiconductor and the nanotubes. The component is finished by applying a counter electrode (typically by thermal evaporation of thin metal layers). The optical absorption can be increased by a suitable choice of the nanotube length and the arrangement of the nanotubes.
Das dritte Beispiel beschreibt eine organische Leuchtdiode (oder ein organisches Display) , basierend auf einer Nanoröh- renelektrode (Nanotubeelektrodenarray) . Zur Kontaktierung werden die Nanoröhren (Nanotubes) entweder auf einem leitfähigen Substrat abgeschieden, als Alternative können die Nanotubes auch auf einem nichtleitfähigem Substrat gewachsen werden, zur Kontaktierung wird die Nanotube Elektrode mit einem leitfähigen (optional semitransparenten Polymer) beschichtet (z. B. durch Druckprozess aus der Lösung). Auf diese Elektrode (bestehend aus Substrat / (optional leitfähige Schicht, z. B. Au, ITO, AI...) / Nanotube / (optional leitfähiges Polymer) ) wird der organische Halbleiter (bevorzugt ein p-Typ Halbleiter) abgeschieden (typischerweise durch Druckprozess aus der Lösung) . Das Bauteil wird durch das Aufbringen einer Gegenelektrode (typischerweise durch thermisches Verdampfen von dünnen Metallschichten) fertiggestellt.The third example describes an organic light-emitting diode (or an organic display) based on a nanotube electrode (nanotube electrode array). For contacting, the nanotubes are either deposited on a conductive substrate, as an alternative, the nanotubes can also be grown on a non-conductive substrate, for contacting, the nanotube electrode is coated with a conductive (optionally semitransparent polymer) (e.g. by printing process from the solution). The organic semiconductor (preferably a p-type semiconductor) is deposited onto this electrode (consisting of substrate / (optionally conductive layer, for example Au, ITO, AI ...) / nanotube / (optionally conductive polymer)) (typically through printing process from solution). The component is completed by applying a counter electrode (typically by thermal evaporation of thin metal layers).
Schließlich wird noch das Kontaktieren einer organischen Solarzelle, einer organischen Leuchtdiode oder eines organischen Photodetektors durch Verpressen mit einer Kohlenstoff- Nanoröhrenelektrode. Das Halbleiterbauelement wird dabei wie folgt zusammengesetzt: Schritt 1: Fertigung der Unterseite: Substrat/Elektrode 1 (Metall)/ organischer Halbleiter
Schritt 2: Verpressen einer gewachsenen Nanoröhrenelektrode in den organischen Halbleiter. Durch das Verpressen dringen die Kohlenstoff-Nanoröhren in den organischen Halbleiter ein und vollziehen die Kontaktierung. Bei dieser Technologie kann entweder die Elektrode 1 oder die Nanoröhrenelektrode semitransparent ausgelegt werden.Finally, there is the contacting of an organic solar cell, an organic light-emitting diode or an organic photodetector by pressing with a carbon nanotube electrode. The semiconductor component is composed as follows: Step 1: Production of the underside: substrate / electrode 1 (metal) / organic semiconductor Step 2: pressing a grown nanotube electrode into the organic semiconductor. By pressing, the carbon nanotubes penetrate into the organic semiconductor and make contact. With this technology, either the electrode 1 or the nanotube electrode can be designed to be semi-transparent.
Die Erfindung betrifft Elektroden, die sphärische Allotrope, insbesondere Silizium- und/oder Kohlenstoff-Nanoröhren umfas- sen sowie deren Verwendung in der organischen Halbleitertechnik. Die Elektroden können entweder nur Allotrope umfassen und/oder Allotrope, die in ein organisches Funktionspolymer eingebettet sind.
The invention relates to electrodes which comprise spherical allotropes, in particular silicon and / or carbon nanotubes, and their use in organic semiconductor technology. The electrodes can either comprise only allotropes and / or allotropes which are embedded in an organic functional polymer.
Claims
1. Elektrode für optoelektronische- und/oder organische Halbleiterbauelemente, die Allotrope umfasst.1. Electrode for optoelectronic and / or organic semiconductor components, which comprises allotropes.
2. Elektrode nach Anspruch 1, bei der das Allotrop in metallischer Form oder halbleitend vorliegt.2. The electrode of claim 1, wherein the allotrope is in metallic form or semiconducting.
3. Elektrode nach einem der Ansprüche 1 oder 2, bei der das Allotrop in einem Verbundmaterial vorliegt.3. Electrode according to one of claims 1 or 2, wherein the allotrope is in a composite material.
4. Elektrode nach einem der vorstehenden Ansprüche, die semitransparent oder transparent ist.4. Electrode according to one of the preceding claims, which is semitransparent or transparent.
5. Elektrode nach einem der vorstehenden Ansprüche, bei der das Allotrop eine Nanoröhre, insbesondere eine Kohlen- stoff-Nanoröhre ist.5. Electrode according to one of the preceding claims, in which the allotrope is a nanotube, in particular a carbon nanotube.
6. Elektrode nach einem der vorstehenden Ansprüche, bei der durch die Längeneinstellung der eingesetzten Allotrope die optischen Eigenschaften der Elektrode gezielt einstellbar sind.6. Electrode according to one of the preceding claims, in which the optical properties of the electrode can be specifically adjusted by the length adjustment of the allotropes used.
7. Verwendung einer Elektrode nach einem der Ansprüche 1 bis 6 in einem optoelektronischen und/oder elektronischen7. Use of an electrode according to one of claims 1 to 6 in an optoelectronic and / or electronic
Bauelement, das zumindest ein organisches Funktionspolymer umfasst. Component comprising at least one organic functional polymer.
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WO2005083751A2 (en) * | 2004-02-20 | 2005-09-09 | University Of Florida Research Foundation, Inc. | Semiconductor device and method using nanotube contacts |
WO2007120175A2 (en) * | 2005-08-24 | 2007-10-25 | The Trustees Of Boston College | Apparatus and methods for solar energy conversion using nanoscale cometal structures |
JP4720426B2 (en) * | 2005-10-19 | 2011-07-13 | 住友金属鉱山株式会社 | Solar cell using carbon nanotubes |
US20100068461A1 (en) * | 2006-06-30 | 2010-03-18 | University Of Wollongong | Nanostructured composites |
US9184317B2 (en) * | 2007-04-02 | 2015-11-10 | Merck Patent Gmbh | Electrode containing a polymer and an additive |
WO2009023778A1 (en) * | 2007-08-14 | 2009-02-19 | William Marsh Rice University | Optical rectification device and method of making same |
KR20170132341A (en) | 2009-04-30 | 2017-12-01 | 유니버시티 오브 플로리다 리서치 파운데이션, 인크. | Single wall carbon nanotube based air cathodes |
KR101744931B1 (en) | 2010-09-24 | 2017-06-09 | 서울바이오시스 주식회사 | Semiconductor Light Emitting Device and Manufacturing Method Thereof |
CA2821163A1 (en) | 2010-12-17 | 2012-06-21 | University Of Florida Research Foundation, Inc. | Hydrogen oxidation and generation over carbon films |
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