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WO2008148705A1 - Organic photo-detector having adjustable transmission and a production method thereof - Google Patents

Organic photo-detector having adjustable transmission and a production method thereof Download PDF

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Publication number
WO2008148705A1
WO2008148705A1 PCT/EP2008/056660 EP2008056660W WO2008148705A1 WO 2008148705 A1 WO2008148705 A1 WO 2008148705A1 EP 2008056660 W EP2008056660 W EP 2008056660W WO 2008148705 A1 WO2008148705 A1 WO 2008148705A1
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WIPO (PCT)
Prior art keywords
layer
transmission
organic
components
blend
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Ceased
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PCT/EP2008/056660
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German (de)
French (fr)
Inventor
Jens FÜRST
Debora Henseler
Edgar Zaus
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Siemens AG
Siemens Corp
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Siemens AG
Siemens Corp
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Publication of WO2008148705A1 publication Critical patent/WO2008148705A1/en
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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
    • 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
    • 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
    • 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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H10K30/211—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions comprising multiple junctions, e.g. double heterojunctions
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/114—Poly-phenylenevinylene; Derivatives thereof
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • 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
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to an organic photodetector having an adjustable transmission and a manufacturing method thereof.
  • Organic photodetectors such as those from the
  • DE 10 2005 037 290.2 are known, usually comprise a layer system of a lower possibly metallic electrode, a photoactive layer which may be, for example, a blend of different components and a counter electrode, which in turn may be metallic.
  • organic photodetectors with an organic photoactive layer can be produced semitransparently.
  • This layer usually comprises two components, which may be present either as separate layers or as a blend.
  • the layer thickness of the layer system is reduced in such a way that the layers alone become translucent due to the reduction in their layer thickness, ie have increased transmission.
  • the disadvantage of this is that the spectral distribution of the transmission can not be influenced by the reduction of the layer thickness, so that only by accepting an otherwise poorer performance of the detector, especially with respect to dark currents, because of the small layer thickness increases the transmission of the detector as a whole can be.
  • the object of the present invention is therefore to provide an organically based photodetector, in 200 6174 96
  • the invention therefore relates to a photodetector based on organic semiconductors, comprising a layer system in which between a lower electrode and an upper
  • Counter-electrode is a photoactive layer containing at least three components in a blend and / or in a layer structure, which act as a hole and / or electron transport component.
  • the invention relates to a method for producing a photodetector, wherein on an at least semitransparent lower electrode, a blend layer is spun onto which in turn a further at least semitransparent top electrode is applied.
  • hole transport components act as electron donors and electron transport components as electron acceptors.
  • two or more hole transport components are combined, since these usually dominate the absorption behavior of the blend.
  • the light distribution associated with the image penetrates the electrode which faces the light distribution and is therefore made of an at least semitransparent material. Furthermore, the semiconductor layer in conjunction with the two electrodes converts the light distribution into electrical signals which are applied to the individual sub-electrodes of the structured electrode.
  • this semiconductor layer is, for example, a blend of the two components P3HT (absorber, electron 200 6174 96
  • the semiconductor layer may be constructed as a multiple monolayer comprising layer in the hole transport component and electron transport component in separate layers.
  • further materials are now added which change the transmission spectrum of the BuIk heterojunction, preferably selectively alter it.
  • further hole transport components are added, for example those which absorb little in the visible range or absorb at wavelengths other than the components present in the blend.
  • the proportions of the additional hole transport components must be selected accordingly.
  • absorber, hole transport, electron acceptor and / or electron transport components which can be introduced into the BuIk heterojunction in addition to the basic components such as P3HT / PCBM, for example copolymers of triarylamine components and fluorene (such as ADS250BE from American Dye Source) and or copolymers of triarylamine components and spirobifluorene components and / or poly (para-phenylenevinylene) derivatives (eg MEH-PPV or MDMO-PPV) and / or further polythiophene derivatives (eg P3OT).
  • copolymers of triarylamine components and fluorene such as ADS250BE from American Dye Source
  • copolymers of triarylamine components and spirobifluorene components and / or poly (para-phenylenevinylene) derivatives eg MEH-PPV or MDMO-PPV
  • polythiophene derivatives eg P3OT
  • the transmission spectrum can be adapted to the respective application.
  • the color with which the detector surface is perceived be influenced.
  • Another advantage is that by substituting the absorbing component, for example P3HT, with a transparent material having similar charge transport properties or a transparent material which does not hinder the electrical transport, the transmission can be varied over a wide range at a constant layer thickness without increasing the dark current and the short circuit susceptibility of the photodetectors.
  • the absorbing component for example P3HT
  • the invention not only relates to photodiodes on a polymer basis, but can also be applied to photoactive layers based on so-called small molecules or nanoparticles.
  • the procedure is, for example, as follows: onto a semitransparent bottom electrode (for example ITO), a blend layer is spin-coated. For this, the blend components are dissolved in a suitable solvent (e.g., chloroform or xylene).
  • a semitransparent top electrode e.g., a thin layer system of Ca and Ag is applied to the blend layer (e.g., by thermal evaporation).
  • Organic-based photodetectors can be produced relatively simply by applying the organic semiconductor layer to the solution using printing methods.
  • organic photodetectors have relatively high compatibility with various electronic driver technologies.
  • An organic photodetector may be used in addition to the photoactive layer, for example P3HT / PCBM, CuPc / PTCBI, 200 6174 96
  • ZNPC / C60 conjugated polymer components or fullerene components, comprise an electron / hole blocking layer.
  • Electron / hole blocking layers are known from organic LED technology.
  • a suitable organic material for the electron blocking layer is, for example, TFB.
  • FIG. 1 shows an example of a layer structure of a photodetector
  • FIG. 2 shows transmission spectra according to the prior art
  • FIG. 3 shows a graph in which transmission spectra are directly compared
  • FIG. 4 shows the influence on the electronic properties of the system
  • FIG. 5 shows an example of an additionally introduced component according to the invention.
  • FIG. 1 An exemplary embodiment of the structure of the organic photodiodes can be seen from FIG.
  • the structure is shown in the form of a stack consisting of top electrode 5, bottom electrode 3, the carrier substrate 1 and the organic photodiode layer 4.
  • Layer 6 shows a hole transporter that may be present but not necessarily present.
  • the actual photoconductive layer is designated by the reference numeral 4.
  • the photoconductive organic layer 4 may be a so-called "bulk heterojunction", for example realized as a blend of a hole-transporting polythiophene and an electron-transporting fullerene derivative.
  • the bottom electrode 3 may consist of indium tin oxide (ITO) or of another metal.
  • the top electrode 5 can consist of aluminum (Al) or, for example, also of a Ca / Ag layer system or of LiF / Al.
  • FIG. 2 shows the state of the art:
  • the transmission spectra of P3HT: PCBM layers as a function of the layer thicknesses can be seen.
  • the top, only 22nm thick layer is the one with the highest transmission, which can be explained simply by the layer thickness.
  • the other layers are in between, both in the layer thicknesses as well as in the transmission. It can be seen that the variation of the layer thicknesses alters the strength of the transmission, but not the shape of the spectrum.
  • the processing technologies of organic materials e.g. Spin coating makes it possible to produce very thin layers and to adjust their thickness within certain limits.
  • the transmission can be increased by reducing the layer thickness, the spectral distribution is not.
  • the electronic performance of the diodes usually becomes significantly worse, since with the low layer thicknesses ( ⁇ 70 nm), the dark currents and also the frequency of device short circuits increase sharply.
  • FIG. 3 shows the transmission spectra of different photoactive layers of approximately the same thickness (about 40 nm).
  • the shape of the spectrum can be changed.
  • the P3HT: PCBM layer (graph with a minimum at about 520 nm) has a higher transmission at about 390 nm, while the layer (maximum at about 420 nm) according to the invention shows a higher transmission in the range of 500 nm.
  • FIG. 4 shows a comparison of the current-voltage characteristics of equally thick photoactive layers, one according to the prior art and one according to the invention with and without illumination. It can be seen that the graphs differ only slightly from each other, so that the influence of the additional component (s) on the electronic properties of the system can be described as low.
  • the layer thicknesses of the layers shown are the same and about 40nm.
  • FIG. 5 shows an example of an additionally introduced component, the material ADS250BE from American Dye Source.
  • the invention features an organic semiconductor blend or organic photoactive layer comprising a layer of a hole transporting and an electron transporting component with optimized transmission properties.
  • the transmission is optimized by introducing into the organic photoactive layer a further component which alters the transmission spectrum of the mixture or of the layers.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Electromagnetism (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention relates to an organic photo-detector having adjustable transmission and to a production method thereof. The invention describes an organic semiconductor blend or an organic photoactive layer, comprising at least one layer made of a hole-transporting component and an electron-transporting component, having optimized transmission properties. Transmission is optimized in that the organic photoactive layer is provided with an additional component, which changes the transmission spectrum of the mixture or the layers.

Description

Beschreibungdescription

Organischer Photodetektor mit einstellbarer Transmission, sowie Herstellungsverfahren dazuOrganic photodetector with adjustable transmission and manufacturing process

Die Erfindung betrifft einen organischen Photodetektor, der eine einstellbare Transmission hat und ein Herstellungsverfahren dazu.The invention relates to an organic photodetector having an adjustable transmission and a manufacturing method thereof.

Organische Photodetektoren, wie sie beispielsweise aus derOrganic photodetectors, such as those from the

DE 10 2005 037 290.2 bekannt sind, umfassen in der Regel ein Schichtsystem aus einer unteren ggf. metallischen Elektrode, einer photoaktiven Schicht, die beispielsweise ein Blend (Mischung) verschiedener Komponenten sein kann und einer Gegen- elektrode, die wiederum metallisch sein kann.DE 10 2005 037 290.2 are known, usually comprise a layer system of a lower possibly metallic electrode, a photoactive layer which may be, for example, a blend of different components and a counter electrode, which in turn may be metallic.

Im Gegensatz zu den meisten handelsüblichen anorganischen Photodetektoren können organische Photodetektoren mit einer organischen photoaktiven Schicht semitransparent hergestellt werden. Diese Schicht umfasst in der Regel zwei Komponenten, die entweder als separate Schichten oder als Blend vorliegen können .In contrast to most commercially available inorganic photodetectors, organic photodetectors with an organic photoactive layer can be produced semitransparently. This layer usually comprises two components, which may be present either as separate layers or as a blend.

Dabei wird, um die Transmission zu erhohen, die Schichtdicke des Schichtsystems derart verringert, dass die Schichten allein schon wegen der Reduktion ihrer Schichtdicke durchscheinend werden, also erhöhte Transmission aufweisen.In this case, in order to increase the transmission, the layer thickness of the layer system is reduced in such a way that the layers alone become translucent due to the reduction in their layer thickness, ie have increased transmission.

Nachteilig daran ist, dass die spektrale Verteilung der Transmission durch die Verringerung der Schichtdicke nicht beeinflusst werden kann, so dass lediglich durch in Kauf nehmen einer ansonsten schlechteren Performance des Detektors, insbesondere im Hinblick auf Dunkelstrome, wegen der geringen Schichtdicke die Transmission des Detektors insgesamt erhöht werden kann.The disadvantage of this is that the spectral distribution of the transmission can not be influenced by the reduction of the layer thickness, so that only by accepting an otherwise poorer performance of the detector, especially with respect to dark currents, because of the small layer thickness increases the transmission of the detector as a whole can be.

Aufgabe der vorliegenden Erfindung ist es deshalb, einen organisch basierten Photodetektor zur Verfugung zu stellen, bei 200 6174 96The object of the present invention is therefore to provide an organically based photodetector, in 200 6174 96

dem die spektrale Verteilung der Transmission gezielt verändert werden kann. Außerdem ist es Aufgabe der Erfindung ein Verfahren zur Herstellung eines Photodetektors anzugeben.in which the spectral distribution of the transmission can be selectively changed. It is another object of the invention to provide a method for producing a photodetector.

Diese Aufgabe wird durch den Gegenstand des unabhängigen Anspruchs 1 gelost.This object is achieved by the subject matter of independent claim 1.

Gegenstand der Erfindung ist daher ein Photodetektor auf Basis organischer Halbleiter, ein Schichtsystem umfassend, bei dem sich zwischen einer unteren Elektrode und einer oberenThe invention therefore relates to a photodetector based on organic semiconductors, comprising a layer system in which between a lower electrode and an upper

Gegenelektrode eine photoaktive Schicht befindet, die in einem Blend und/oder in einem Schichtaufbau zumindest drei Komponenten enthalt, die als Loch- und/oder Elektronentransportkomponente wirken. Außerdem ist Gegenstand der Erfindung ein Verfahren zur Herstellung eines Photodetektors, wobei auf eine zumindest semitransparente untere Elektrode eine Blendschicht aufgeschleudert wird, auf die wiederum eine weitere zumindest semitransparente Topelektrode aufgebracht wird.Counter-electrode is a photoactive layer containing at least three components in a blend and / or in a layer structure, which act as a hole and / or electron transport component. In addition, the invention relates to a method for producing a photodetector, wherein on an at least semitransparent lower electrode, a blend layer is spun onto which in turn a further at least semitransparent top electrode is applied.

In der Regel fungieren Lochtransportkomponenten als Elektronendonatoren und Elektronentransportkomponenten als Elektronenakzeptoren .As a rule, hole transport components act as electron donors and electron transport components as electron acceptors.

Nach einer bevorzugten Ausfuhrungsform werden zwei oder meh- rere Lochtransportkomponenten kombiniert, da in der Regel diese das Absorptionsverhalten des Blends dominieren.According to a preferred embodiment, two or more hole transport components are combined, since these usually dominate the absorption behavior of the blend.

Soll ein Bild mit dem Flachbilddetektor aufgenommen werden, so durchdringt die dem Bild zugeordnete Lichtverteilung die der Lichtverteilung zugewandte Elektrode, die daher aus einem zumindest semitransparentem Material gefertigt ist. Des Weiteren wandelt die Halbleiterschicht in Verbindung mit den beiden Elektroden die Lichtverteilung in elektrische Signale um, die an den einzelnen Teilelektroden der strukturierten Elektrode anliegen.If an image is to be recorded with the flat-panel detector, the light distribution associated with the image penetrates the electrode which faces the light distribution and is therefore made of an at least semitransparent material. Furthermore, the semiconductor layer in conjunction with the two electrodes converts the light distribution into electrical signals which are applied to the individual sub-electrodes of the structured electrode.

In dieser Halbleiterschicht befindet sich beispielsweise ein Blend aus den beiden Komponenten P3HT (Absorber-, Elektronen- 200 6174 96In this semiconductor layer is, for example, a blend of the two components P3HT (absorber, electron 200 6174 96

donator und Lochtransportkomponente) und PCBM (Elektronenakzeptor und -transportkomponente) , die als Bulk-Heterojunction wirkt, das heißt die Trennung der Ladungsträger erfolgt an den Grenzflachen der beiden Materialien, die sich innerhalb des gesamten Schichtvolumens ausbilden. Ebenso gut kann die Halbleiterschicht als eine mehrere Einzelschichten umfassende Schicht aufgebaut sein, in der Lochtransportkomponente und Elektronentransportkomponente in separaten Schichten vorliegen .donor and hole transport component) and PCBM (electron acceptor and transport component), which acts as a bulk heterojunction, that is, the separation of the charge carriers occurs at the interfaces of the two materials that form within the entire layer volume. As well, the semiconductor layer may be constructed as a multiple monolayer comprising layer in the hole transport component and electron transport component in separate layers.

Gemäß der Erfindung werden nun weitere Materialien zugegeben, die das Transmissionsspektrum der BuIk Heterojunction verandern, bevorzugt gezielt verandern. So können z.B. neben P3HT weitere Lochtransportkomponenten zugegeben werden, beispiels- weise solche, die im sichtbaren Bereich wenig absorbieren o- der bei anderen Wellenlangen als die im Blend vorliegenden Komponenten absorbieren. Je nach gewünschtem Transmissionsspektrum müssen die Anteile der zusatzlichen Lochtransportkomponenten entsprechend gewählt werden.According to the invention, further materials are now added which change the transmission spectrum of the BuIk heterojunction, preferably selectively alter it. Thus, e.g. in addition to P3HT further hole transport components are added, for example those which absorb little in the visible range or absorb at wavelengths other than the components present in the blend. Depending on the desired transmission spectrum, the proportions of the additional hole transport components must be selected accordingly.

Es gibt verschiedene Absorber-, Lochtransport-, Elektronenakzeptor- und/oder Elektronentransportkomponenten, die zusatzlich zu den Basiskomponenten wie P3HT/PCBM in die BuIk Heterojunction eingebracht werden können, beispielsweise Kopoly- mere aus Triarylaminkomponenten und Fluorenen (wie ADS250BE von American Dye Source) und/oder Kopolymere aus Triarylaminkomponenten und Spirobifluorenkomponenten und/oder PoIy (para- phenylenvinylen) -Derivate (z.B. MEH-PPV oder MDMO-PPV) und/oder weitere Polythiophen-Derivate (z.B. P3OT) .There are various absorber, hole transport, electron acceptor and / or electron transport components which can be introduced into the BuIk heterojunction in addition to the basic components such as P3HT / PCBM, for example copolymers of triarylamine components and fluorene (such as ADS250BE from American Dye Source) and or copolymers of triarylamine components and spirobifluorene components and / or poly (para-phenylenevinylene) derivatives (eg MEH-PPV or MDMO-PPV) and / or further polythiophene derivatives (eg P3OT).

Durch die Einfuhrung zumindest einer dritten Komponente in die Bulk-Heterojunction und/oder den Schichtaufbau der Photoaktiven Schicht kann - bei nur geringem Einfluss auf die elektronischen Eigenschaften der photoaktiven Schicht - deren spektrale Eigenschaften, also das Transmissionsverhalten spektral und/oder prozentual verändert werden. 200 6174 96By introducing at least one third component into the bulk heterojunction and / or the layer structure of the photoactive layer, its spectral properties, ie the transmission behavior, can be altered spectrally and / or percent-with only a slight influence on the electronic properties of the photoactive layer. 200 6174 96

Durch die Herstellung von Photodioden aus geeigneten Gemischen organischer Materialien kann das Transmissionsspektrum an die jeweilige Anwendung angepasst werden. So kann z.B. die Farbe, mit der die Detektoroberflache wahrgenommen wird, be- einflusst werden.By producing photodiodes from suitable mixtures of organic materials, the transmission spectrum can be adapted to the respective application. Thus, e.g. the color with which the detector surface is perceived, be influenced.

Ein weiterer Vorteil dabei ist, dass durch Substitution der absorbierenden Komponente, beispielsweise des P3HT, durch ein transparentes Material mit ahnlichen Ladungstransporteigen- Schäften oder ein transparentes Material, das den elektrischen Transport nicht behindert, die Transmission bei konstanter Schichtdicke ein einem weiten Bereich verändert werden kann, ohne den Dunkelstrom und die Kurzschlussanfallig- keit der Photodetektoren zu erhohen.Another advantage is that by substituting the absorbing component, for example P3HT, with a transparent material having similar charge transport properties or a transparent material which does not hinder the electrical transport, the transmission can be varied over a wide range at a constant layer thickness without increasing the dark current and the short circuit susceptibility of the photodetectors.

Die Erfindung betrifft nicht nur Photodioden auf polymerer Basis, sondern kann auch auf photoaktive Schichten, die auf so genannten small molecules oder auf Nanopartikel basieren, angewendet werden.The invention not only relates to photodiodes on a polymer basis, but can also be applied to photoactive layers based on so-called small molecules or nanoparticles.

Bei der Herstellung des Photodetektors nach der Erfindung wird beispielsweise wie folgt vorgegangen: Auf eine semitransparente Bottomelektrode (z.B. ITO) wird eine Blendschicht aufgeschleudert . Dazu werden die Blendkomponenten in einem geeigneten Losungsmittel (z.B. Chloroform oder Xylol) gelost. Auf die Blendschicht wird eine semitransparente Topelektrode (z.B. ein dünnes Schichtsysteme aus Ca und Ag) aufgebracht (z.B. durch thermisches Aufdampfen) .In the manufacture of the photodetector according to the invention, the procedure is, for example, as follows: onto a semitransparent bottom electrode (for example ITO), a blend layer is spin-coated. For this, the blend components are dissolved in a suitable solvent (e.g., chloroform or xylene). A semitransparent top electrode (e.g., a thin layer system of Ca and Ag) is applied to the blend layer (e.g., by thermal evaporation).

Organisch basierte Photodetektoren können relativ einfach hergestellt werden, indem die organische Halbleiterschicht mit drucktechnischen Methoden aus der Losung aufgebracht wird. Außerdem weisen organische Photodetektoren eine relativ hohe Kompatibilität zu verschiedenen elektronischen Ansteue- rungstechnologien auf.Organic-based photodetectors can be produced relatively simply by applying the organic semiconductor layer to the solution using printing methods. In addition, organic photodetectors have relatively high compatibility with various electronic driver technologies.

Ein organischer Photodetektor kann zusatzlich zur photoaktiven Schicht, die beispielsweise P3HT/PCBM, CuPc/PTCBI, 200 6174 96An organic photodetector may be used in addition to the photoactive layer, for example P3HT / PCBM, CuPc / PTCBI, 200 6174 96

ZNPC/C60, konjugierte Polymer-Komponenten oder Fulleren- Komponenten umfasst, eine Elektron/ Loch blockierende Schicht umfassen. Elektron/ Loch blockierende Schichten sind aus der Technologie für organische LEDs bekannt. Ein geeignetes orga- nisches Material für die Elektron blockierende Schicht ist zum Beispiel TFB.ZNPC / C60, conjugated polymer components or fullerene components, comprise an electron / hole blocking layer. Electron / hole blocking layers are known from organic LED technology. A suitable organic material for the electron blocking layer is, for example, TFB.

Im Folgenden wird die Erfindung noch anhand einiger Figuren, die verschiedene Ausfuhrungsformen zeigen, naher erläutert:In the following, the invention will be explained in more detail with reference to some figures which show different embodiments:

Figur 1 zeigt ein Beispiel für einen Schichtaufbau eines Photodetektors ,FIG. 1 shows an example of a layer structure of a photodetector,

Figur 2 zeigt Transmissionsspektren nach dem Stand der Tech- nik,FIG. 2 shows transmission spectra according to the prior art,

Figur 3 zeigt eine Graphik in der Transmissionsspektren direkt verglichen werden,FIG. 3 shows a graph in which transmission spectra are directly compared;

Figur 4 zeigt den Einfluss auf die elektronischen Eigenschaften des Systems undFIG. 4 shows the influence on the electronic properties of the system and

Figur 5 schließlich zeigt ein Beispiel für eine zusatzlich eingebrachte Komponente gemäß der Erfindung.Finally, FIG. 5 shows an example of an additionally introduced component according to the invention.

Ein Ausfuhrungsbeispiel für den Aufbau der organischen Photodioden ist aus Figur 1 ersichtlich. Der Aufbau ist in Form eines Stacks dargestellt, bestehend aus Topelektrode 5, Bottomelektrode 3, dem Tragersubstrat 1 sowie der organischen Photodiodenschicht 4.An exemplary embodiment of the structure of the organic photodiodes can be seen from FIG. The structure is shown in the form of a stack consisting of top electrode 5, bottom electrode 3, the carrier substrate 1 and the organic photodiode layer 4.

Es ist ein Beispiel für den Aufbau eines organischen Photodetektors im Schichtaufbau (Stack) mit zwei aktiven organischen Schichten 4 und 6 zu sehen. Die Schicht 6 zeigt einen Loch- transporter, der vorhanden sein kann, aber nicht unbedingt vorhanden sein muss. Die eigentliche photoleitfahige Schicht ist mit der Bezugsziffer 4 bezeichnet. Zusatzlich zu den gezeigten Schichten 5, 3, 1, 4 und ggf. 6 ist noch der Schutz 200 6174 96An example of the construction of an organic photodetector in the stacked structure with two active organic layers 4 and 6 can be seen. Layer 6 shows a hole transporter that may be present but not necessarily present. The actual photoconductive layer is designated by the reference numeral 4. In addition to the shown layers 5, 3, 1, 4 and possibly 6 is still the protection 200 6174 96

des Photodetektors mittels einer Verkapselung zweckmäßig. Die photoleitfahige organische Schicht 4 kann eine so genannte „Bulk Heterojunction" sein, z. B. realisiert als Blend aus einem lochtransportierenden Polythiophen und einem Elektronen transportierenden Fulleren-Derivat .of the photodetector by means of an encapsulation appropriate. The photoconductive organic layer 4 may be a so-called "bulk heterojunction", for example realized as a blend of a hole-transporting polythiophene and an electron-transporting fullerene derivative.

Die Bottomelektrode 3 (Anode) kann aus Indium-Zinn-Oxid bestehen (ITO) oder aus einem anderen Metall. Die Topelektrode 5 (Kathode) kann aus Aluminium (Al) bestehen oder beispiels- weise auch aus einem Ca/Ag-Schichtsystem oder auch aus LiF/Al.The bottom electrode 3 (anode) may consist of indium tin oxide (ITO) or of another metal. The top electrode 5 (cathode) can consist of aluminum (Al) or, for example, also of a Ca / Ag layer system or of LiF / Al.

Figur 2 zeigt den Stand der Technik: Zu sehen sind die Transmissionsspektren von P3HT : PCBM-Schichten in Abhängigkeit von den Schichtdicken. Die oberste, nur noch 22nm dicke Schicht ist die mit der höchsten Transmission, was einfach durch die Schichtdicke zu erklaren ist. Ganz unten mit der geringsten Transmission ist das Spektrum der dicksten Vergleichsschicht, eine 130nm dicke Schicht, zu sehen. Die anderen Schichten liegen dazwischen, sowohl in den Schichtdicken, als auch in der Transmission. Man erkennt, dass sich durch die Variation der Schichtdicken zwar die Starke der Transmission ändert, nicht aber die Form des Spektrums .FIG. 2 shows the state of the art: The transmission spectra of P3HT: PCBM layers as a function of the layer thicknesses can be seen. The top, only 22nm thick layer is the one with the highest transmission, which can be explained simply by the layer thickness. At the bottom, with the lowest transmission, is the spectrum of the thickest comparative layer, a 130nm thick layer. The other layers are in between, both in the layer thicknesses as well as in the transmission. It can be seen that the variation of the layer thicknesses alters the strength of the transmission, but not the shape of the spectrum.

Die Prozessierungstechnologien organischer Materialien, wie z.B. Spin Coating, ermöglicht es, sehr dünne Schichten herzustellen und in gewissen Grenzen deren Dicke einzustellen. Durch die Reduktion der Schichtdicke kann zwar die Transmission erhöht werden, allerdings die spektrale Verteilung nicht. Hinzu kommt, dass bei hohen Transmissionswerten (z.B. >50% im Sichtbaren) die elektronische Performance der Dioden normalerweise deutlich schlechter wird, da bei den geringen Schichtdicken (< 70nm) die Dunkelstrome und auch die Häufigkeit von Device-Kurzschlussen stark ansteigen.The processing technologies of organic materials, e.g. Spin coating makes it possible to produce very thin layers and to adjust their thickness within certain limits. Although the transmission can be increased by reducing the layer thickness, the spectral distribution is not. In addition, at high transmission values (for example,> 50% in the visible), the electronic performance of the diodes usually becomes significantly worse, since with the low layer thicknesses (<70 nm), the dark currents and also the frequency of device short circuits increase sharply.

Figur 3 zeigt die Transmissionsspektren unterschiedlicher photoaktiver Schichten etwa gleicher Dicke (ca. 40nm) . Durch teilweises Ersetzen des P3HT durch das Material ADS250BE der 200 6174 96FIG. 3 shows the transmission spectra of different photoactive layers of approximately the same thickness (about 40 nm). By partially replacing the P3HT with the material ADS250BE the 200 6174 96

Firma American Dye Source (Struktur siehe Figur 5) kann die Form des Spektrums verändert werden. So weist die P3HT: PCBM- Schicht (Graph mit einem Minimum bei ca. 520nm) eine höhere Transmission bei etwa 390nm auf, wahrend die Schicht (Maximum bei ca. 420nm) gemäß der Erfindung im Bereich von 500nm eine höhere Transmission zeigt.Company American Dye Source (structure see Figure 5), the shape of the spectrum can be changed. Thus, the P3HT: PCBM layer (graph with a minimum at about 520 nm) has a higher transmission at about 390 nm, while the layer (maximum at about 420 nm) according to the invention shows a higher transmission in the range of 500 nm.

Figur 4 zeigt einen Vergleich der Stromspannungskennlinien von gleich dicken photoaktiven Schichten, eine nach dem Stand der Technik und eine gemäß der Erfindung mit und ohne Beleuchtung. Zu erkennen ist, dass die Graphen jeweils nur wenig voneinander abweichen, so dass der Einfluss der zusatzlichen Komponente (n) auf die elektronischen Eigenschaften des Systems als gering bezeichnet werden kann. Die Schichtdicken der gezeigten Schichten sind gleich und ungefähr 40nm.FIG. 4 shows a comparison of the current-voltage characteristics of equally thick photoactive layers, one according to the prior art and one according to the invention with and without illumination. It can be seen that the graphs differ only slightly from each other, so that the influence of the additional component (s) on the electronic properties of the system can be described as low. The layer thicknesses of the layers shown are the same and about 40nm.

Figur 5 schließlich zeigt ein Beispiel für eine zusatzlich eingeführte Komponente, das Material ADS250BE der Firma American Dye Source.Finally, FIG. 5 shows an example of an additionally introduced component, the material ADS250BE from American Dye Source.

Die Erfindung zeigt ein organisches Halbleiterblend oder eine organische photoaktive Schicht, die eine Schicht einer lochtransportierenden und einer Elektronen transportierenden Komponente umfasst, mit optimierten Transmissionseigenschaften. Die Transmission wird dadurch optimiert, dass in der organischen photoaktiven Schicht eine weitere Komponente eingebracht wird, die das Transmissionsspektrum der Mischung oder der Schichten verändert. The invention features an organic semiconductor blend or organic photoactive layer comprising a layer of a hole transporting and an electron transporting component with optimized transmission properties. The transmission is optimized by introducing into the organic photoactive layer a further component which alters the transmission spectrum of the mixture or of the layers.

Claims

200 6174 96Patentansprüche : 200 6174 96Patent claims: 1. Photodetektor auf Basis organischer Halbleiter, ein Schichtsystem umfassend, bei dem sich zwischen einer unteren Elektrode und einer oberen Gegenelektrode eine photoaktive Schicht befindet, die in einem Blend und/oder in einem Schichtaufbau zumindest drei Komponenten enthalt, die als Loch- und/oder Elektronentransportkomponente wirken.1. A photodetector based on organic semiconductors, comprising a layer system in which between a lower electrode and an upper counter electrode is a photoactive layer containing at least three components in a blend and / or in a layer structure, as a perforated and / or Electron transport component act. 2. Photodetektor nach Anspruch 1, wobei in der photoaktiven Schicht zumindest zwei Lochtransportkomponenten kombiniert vorliegen .2. Photodetector according to claim 1, wherein in the photoactive layer at least two hole transport components are combined. 3. Photodetektor nach einem der vorstehenden Ansprüche, wobei die photoaktive Schicht ein Blend aus den Komponenten3. Photodetector according to one of the preceding claims, wherein the photoactive layer is a blend of the components P3HT/PCBM/ADS250BE umfasst.P3HT / PCBM / ADS250BE. 4. Verfahren zur Herstellung eines Photodetektors, wobei auf eine zumindest semitransparente untere Elektrode (3) eine Blendschicht (4) aufgeschleudert wird, auf die wiederum eine weitere zumindest semitransparente Topelektrode (5) aufgebracht wird. 4. A method for producing a photodetector, wherein on an at least semitransparent lower electrode (3) a blend layer (4) is spun onto which in turn a further at least semi-transparent top electrode (5) is applied.
PCT/EP2008/056660 2007-06-04 2008-05-30 Organic photo-detector having adjustable transmission and a production method thereof Ceased WO2008148705A1 (en)

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