Patent Application
20200035924
This invention relates to organic photodetectors.
There is an increased interest in the development of organic photosensitive electronic devices as alternatives to inorganic photoelectronic devices because they provide high flexibility and may be manufactured and processed at relatively low costs by using low temperature vacuum deposition or solution processing techniques.
As examples of organic photosensitive electronic devices, organic photovoltaic devices (OPVs) and organic photodetectors (OPDs) may be mentioned. Such an organic photosensitive electronic device may include as a photoactive layer a p-n junction of a donor/acceptor blend which enables the device to convert incident radiation into electrical current.
Examples of p-type (electron donor) materials are conjugated organic oligomers or polymers (e.g. oligomers or polymers of thiophenes, phenylenes, fluorenes, polyacetylenes, benzathiadiazoles and combinations thereof), whereas fullerene and fullerene derivatives (e.g. C60PCBM and C70PCBM) are known n-type (electron acceptor) materials (see e.g. EP 1 447 860 A1 and US 2012/205596).
In the case of an organic photodetector device, the current flowing through the device in the absence of any photons incident on the device, known as dark current, may affect the limit of detection of the device.
US 2005/110007 discloses an organic photodetector comprising an anode having a work function greater than about 4.6 eV, one or more subcells in series, each subcell comprising an organic electron donor layer and an organic electron acceptor layer having a thickness low enough to allow tunneling, an exciton blocking layer and a cathode.
U.S. Pat. No. 9,484,537 discloses an organic photodiode having dual electron blocking layers formed next to the anode.
US 2014/0134781 discloses an organic photovoltaic device comprising an indium-tin oxide (ITO) anode and a hole-transporting layer thereon.
It is an object of the invention to provide organic photodetectors having low dark current.
It is a further object of the invention to provide organic photodetectors having low dark current and high efficiency.
The present inventors have found that dark current may be reduced by using an anode having a work function greater than 5.0 eV.
Accordingly, in a first aspect the invention provides an organic photodetector comprising an anode, a cathode and a photoactive layer comprising an organic electron donor and an organic electron acceptor between the anode and the cathode wherein the anode comprises a material having a work function of at least 5.0 eV from vacuum level.
The present inventors have found that dark current of an organic photodetector may be reduced by selecting the anode-electron acceptor LUMO level gap.
Accordingly, in a second aspect the invention provides an organic photodetector comprising an anode, a cathode and a photoactive layer comprising an organic electron donor and an organic electron acceptor between the anode and the cathode wherein the LUMO of the electron acceptor is at least 1.2 eV closer to vacuum than the work function of the anode.
The materials of the organic photodetector including, without limitation, the anode, the cathode, the photoactive layer, the organic electron donor and the organic electron acceptor may be as described anywhere herein with reference to the first aspect.
In a third aspect the invention provides a method of forming an organic photodetector according to the first or second aspect, the method comprising:
The invention will now be described in more detail with reference to the Figures in which:
The bulk heterojunction layer optionally has a thickness in the range of about 50-3000 nm, preferably 300-1500 nm.
The photoactive layer may have a substantially uniform ratio of electron acceptor and electron donor throughout the thickness of the photoactive layer or the ratio thereof may vary gradually or stepwise throughout the thickness of the photoactive bulk heterojunction layer.
One or more further layers may be provided between the anode and the cathode. A hole-transporting layer may be provided between the anode and the bulk heterojunction layer. An electron-transporting layer may be provided between the cathode and the bulk heterojunction layer. Preferably, the anode consists of a single layer in direct contact with the bulk heterojunction layer.
In another arrangement, the bulk heterojunction layer is between the cathode and the substrate. In this case, the anode may be supported on the substrate and the bulk heterojunction layer and the cathode may be formed over the anode.
The anode 103 and the cathode 107 are connected to circuitry which may include a voltage source for applying a reverse bias to the device and a detector (e.g. current meter or readout device, wired in series with the reverse bias voltage source, as detection circuit), for example, to measure the generated photocurrent. Conversion of light incident on the bulk heterojunction layer into electrical current may be detected in reverse bias mode.
The electron donor material has a LUMO that is shallower than the LUMO of the electron acceptor material. Optionally, the gap between the LUMO acceptor and the LUMO donor is at least 0.1 eV.
Optionally, the electron donor material has a LUMO of up to 3.5 eV from vacuum level, optionally 3.0-3.5 eV from vacuum level.
Optionally, the electron donor material has a HOMO level of no more than 5.5 eV from vacuum level.
Optionally, the electron acceptor material has a LUMO level more than 3.5 eV from vacuum level, optionally 3.6-4.0 eV from vacuum level.
Preferably, the LUMO of the electron acceptor is at least 1.2 eV, optionally at least 1.4 eV closer to vacuum than the work function of the anode
HOMO and LUMO levels as described herein are as measured by square wave voltammetry.
The anode preferably comprises or consists of a material having a work function of at least 5.0 eV, preferably at least 5.1 eV, at least 5.2 eV or at least 5.3 eV. The anode may have a work function in the range of 5.0-6.0 eV.
The anode preferably consists of the material having a work function of at least 5.0 eV. If one or more further materials are present in the anode then the material having a work function of at least 5.0 eV preferably makes up at least 60 wt % of the anode.
The material having a work function of at least 5.0 eV may be, without limitation, a metal for example gold; a conductive metal compound for example a conductive metal oxide such as molybdenum, or a conductive polymer. The material is preferably a conductive polymer. Exemplary conductive polymers are fused or unfused polythiophenes, optionally poly(ethylenedioxythiophene) (PEDOT) having a charge-balancing polyanion, optionally polystyrene sulfonate (PSS). The anode may comprise, in addition to the conductive polymer, a charge-neutral derivative of the polyanion, for example a protonated polyacid or a salt thereof, such as polystyrene sulfonic acid (PSSH) or a salt thereof.
The anode may be deposited from an anode formulation comprising or consisting of the material or materials of the anode dissolved or dispersed in one or more liquid materials. Preferably, the only liquid material is water, or the liquid materials comprise water and one or more water-miscible liquid materials, optionally one or more protic or aprotic organic liquid materials, optionally DMSO. The anode formulation may comprise a surfactant. The surfactant may be a non-ionic or ionic surfactant. The surfactant may be a fluorinated surfactant.
Following deposition of the anode formulation, the anode layer may be heated. If the anode formulation is deposited over the bulk heterojunction layer then heating is preferably at a temperature below 150° C., optionally at a temperature in the range of 80-150° C.
The work function of the anode may be affected by factors including, without limitation: the anode material; constituents of an anode formulation other than the anode material, for example the liquids of the anode formulation and any additives present in the anode layer, for example any surfactants; the heating temperature of an anode layer.
If the anode formulation is deposited directly onto the bulk heterojunction layer then the materials of the bulk heterojunction layer preferably undergo little or no dissolution on contact with the liquid material or materials of the anode formulation. Optionally, the bulk heterojunction layer is deposited from a formulation comprising one or more non-polar solvents, optionally a substituted benzene as described in more detail below, and the anode is deposited onto the bulk heterojunction layer from an anode formulation.
It will be understood that the electron donor may be a single electron donor material or a mixture of two or more electron donor materials, and the electron acceptor may consist of a single electron acceptor material or may be a mixture of two or more electron acceptor materials.
The electron acceptor and the electron donor may each independently be a polymeric material or a non-polymeric material.
Preferably, the electron donor is a polymer. Electron donor polymers are optionally selected from conjugated hydrocarbon or heterocyclic polymers including polyacene, polyaniline, polyazulene, polybenzofuran, polyfluorene, polyfuran, polyindenofluorene, polyindole, polyphenylene, polypyrazoline, polypyrene, polypyridazine, polypyridine, polytriarylamine, poly(phenylene vinylene), poly(3-substituted thiophene), poly(3,4-bisubstituted thiophene), polyselenophene, poly(3-substituted selenophene), poly(3,4-bisubstituted selenophene), poly(bisthiophene), poly(terthiophene), poly(bisselenophene), poly(terselenophene), polythieno[2,3-b]thiophene, polythieno[3,2-b]thiophene, polybenzothiophene, polybenzo[1,2-b:4,5-b′]dithiophene, polyisothianaphthene, poly(monosubstituted pyrrole), poly(3,4-bisubstituted pyrrole), poly-1,3,4-oxadiazoles, polyisothianaphthene, derivatives and co-polymers thereof. Preferred examples electron-donor polymers are copolymers of polyfluorenes and polythiophenes, each of which may be substituted, and polymers comprising benzothiadiazole-based and thiophene-based repeating units, each of which may be substituted. The electron donor preferably comprises a repeat unit of formula (I):
wherein R1 in each occurrence is independently H or a substituent.
Optionally, each R1 is independently selected from the group consisting of:
C1-20 alkyl wherein one or more non-adjacent, non-terminal carbon atoms of the alkyl group may be replaced with O, S or C═O and wherein one or more H atoms of the C1-20 alkyl may be replaced with F; an aryl or heteroaryl group, preferably phenyl, which may be unsubstituted or substituted with one or more substituents; and fluorine.
Substituents of an aryl or heteroaryl group are optionally selected from F, CN, NO2 and C1-20 alkyl wherein one or more non-adjacent, non-terminal carbon atoms of the alkyl group may be replaced with O, S or C═O.
By “non-terminal” as used herein is meant a carbon atom other than the methyl group of a linear alkyl (n-alkyl) chain and the methyl groups of a branched alkyl chain.
A polymer comprising a repeat unit of formula (I) is preferably a copolymer comprising one or more co-repeat units.
The one or more co-repeat units may comprise or consist of one or more of C6-20 monocyclic or polycyclic arylene repeat units which may be unsubstituted or substituted with one or more substituents; 5-20 membered monocyclic or polycyclic heteroarylene repeat units which may be unsubstituted or substituted with one or more substituents.
The one or more co-repeat units may have formula (II):
wherein Ar1 in each occurrence is an arylene group or a heteroarylene group; m is at least 1; R2 is a substituent; R2 in each occurrence is independently a substituent; n is 0 or a positive integer; and two groups R2 may be linked to form a ring.
Optionally, each R2 is independently selected from the group consisting of a linear, branched or cyclic C1-20 alkyl wherein one or more non-adjacent, non-terminal C atoms of the C1-20 alkyl may be replaced with O, S, COO or CO.
Two groups R2 may be linked to form a C1-10 alkylene group wherein one or more non-adjacent C atoms of the alkylene group may be replaced with O, S, COO or CO.
Optionally, m is 2.
Optionally, each Ar1 is independently a 5 or 6 membered heteroarylene group, optionally a heteroarylene group selected from the group consisting of thiophene, furan, selenophene, pyrrole, diazole, triazole, pyridine, diazine and triazine, preferably thiophene.
Optionally, the repeat unit of formula (II) has formula (IIa):
Optionally, the groups R2 are linked to form a 2-5 membered bridging group. Optionally, the bridging group has formula —O—C(R16)2— wherein R16 in each occurrence is independently H or a substituent. Substituents R16 are optionally selected from C1-20 alkyl. Preferably each R16 is H.
An electron-accepting polymer, an electron-donating polymer or an anode polymer as described herein may have a polystyrene-equivalent number-average molecular weight (Mn) measured by gel permeation chromatography in the range of about 1×103 to 1×108, and preferably 1×103 to 5×106. The polystyrene-equivalent weight-average molecular weight (Mw) of the polymers described herein may be 1×103 to 1×108, and preferably 1×104 to 1×107
Preferably, the electron acceptor is a non-polymeric compound, more preferably a fullerene.
The fullerene may be a C60, C70, C76, C78 and C84 fullerene or a derivative thereof including, without limitation, PCBM-type fullerene derivatives (including phenyl-C61-butyric acid methyl ester (C60PCBM), TCBM-type fullerene derivatives (e.g. tolyl-C61-butyric acid methyl ester (C60TCBM)), and ThCBM-type fullerene derivatives (e.g. thienyl-C61-butyric acid methyl ester (C60ThCBM).
Fullerene derivatives may have formula (III):
wherein A, together with the C—C group of the fullerene, forms a monocyclic or fused ring group which may be unsubstituted or substituted with one or more substituents.
Exemplary fullerene derivatives include formulae (IIIa), (IIIb) and (IIIc):
wherein R3-R15 are each independently H or a substituent.
Substituents R3-R15 are optionally and independently in each occurrence selected from the group consisting of aryl or heteroaryl, optionally phenyl, which may be unsubstituted or substituted with one or more substituents; and C1-20 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, CO or COO and one or more H atoms may be replaced with F.
Substituents of aryl or heteroaryl, where present, are optionally selected from C1-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, CO or COO and one or more H atoms may be replaced with F.
At least one of the anode and cathode electrodes is transparent so that light incident on the device may reach the bulk heterojunction layer.
The or each transparent electrode preferably has a transmittance of at least 70%, optionally at least 80%, to wavelengths in the range of 400-900 nm.
Optionally, the cathode comprises
The device may be formed by forming the bulk heterojunction layer over one of the anode and cathode supported by a substrate and depositing the other of the anode or cathode over the bulk heterojunction layer.
The substrate may be, without limitation, a glass or plastic substrate. The substrate is transparent if, in use, incident light is to be transmitted through the substrate and the electrode supported by the substrate.
The substrate supporting one of the anode and cathode may or may not be transparent if, in use, incident light is to be transmitted through the other of the anode and cathode.
The cathode optionally comprises or consists of one or more metals, for example silver or Ag:Mg alloy, or a conductive metal oxide.
Optionally, the cathode comprises or consists of a layer of conductive metal oxide, optionally ITO, wherein a cathode modification layer is provided between the cathode and the bulk heterojunction layer.
The bulk heterojunction layer may be formed by any process including, without limitation, thermal evaporation and solution deposition methods.
Preferably, the bulk heterojunction layer is formed by depositing a formulation comprising the acceptor material and the electron donor material dissolved or dispersed in a solvent or a mixture of two or more solvents. The formulation may be deposited by any coating or printing method including, without limitation, spin-coating, dip-coating, roll-coating, spray coating, doctor blade coating, slit coating, dispense printing, ink jet printing, screen printing, gravure printing and flexographic printing.
In dispense printing, a continuous flow of ink is deposited from a nozzle positioned at a defined distance from the substrate. A desired pattern may be created by a relative movement of the nozzle and the substrate.
By controlling the nozzle dispense rate (solution flow rate), the pattern density (line spacing), the nozzle movement speed (line speed) as well as the ink concentration, the uniformity of the photoactive layer film may be tuned.
The one or more solvents of the formulation may optionally comprise or consist of benzene substituted with one or more substituents selected from chlorine, C1-10 alkyl and C1-10 alkoxy wherein two or more substituents may be linked to form a ring which may be unsubstituted or substituted with one or more C1-6 alkyl groups, optionally toluene, xylenes, trimethylbenzenes, tetramethylbenzenes, anisole, indane and its alkyl-substituted derivatives, and tetralin and its alkyl-substituted derivatives.
The formulation may comprise a mixture of two or more solvents, preferably a mixture comprising at least one benzene substituted with one or more substituents as described above and one or more further solvents. The one or more further solvents may be selected from esters, optionally alkyl or aryl esters of alkyl or aryl carboxylic acids, optionally a C1-10 alkyl benzoate or benzyl benzoate.
The formulation may comprise further components in addition to the electron acceptor, the electron donor and the one or more solvents. As examples of such components, adhesive agents, defoaming agents, deaerators, viscosity enhancers, diluents, auxiliaries, flow improvers colourants, dyes or pigments, sensitizers, stabilizers, nanoparticles, surface-active compounds, lubricating agents, wetting agents, dispersing agents and inhibitors may be mentioned.
The organic photodetector as described herein may be used in a wide range of applications including, without limitation, detecting the presence and/or brightness of ambient light and in a sensor comprising the organic photodetector and a light source. The photodetector may be configured such that light emitted from the light source is incident on the photodetector and changes in wavelength and/or brightness of the light may be detected. The sensor may be, without limitation, a gas sensor, a biosensor, an X-ray imaging device, a motion sensor (for example for use in security applications) a proximity sensor or a fingerprint sensor.
An organic photodetector as described herein may be used in a wide range of applications including, without limitation, detecting the presence and/or brightness of ambient light and in a sensor comprising at least one organic photodetector as described herein and at least one light source. The photodetector may be configured such that light emitted from a light source is incident on the photodetector and changes in wavelength and/or brightness of the light may be detected. An array of photodetectors as described herein may be configured to detect light emitted from a single light source or from two or more light sources. The sensor may be, without limitation, a gas sensor, a biosensor, X-ray imaging or a motion sensor, for example a motion sensor used in security applications, a proximity sensor or a fingerprint sensor.
Work function values as described herein are as measured by an AC2 photoelectron yield spectrometer from Riken Keiki Instruments. Measurements are made in an ambient air environment.
HOMO and LUMO values herein are as measured by square wave voltammetry at room temperature.
In square wave voltammetry, the current at a working electrode is measured while the potential between the working electrode and a reference electrode is swept linearly in time. The difference current between a forward and reverse pulse is plotted as a function of potential to yield a voltammogram.
The apparatus to measure HOMO or LUMO energy levels by SWV may comprise a cell containing tertiary butyl ammonium perchlorate or tertiary butyl ammonium hexafluorophosphate in acetonitrile; a glassy carbon working electrode; a platinum counter electrode and a leak free Ag/AgCl reference electrode. Ferrocene is added directly to the existing cell at the end of the experiment for calculation purposes where the potentials are determined for the oxidation and reduction of ferrocene versus Ag/AgCl using cyclic voltammetry (CV).
Apparatus:
Method
LUMO=4.8-E ferrocene (peak to peak average)−E reduction of sample (peak maximum)
HOMO=4.8-E ferrocene (peak to peak average)+E oxidation of sample (peak maximum)
A typical SWV experiment runs at 15 Hz frequency; 25 mV amplitude and 0.004V increment steps. Results are calculated from 3 freshly spun film samples for both the HOMO and LUMO data.
All experiments are run under an Argon gas purge.
Devices having the following structure were prepared:
A glass substrate coated with silver and a layer of indium-tin oxide (ITO) was treated with polyethyleneimine (PETE) to modify the work function of the ITO. A composition of Donor Polymer 1, illustrated below, and fullerene acceptor C70 PCBM 1:2 w/w was applied by wire bar coating onto the PEIE to form a photoactive layer having a thickness of about 900 nm. The anode was fanned over the photoactive layer by spin-coating a layer of a hole-transporting material supplied by Heraeus, Inc. as set out in Table 1 followed by annealing at 130° C.
HIL E100 and HIL E200 as supplied were diluted with an equal volume of water and 2 wt % of Capstone FS-30 surfactant, available from DuPont, before spin-coating. 5 wt % of DMSO was added to HTL Solar before spin-coating.
Dark current of Device Examples 1 and 2 and Comparative Device 1 were measured. As shown in
External quantum efficiencies of the devices is shown in
Devices were prepared as described with reference to Device Examples 1 and 2 except that fullerene acceptor C70 IPH was used in place of C70 PCBM in a weight ratio of 1:1.7 and the donor/acceptor layer was formed to a thickness of 1.1-1.2 microns and hole transporting materials as set out in Table 2 were used to form the anode in which HIL E100 was supplied by Heraeus, Inc. and AQ1300 was supplied by Solvay. HIL E100 as supplied was modified as described in Device Examples 1 and 2 before spin-coating. AQ1300 was used as supplied.
With reference to
Although the present invention has been described in terms of specific exemplary embodiments, it will be appreciated that various modifications, alterations and/or combinations of features disclosed herein will be apparent to those skilled in the art without departing from the scope of the invention as set forth in the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1704481.9 | Mar 2017 | GB | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/GB2018/050570 | 3/7/2018 | WO | 00 |
