(19)
(11)EP 2 942 826 A2

(12)EUROPEAN PATENT APPLICATION

(43)Date of publication:
11.11.2015 Bulletin 2015/46

(21)Application number: 15167145.0

(22)Date of filing:  11.05.2015
(51)International Patent Classification (IPC): 
H01L 51/42(2006.01)
H01L 51/50(2006.01)
H01L 51/44(2006.01)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
MA

(30)Priority: 09.05.2014 EP 14001735

(71)Applicant: Technische Universität Dresden
01069 Dresden (DE)

(72)Inventors:
  • Polander, Lauren, Dr.
    01159 Dresden (DE)
  • Körner, Christian, Dr.
    01237 Dresden (DE)
  • Leo, Karl, Prof. Dr.
    01062 Dresden (DE)

(74)Representative: Kailuweit & Uhlemann Patentanwälte Partnerschaft mbB 
Bamberger Straße 49
01187 Dresden
01187 Dresden (DE)

  


(54)DOPED PEROVSKITES AND THEIR USE AS ACTIVE AND/OR CHARGE TRANSPORT LAYERS IN OPTOELECTRONIC DEVICES


(57) The invention relates to doped perovskites and their use as active and/or charge transport layers in optoelectronic devices and the manufacturing of an optoelectronic device. The optoelectronic device is arranged on a substrate comprising a first electrode (2) adjacent to the substrate (3) and a second electrode (7) which is arranged on top of the device and at least one layer comprising an perovskite structure which is arranged between the first and the second electrode (2, 7), and wherein the perovskite is doped from 0.001 to 30 wt.-% with a n-type or p-type dopant material based on the total weight of the finished layer or layered in combination with charge-transport materials that are doped from 0.001 to 30 wt.-% with a n-type or p-type dopant material based on the total weight of the finished layer.




Description

TECHNICAL FIELD



[0001] The present invention relates to doped perovskites and/or doped charge-transport layers and their use as active and/or charge transport layers in perovskite-based optoelectronic devices.

BACKGROUND OF INVENTION



[0002] Most modern semiconductor devices use single crystalline layers. For modern electronics, however, using thin films is often advantageous, e.g. for flexible devices. For this purpose, a number of different organic and inorganic materials have been considered. Recently, organic-inorganic perovskites have gained much interest due to their excellent device performance with conversion efficiencies of over 20% (KRICT (2015) New ion continues perovskite solar's flat-out progress Press Release).

[0003] Organic-inorganic perovskites are a particularly promising class of crystalline organic-inorganic hybrids. Their crystalline nature and the rigid, extended inorganic framework provide an opportunity for higher electrical mobility, better thermal stability, and templating of the organic component of the structure. The organic component may consist of a bilayer (e.g. monoammonium) or monolayer (e.g. diammonium) of organic cations.

[0004] The most commonly used organic-inorganic perovskite-structured semiconductors in photovoltaics incorporate methylammonium and lead cations along with halide anions to form the general structure CH3NH3PbX3 where X can be Br, Cl, I, or a mixture therefrom. They exhibit high charge carrier mobility values and remarkably long charge carrier diffusion lengths (> 1 µm) making them particularly well suited for photovoltaic applications (Grätzel, M. (2014) The light and shade of perovskite solar cells. Nat Mater 13, 838-842; Hodes, G. (2013). Perovskite-Based Solar Cells. Science 342 (6156): 317-318). Additionally, the inexpensive precursors and low-temperature deposition techniques compatible for thin-film production make perovskites intriguing for commercial applications.

[0005] Solar cells based on methylammonium trihalide (CH3NH3PbX3, X= Cl, Br, I) pervoskites have been realized in combination with various materials and in different device designs. Examples include a solid-state electrolyte based dye-sensitized configuration using a mesoporous TiO2 photoanode, a meso-superstructured device configuration consisting of a mesoporous alumina insulator scaffold, and a simple planar heterojunction configuration. In these devices, perovskite thin films are most commonly deposited by solution methods (typically spin-coating), but vacuum deposition methods have also been successfully implemented to achieve highly uniform layers (Malinkiewicz, O. et al. (2014) Perovskite solar cells employing organic charge-transport layers. Nat Photon 8, 128-132). Specifically, Liu, et al. described planar heterojunction cells using CH3NH3PbX3 (X = Cl, I) demonstrating efficiencies of 8.6 % for solution processed cells and up to 15.4 % for vacuum deposited analogues (Liu, M. et al. (2013) Efficient planar heterojunction perovskite solar cells by vapor deposition. Nature 501, 395-398).

[0006] Regardless of the form, most of these optoelectronic device architectures use a photoactive perovskite layer combined with solid-state hole- and electron-transport materials to form heterojunctions - designs modeled after those typically used for dye-sensitized solar cells and organic-based photovoltaics. However, in contrast to most inorganic and organic solar cells, active Fermi level control has not yet been employed in the emerging field of perovskite photovoltaics.

[0007] Therefore, it is an object of the present invention to extensively reduce recombination losses in perovskite-based optoelectronic devices (e.g. transistors, light-emitting diodes, solar cells), while favoring high charge-extraction rates and achieve efficiencies beyond the current status.

SUMMARY OF INVENTION



[0008] The present invention is focused on the previously unexplored use of molecular or atomic dopants to achieve Fermi level control within the surrounding layer(s) (preferably charge transport layers) and/or perovskite layer(s) in order improve the performance of hetero-junction perovskite-based optoelectronic devices (e.g., transistors, light-emitting diodes, solar cells) beyond the state-of-the art, but also to fabricate, for the first time, homo-junction perovskite-based devices that could not be otherwise achieved without the use of active Fermi level control. The realization of such devices could specifically revolutionize the solar cell industry by enabling the fabrication of high performance solar cells using readily available precursors, potentially opening the door for very inexpensive, marketable devices.

[0009] In particular, Fermi level control has several key advantages, such as
  • in transistors:

    ∘ reduction of the contact resistance;

    ∘ improvement of the on-off ratio by control of charge carrier concentration in the channel;

  • in light-emitting diodes (LEDs):

    ∘ reduction of the voltage due to lower transport layer and interface resistance;

    ∘ wider choice or possible electrodes;

  • in solar cells:

    ∘ formation of a p-n or p-i-n homojunction, thus avoiding hetero-interfaces in the active region;

    ∘ optimization of the built-in voltage, which helps to extract carriers from the device;

    ∘ the realization of good electrode contact regardless of energy barriers;

    ∘ the use of highly conductive layers, avoiding ohmic losses.



[0010] To achieve these benefits, we propose to use doping techniques. In organic LEDs and solar cells, this technique can be applied both for the perovskites and the other layers in the device architecture. As the doping techniques, we propose to use atomic or molecular addenda to the layers, e.g. such as discussed in a recent article (Walzer, K. et al. (2007) Highly efficient organic devices based on electrically doped transport layers. Chem. Rev. 107, 1233-1271 ), as well as stoichiometric control of the perovskite material itself to achieve Fermi level shift. It has been shown in recent articles that the Fermi level of the perovskite layer can be significantly shifted by substituting one or more atoms in the chemical structure; however, very limited examples have been explored thus far and this approach has been focused on absorption tuning rather than Fermi level alignment in the device.

[0011] In a first aspect, the present invention provides an optoelectronic device that is arranged on a substrate comprising
  1. a) a first electrode adjacent to the substrate and a second electrode which is arranged on top of the device
  2. b) at least one layer comprising an organic-inorganic or inorganic pervoskite structure which is arranged between the first and the second electrode,
wherein the perovskite is doped from 0.001 to 30 percent by weight (wt.-%) with a n-type or p-type dopant material based on the total weight of the finished layer.

[0012] For the sake of clarity, doping hereinafter refers to adding small percentage of an inorganic and/or organic monomolecular interference (e.g. ions ore molecules) into the (poly-)crystalline structure of the perovskite leading to a mixed layer with tuned Fermi level and increased conductivity. The dopant is preferably an electrical dopant. Electrical dopants are classified in p-dopants and n-dopants. Herein "n" or "p" denotes a n(egative) doping or p(ositive) doping which results in an increase in the density of free electrons and holes in the thermal equilibrium state of the doped material, respectively.

[0013] Preferably, the dopant concentration organic-inorganic pervoskite structure is between 0.001 and 30 wt%, more preferably between 0.01 and 15 wt%, most preferably between 0.1 and 10 wt%.

[0014] Advantageously, selecting a doped perovskite as layer material in optoelectronic devices minimizes energy losses while favoring high charge-extraction rates and achieve efficiencies beyond the current status.

[0015] The optoelectronic device is arranged on a substrate, e.g. glass, polymer foil or the like, comprising of a first electrode adjacent to a substrate and a second electrode which is arranged on top of the device acting as a counter electrode. Preferably, between the first and second electrode, at least two layers are present comprising a perovskite and/or other charge transport material(s) that can be doped to control the Fermi level. The optoelectronic device of the invention may and thus function without such a charge transporting material layer.

[0016] In one preferred embodiment of the invention the doped perovskite can simultaneously act as the active layer as well as a charge-transport layer.

[0017] In one preferred embodiment of the invention the layer comprising doped perovskite is the active layer.

[0018] In a further aspect, the invention provides an optoelectronic device as described above, wherein the layer comprising the doped perovskite is at least one charge-transport layer.

[0019] In an embodiment of the invention the charge-transport layer can be a hole-transport layer (HTL) or an electron-transport layer (ETL). Additionally, by doping the perovskite layer, the Fermi level of this layer can be shifted in that way that the perovskite layer can also serve as HTL or ETL.

[0020] In an embodiment of the invention the pervoskite is p-doped wherein the dopant is a molecular dopant chosen to have an electron affinity (EA) larger than 5.0 eV (e.g., F4-TCNQ (Tetrafluoro-tetracyano-quinodimethane, EA = 5.2 eV), F6-TCNNQ (1,3,4,5,7,8-hexafluorotetracyanonaphthoquinodimethane, EA = 5.7 eV), C60F36 (EA = 5.4 eV), NDP9 (proprietary dopant from Novaled, GmbH), molybdenum oxide (EA = 6.7 eV), an inorganic dopant containing atoms selected form group III of the Periodic Table of Elements, or a dopant containing varied halogen atoms such as F, Cl, I and/or organic cations that can incorporate into the perovskite lattice structure.

[0021] In a further embodiment of the invention the pervoskite is n-doped wherein the dopant is a molecular dopant chosen to have an ionization potential (IP) smaller than 4.5 eV (e.g., W2(hpp)4 (Tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)-ditungsten (II), IP = 2.7 eV) or Cr2(hpp)4 (tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)-dichromium (II), IP = 3.9 eV), an inorganic dopant containing atoms selected form group V of the Periodic Table of Elements, or a dopant containing varied halogen atoms such as F, Cl, I and/or organic cations that can incorporate into the perovskite lattice structure.

[0022] In an embodiment of the invention the charge carrier transport layer with doped pervoskite is a hole transport layer (HTL) wherein the dopant is a molecular dopant chosen to have an electron affinity (EA) larger than 5.0 eV (e.g., F4-TCNQ (Tetrafluoro-tetracyano-quinodimethane, EA = 5.2 eV), F6-TCNNQ (1,3,4,5,7,8-hexafluorotetracyanonaphthoquinodimethane, EA = 5.7 eV), C60F36 (EA = 5.4 eV), NDP9 (proprietary dopant from Novaled, GmbH), molybdenum oxide (EA = 6.7 eV).

[0023] In an embodiment of the invention the doped pervoskite layer is an electron transport layer (ETL) wherein the dopant is chosen to have an ionization potential (IP) smaller than 3.5 eV (e.g., W2(hpp)4 (Tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)-ditungsten (II), IP = 2.7 eV) or Cr2(hpp)4 (tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)-dichromium (II), IP = 3.9 eV).

[0024] In a further embodiment of the invention a stack of several layers is arranged between the first and second electrode comprising at least a hole transport layer (HTL) and an electron transport layer (ETL), wherein the perovskite active layer is arranged between HTL and ETL and wherein at least one of the hole transport layer (HTL) or electron transport layer (ETL) is doped.

[0025] In a further embodiment of the invention the HTL and/or ETL comprise several layers, wherein the perovskite active layer is arranged between HTL and ETL and wherein at least one of the hole transport layer (HTL) or electron transport layer (ETL) is doped.

[0026] In a further embodiment of the invention the hole transport layer (HTL) comprises at least one small organic molecule with IP in the range of 4.5-6.0 eV such as selected from, but not limited to the group consisting of Spiro-MeO-TAD, MeO-TPO, Spiro-MeO-TPD, Spiro-TTB, Spiro-TAD or BPAPF, etc.

[0027] In a further embodiment of the invention the electron transport layer (ETL) comprises at least one small organic molecule with EA in the range of 3.0-4.5 eV (e.g., a fullerene, fullerene derivative, etc).

[0028] In a further embodiment of the invention the HTL and/or ETL comprises at least one doped perovskite layer.

[0029] In a further embodiment the electrode is selected of transparent conducting oxide (TCO, ITO, etc.), metal nanowire, metal layer, transparent thin metal layer, conductive polymer, DMD, carbon nanotube or graphene.

[0030] In one preferred embodiment of the invention, the perovskite structure is an organic-inorganic perovskite structure comprising a perovskite of the formula (I), (II) or (III)

         A2MX4     (I)

         AMX3     (II)

         BMX4     (III),

wherein M is a bivalent metal cation selected from the group consisting of Cu2+, Ni2+, Co2+, Fe2+, Mn2+, Cr2+, Pd2+, Cd2+, Ge2+, Pb2+ or Sn2+,

A is potassium or a monovalent organic cation selected from primary, secondary, tertiary or quaternary alkyl ammonium compounds,

B is a bivalent organic cation selected from primary, secondary, tertiary or quaternary alkyl ammonium compounds,

wherein the alkyl-groups independently comprises 1 to 15 aliphatic carbon atoms,

X is a halide such as I, Cl or Br.



[0031] Preferably, M is selected from the group consisting of Pb2+ or Sn2+. Most preferably, M is Pb2+.

[0032] According to an embodiment, A is a primary or secondary alkyl ammonium compound, more preferably A is a primary alkyl ammonium compound.

[0033] According to an embodiment, any one of the alkyl-groups independently comprises 1 to 8, preferably 1 to 4, more preferably 1 to 2 aliphatic carbon atoms, wherein said alkyl if comprises 3 or more carbons, may be linear, branched or cyclic, and wherein several or all hydrogens in said substituent may be replaced by halogen. Most preferably, any one of the alkyl-groups is methyl.

[0034] In the methods of the invention, the perovskite layer may be applied by any one or more selected from vapor deposition, drop casting, spin-coating, dip-coating and spray-coating, for example.

[0035] In a further aspect of the invention the optoelectronic device that is arranged on a substrate comprises
  1. a) a first electrode adjacent to the substrate and a second electrode which is arranged on top of the device,
  2. b) at least one layer comprising an organic-inorganic or inorganic perovskite structure, wherein the perovskite is doped or undoped,
  3. c) at least one charge transport layer,
which is arranged between the first and the second electrode,
characterized in that the charge transport layer is doped from 0.001 to 15 percent by weight (wt.-%) with a dopant material based on the total weight of the finished layer.

[0036] Preferably, the dopant concentration in the charge transport layer (6) is between 0.01 and 12 wt%, more preferably between 0.1 and 10 wt%.

[0037] Preferably, the active layer of the optoelectronic device comprises at least one organic-inorganic pervoskite, wherein the pervoskite is doped or undoped.

[0038] In an embodiment of this aspect the pervoskite is doped with dopants exemplarily selected form the group consisting of F4-TCNQ (Tetrafluoro-tetracyano-quinodimethane) or F6-TCNNQ (1,3,4,5,7,8-hexafluorotetracyanonaphthoquinodimethane) or C60F36 or NDP9 (proprietary dopant from Novaled, GmbH) or molybdenum oxide.

[0039] In a further embodiment of this aspect the pervoskite is doped with dopants exemplarily selected form the group consisting of AOB (acridine orange base), BEDT-TTF (bis(ethylene-dithio)tetrathiafulvalene), W2(hpp)4 (Tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)-ditungsten (II)) or Cr2(hpp)4 (Tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)-dichromium (II)).

[0040] In a further embodiment of the invention the HTL and/or ETL comprise several layers, wherein the perovskite active layer is arranged between HTL and ETL and wherein at least one of the HTL or ETL is doped.

[0041] According to an embodiment, the optoelectronic device according to the invention contains molecular organic layers where the Fermi level is controlled by adding a dopant ion or molecules. Preferably, the dopant ions or molecules are selected from the group consisting of n-type dopants (e.g. AOB, W2(hpp)4, Cr2(hpp)4, V2(hpp)4, Mo2(hpp)4) and p-type dopants (e.g. F4-TCNQ, F6-TCNNQ, NDP9, C60F36).

[0042] Preferably, the matrix material of the molecular organic layer comprises organic polymers and/or small molecules. Typically, the molecular weight of small molecules is below 1000 g/mol such as fullerenes (e.g. C60) or phthalocyanine. A plurality of organic polymer and/or small molecule based optoelectronic devices are well known from prior art (e.g. Walzer et al., Chemical reviews 2007, 107(4), 1233-1271; Peumann et al., J. Appl. Phys. 2003, 93(7), 3693-3722).

[0043] For example, the matrix material of the molecular organic layers is selected from, but not limited to the group of small molecules consisting of Spiro-MeO-TAD, MeO-TPO, Spiro-MeO-TPD, Spiro-TTB, Spiro-TAD, BPAPF, pentacene, C60, F16CuPc (Copper(II)-1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluor-29H,31H-phthalocyanin), Ir(piq)3 (Tris(1-phenylisoquinoline)iridium(III)), ZnPC (Zinc phthalocyanine).

[0044] In one preferred embodiment, an charge injection layer is provided adjacent to at least one of the first and second electrode. The charge injection layer improves an injection of minority carriers from the first and or second electrode into the inversion channel, respectively.

[0045] In still a further embodiment, the charge injection layer is a hole injection layer (HIL) or an electron injection layer (EIL). It may be useful that the charge injection layer is doped with a dopant ion or molecule of opposite type than a dopant of the doped organic semiconducting layer. The doped semiconducting layer has to be n-doped for p-doped injection layers and p-doped for n-doped injection layers.

[0046] Typically, the matrix material of the molecular organic layers and the dopant ions or molecules are chosen with respect to the energy level of both components. For a preferable combination of matrix material and dopant the activation energy required for doping is less than the 50 meV.

[0047] In a further embodiment of the invention the optoelectronic device is a photo emissive device, a photoabsorptive device, a switching device, or a sensor device.

[0048] Preferably, the optoelectronic device according to the invention is a photoactive device such as a solar cell.

[0049] In a further embodiment of the invention the optoelectronic device comprises a p-n or p-i-n structure. The p-n or p-i-n structure may be formed as homo- or heterojunction.

[0050] In a further aspect the present invention provides a method for manufacturing an optoelectronic device according to the present invention, wherein the deposition of the doped transport layers and un-doped/doped perovskite layers is performed by co-evaporation of a the material and/or perovskite and a dopant material. The evaporation is performed under vacuum conditions.

[0051] The optoelectronic device according to the present invention comprising at least one perovskite layer, wherein the perovskite layer is a charge carrier transport layer and/or active layer and is either doped or un-doped. In particular the perovskite layer of the present invention is a hole transport layer (HTL) and/or an electron transport layer (ETL). By doping the perovskite layer, Fermi level control is achieved. The control of the Fermi level has several key advantages like reduction of contact resistance an improvement of the on-off ratio by control of charge carrier concentration in the channel in transistors. In light emitting diodes a reduction of the voltage due to lower transport layer and interference resistance and a wider choice of possible electrodes are achieved. Further to that in solar cells the formation of p-n or p-i-n homojuctions is achieved, this avoiding hetero-interfaces in the active region. In addition an optimization of the built-in voltage which helps to extract carriers from the device. Another advantage of Fermi control is the realization of good electrode contact regardless of energy barriers and the use of highly conductive layers avoiding ohmic losses.

[0052] The invention will be explained in more detail with the aid of the following figures and embodiments without limiting the invention to them.

DETAILED DESCRIPTION OF FIGURES



[0053] 

Fig. 1: depicts a schematic illustration of an optoelectronic device according to the present invention.

Fig. 2: depicts a schematic illustration of an optoelectronic device with and with out p-n or p-i-n hetero-/homo-junctions.

Fig. 3: Current-thickness data taken during vacuum deposition of intrinsic (bottom) and NDP9 (top) doped perovskite layers.

Fig. 4: Current-thickness data taken during vacuum deposition of intrinsic (bottom) and C60F36 (top) doped perovskite layers.

Fig. 5: General device architecture, corresponding energy level diagram for the materials used in this study, and average (a) short-circuit current density, (b) open-circuit voltage, (c) fill factor, and (d) efficiency values for devices employing these materials Numerical values correspond to the absolute value of the IP and EA as determined by UPS and IPES, respectively.


DETAILED DESCRIPTION OF INVENTION



[0054] In a first embodiment Fig. 1 depicts a simplified schematic illustration of an optoelectronic device according to the present invention. The optoelectronic device 1 is a solar cell and comprises a first electrode 2 (ITO), which is arranged on a substrate 3 (glass). On the first electrode 2 a hole transport layer (HTL) 4 is deposited. The hole transport layer (HTL) 4 comprises CH3NH3PblX3 doped with F4-TCNQ. On the hole transport layer (HTL) 4 an active layer 5 is deposited. The active layer 5 comprises an undoped pervoskite, e.g. CH3NH3PblX3. On the active layer an electron transport layer 6 is deposited. The electron transport layer (ETL) 6 comprises C60. On the top of the electron transport layer 6 is a second electrode deposited, wherein the second electrode comprises at least a metal, wherein the metal is selected from Al, Ag, Au, Ti, Pt, Cr, Zn, Sn, Sr, In, Sc, Hf or a mixture thereof.

[0055] In a further embodiment the optoelectronic device 1 is made in accordance to the aforementioned embodiment except that the hole transport layer (HTL) 4 comprises CH3NH3Pbl(I,Cl)3 doped with F6-TCNNQ.

[0056] In a further embodiment the optoelectronic device 1 comprises a first electrode 2 (ITO), which is arranged on a substrate 3 (glass). On the first electrode 2 a hole transport layer (HTL) 4 is deposited. The hole transport layer (HTL) 4 comprises Spiro-MeO-TAD. On the hole transport layer (HTL) 4 an active layer 5 is deposited. The active layer 5 comprises an undoped pervoskite, e.g. CH3NH3PbX3. On the active layer an electron transport layer 6 is deposited. The electron transport layer (ETL) 6 comprises CH3NH3PbX3 doped with W2(hpp)4. On the top of the electron transport layer 6 is a second electrode deposited, wherein the second electrode comprises at least a metal, e.g. Ag.

[0057] In a further embodiment the optoelectronic device 1 is made in accordance to the aforementioned embodiment except that the electron transport layer (ETL) 6 comprises CH3NH3PbX3 doped with Cr2(hpp)4.

[0058] In a further embodiment the optoelectronic device 1 comprises a first electrode 2 (ITO), which is arranged on a substrate 3 (glass). On the first electrode 2 a hole transport layer (HTL) 4 is deposited. The hole transport layer (HTL) 4 comprises p-doped perovskite. On the hole transport layer (HTL) 4 an active layer 5 is deposited. The active layer 5 comprises an undoped pervoskite, e.g. CH3NH3PbX3. On the active layer an electron transport layer 6 is deposited. The electron transport layer (ETL) 6 comprises n-doped CH3NH3PbX3. On the top of the electron transport layer 6 is a second electrode deposited, wherein the second electrode comprises at least a metal, e.g. Ag.

[0059] In a further embodiment the manufacturing of the optoeletronic device is performed by a thermal evaporation under vacuum conditions. Thin film samples are prepared by thermal vapor deposition in ultra-high vacuum (UHV) with a base pressure at or below 10-7 mbar. The layers in a multi layer device are deposited sequentially and their thicknesses are determined during evaporation using quartz crystal monitors calibrated for the respective material prior to evaporation.

[0060] A typical layer structure of substrate, electrode, charge injection layer and charge carrier transport layer or a layout as an optoelectronic device (1) according to the invention as depicted in Fig. 1 comprises independently on the intended purpose
Optoelectronic device (1),
First electrode or anode (2),
Substrate (3),
Hole transport layer (4),
Active layer (5),
Electron transport layer (6),
Second electrode or cathode (7),
optionally one or more charge injection layer (8) or buffer layer to
compensate for unevenness of the electrode,
optionally one or more charge blocking layer (9),
encapsulation (10),
but can be customized for each application.

[0061] Preferably, all layers are deposited by thermal evaporation in an ultra-high vacuum chamber and/or applied by coating from solution. The production of a multilayer organic structure by coating from solution, however, requires that the solvent is incompatible with the respective preceding layer to solve this not to swell again, or even destroy.

Examples



[0062] The present invention is further described in the following comparative, experiments and examples, which are not intended to limit the scope of the invention.

Example 1 - Doped Perovskite Layers:



[0063] Attempts have been made towards the controlled p-doping of the perovskite active layer. The intrinsic conductivity of the perovskite layer was first measured by in situ monitoring of the current response under a pulsed bias during deposition of an intrinsic perovskite film. Doping tests involved the triple-source vapor deposition of the perovskite precursors along with a molecular p-dopant (both NDP9 and C60F36 have been investigated). These studies exhibited up to two orders of magnitude improvement in the conductivity (Fig. 3 and Fig. 4) indicating possible doping of the perovskite layer.

[0064] The current increase upon an applied voltage (10 V) was measured between the contacts of a meander-like structure (1 nm Cr / 40 nm Au) upon increasing layer thickness of the matrix:dopant films in the channel (b = 500 µm, / = 0.111 m) during deposition (applied bias: 10 V).

Example 2 - Doped Transport Layers with Undoped Perovskite Active Layers:



[0065] The effect of energy level alignment between the hole-transporting material and the active layer in vacuum deposited, planar-heterojunction CH3NH3Pblx-3Clx perovskite solar cells was addressed. Though a series of hole-transport materials (cf. Table 1: Spiro-MeO-TAD; MeO-TPD [IP = 5.1 eV]; Spiro-MeO-TPD [IP = 5.1 eV], Spiro-TTB [IP = 5.3 eV], Spiro-TAD [IP = 5.4 eV], BPAPF [IP = 5.6 eV]), with conductivity values set though controlled p-doping of the layer, the ionization potentials (IP) with the open-circuit voltage of the device was correlated. With ionization potentials beyond 5.3 eV, a substantial decrease in both current density and voltage is observed, which highlights the delicate energetic balance between driving force for hole-extraction and maximizing the photovoltage (Fig. 5). In contrast, when an optimal ionization potential match was found, the open-circuit voltage could be maximized, leading to power conversion efficiencies of up to 10.9%. These values were obtained with hole-transport materials that differ from the commonly used Spiro-MeOTAD and correspond to a 40% performance increase compared to this reference. Additionally, this report demonstrates the first example of perovskite active layers being used in combination with doped transport layers.
Table 1: Ionization potential determined by ultraviolet photoelectron spectroscopy and short-circuit current density, open-circuit voltage, fill-factor, and power-conversion efficiency values measured under simulated AM 1.5 G sunlight (100 mW cm-2).
HTMIPUPS (eV)JSC (mA cm-2)VOC (V)FF (%)η (%)
1 5.0 14.4 (14.1 ± 0.5) 795 (820 ± 30) 69 (63 ± 5) 7.8 (7.2 ± 0.5)
2 5.0 14.9 (14.5 ± 0.3) 863(863 ± 10) 69 (63 ± 7) 8.7 (7.8 ± 1.0)
3 5.1 16.0 (15.5 ± 0.5) 1030 (940 ± 70) 66 (66 ± 3) 10.9 (9.6 ± 0.8)
4 5.3 16.1 (14.9 ± 0.9) 968 (970 ± 30) 70 (63 ± 6) 10.9 (9.1 ± 1.3)
5 5.4 12.4 (12.2 ± 0.5) 820 (815 ± 10) 58 (58 ± 8) 6.7 (5.8 ± 0.8)
6 5.6 0.72 835 13 0.08



Claims

1. Optoelectronic device (1) that is arranged on a substrate (3) comprising

a) a first electrode (2) adjacent to the substrate (3) and a second electrode (7) which is arranged on top of the device

b) at least one layer comprising a perovskite structure which is arranged between the first and the second electrode (2, 7),

characterized in that the perovskite is doped from 0.001 to 30 percent by weight (wt.-%) with a n-type or p-type dopant material based on the total weight of the finished layer.
 
2. Optoelectronic device according to claim 1 wherein the layer with the doped perovskite is the active layer (5).
 
3. Optoelectronic device according to claim 1 or 2, characterized in that the layer with the doped perovskite is a hole transport layer (4) or a electron transport layer (6).
 
4. Optoelectronic device according to one or more of claims 2 to 3, characterized in that the charge carrier transport layer with doped perovskite is a hole transport layer (4) wherein the dopant is F4-TCNQ, F6-TCNNQ, C60F36, NDP9 or molybdenum oxide.
 
5. Optoelectronic device according to one or more of claims 2 to 4 wherein the charge carrier transport layer with doped perovskite is an electron transport layer (6) and wherein the dopant is W2(hpp)4 or Cr2(hpp)4.
 
6. Optoelectronic device according to claims 1 to 5 wherein the electrode (2,7) is selected of transparent conducting oxide, metal nanowire, metal layer, transparent thin metal layer, conductive polymer, DMD, carbon nanotube or graphene.
 
7. Optoelectronic device (1) which is arranged on a substrate (3) comprising

a) a first electrode (2) adjacent to the substrate (3) and a second electrode (7) which is arranged on top of the device

b) at least one layer comprising an perovskite structure

c) at least one charge transport layer (6)

which is arranged between the first and the second electrode (2,7),
characterized in that the charge transport layer is doped from 0.001 to 15 percent by weight (wt.-%) with a dopant material based on the total weight of the finished layer.
 
8. Optoelectronic device according to any one of the preceding claims, wherein the perovskite structure is perovskite structure comprising a perovskite of the formula (I), or (III)

         A2MX4     (I),

         AMX3     (II),

         BMX4     (III),

wherein M is a bivalent metal cation selected from the group consisting of Cu2+, Ni2+, Co2+, Fe2+, Mn2+, Cr2+, Pd2+, Cd2+, Ge2+, Pb2+ or Sn2+,

A is potassium or a monovalent organic cation selected from primary, secondary, tertiary or quaternary alkyl ammonium compounds,

B is a bivalent organic cation selected from primary, secondary, tertiary or quaternary alkyl ammonium compounds,

wherein the alkyl-groups independently comprises 1 to 15 aliphatic carbon atoms,

X is a halide such as I, Cl or Br.


 
9. Optoelectronic device according to claims 1 to 8 wherein the optoelectronic device is a light emitting device, a solar cell, a field effector transistor or a sensor.
 
10. Optoelectronic device according to claims 1 to 9 wherein the optoelectronic device comprises a p-n or p-i-n structure.
 
11. Method of manufacturing an optoelectronic device according to any of claims 1 to 10 wherein the deposition of the doped perovskite layer is performed by co evaporation of a perovskite and a dopant material.
 
12. Use of a doped perovskite layer as a charge carrier transport layer to control the Fermi level of the active layer and/or surrounding layers in an optoelectronic device according to any of claims 1 to 11.
 




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Cited references

REFERENCES CITED IN THE DESCRIPTION



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Non-patent literature cited in the description