EP3931878A1 - Perovskite photoelectronic device with defect passivation - Google Patents

Perovskite photoelectronic device with defect passivation

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Publication number
EP3931878A1
EP3931878A1 EP20766113.3A EP20766113A EP3931878A1 EP 3931878 A1 EP3931878 A1 EP 3931878A1 EP 20766113 A EP20766113 A EP 20766113A EP 3931878 A1 EP3931878 A1 EP 3931878A1
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EP
European Patent Office
Prior art keywords
passivation
optoelectronic device
group
perovskite
inductive
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German (de)
French (fr)
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EP3931878A4 (en
Inventor
Weidong Xu
Feng Gao
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Linxole AB
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Individual
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic Table
    • H01L29/167—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic Table further characterised by the doping material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table
    • H01L31/0288—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table characterised by the doping material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a metal halide perovskite photoelectronic device and organic passivating agents.
  • the invention relates to a metal halide perovskite
  • Metal-halide perovskites have received growing attention over the last decade as promising functional material for optoelectronic devices such as solid-state light emitting devices and photovoltaic devices.
  • Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as broad tunability of bandgap, defect tolerance, high photoluminescence quantum efficiency and high emission color purity.
  • PeLEDs In order to achieve high-efficiency perovskite based light emitting diodes, PeLEDs, extensive efforts have been carried out to enhance radiative recombination rates by confining the electrons and holes. These confinement efforts include the use of ultra-thin emissive layers, the fabrication of nano-scaled polycrystalline features, the design of low-dimensional or multiple quantum well structures and the synthesis of perovskite quantum dots. As a result, the EQE values of PeLEDs have improved from less than 1% to ⁇ 14%.
  • TOPO trioctylphosphine oxide
  • the object of the present invention is to provide a method and devices that overcome the drawbacks of prior art techniques.
  • an optoelectronic device based on a perovskite material comprising a passivation agent comprising at least one passivation molecule.
  • the passivation molecule is a hydrocarbon compound comprising at least one passivation group, PG, at least one inductive group, IG, and an alkyl chain arranged as an structural unit according to the general formula:
  • the passivation molecule may comprise at least two passivation groups and two inductive groups wherein each passivation group has a corresponding inductive group at a distance corresponding to a value of n between 1 and 4.
  • the passivation molecule comprises at least two passivation groups and one inductive groups associated with the two passivation groups wherein each passivation group has the inductive group at a distance corresponding to a value of n between 1 and 4.
  • n is between 1 and 3.
  • the passivation molecule is an aromatic compound which is substituted at least by one PG and at least by one inductive group, IG, arranged as a structural unit according to the general formula:
  • Ar is a substituted aryl group comprising C5 to C50.
  • the passivation molecule is an aromatic compound which is substituted at least by one PG and at least by one inductive group, IG, arranged as a structural unit according to the general formula:
  • Ar is a substituted aryl group comprising C5 to C50.
  • the passivation agent comprises one of or a combination of molecules with following general structural formula:
  • n is from 1 to 5,000,000.
  • the inductive group is selected from O, S, F, Cl, Br, I and N.
  • passivation agent comprises one of or a combination of EDEA, ODEA, TTDDA and DDDA.
  • the optoelectronic device is a photovoltaic device, a laser device, a photo detector, an X-ray detector or a light emitting diode.
  • the method of producing the optoelectronic device according to the invention comprises the steps of
  • one advantage of the present invention is that it allows to prepare perovskite LEDs with exceptional high EQE up to 21.6%, which is comparable to the best solution processed LEDs with organic and quantum dot
  • a further advantage is that the perovskite LEDs with efficient passivation results in slow current-efficiency roll off, which maintain a high EQE of 20.1% and a Wall-plug efficiency of 11.0% at a high current density of 200 mA cm-2, making them more attractive than the most efficient organic and quantum-dot LEDs at high excitations.
  • the inventors have recognized that the efficient passivation invented here can improve the operational lifetime of perovskite optoelectronic devices, e.g. LEDs.
  • Fig.1 is a schematic illustration of the inductive effect utilized in embodiments of the invention.
  • Fig.2 are structures of candidate passivation agents investigated
  • Fig.3 is a graph showing dependence of average peak EQE values from candidate passivation agents treated PeLEDs on DE ad ;
  • Fig.4 is a schematic illustration of a PeLED according to the invention.
  • Fig.5 is a schematic illustration of a photovoltaic device according to the invention.
  • Fig.6a-h the PeLED architecture, performance and perovskite film characteristics: (a) the molecular structures of HMDA and EDEA, (b) a high-angle annular dark field (HAADF) cross-sectional image of an EDEA-treated device (left, scale bar 500 nm) and a zoom-in image (right, scale bar 100 nm) with an architecture of indium tin oxide
  • Fig.7a-c top-view SEM images of the perovskite films according to the invention,( a) the control perovskite films prepared with and w/o anti-solvent (AS) treatment. b, c, EDEA- (b) and HMDA (c) -treated perovskite films with various PA contents from 10% to 30%; the scale bars for the images are 200 nm;
  • Fig.8a-e (a) temperature dependence of capacitance-frequency plots for control, HMDA- treated and EDEA-treated devices (from 320 ⁇ 240 K). (b), (c) trap density deduced from the room temperature C-f plots for the control (b) and the HMDA-treated (c) samples, (d) fluence-dependent PLQYs. (e) time-correlated single photon counting (TCSPC) probed PL lifetime.
  • TCSPC time-correlated single photon counting
  • Fig.9a-f The dependence of EL performance on passivation effects determined by the hydrogen bonds, (a) the molecular structures of selected PAs (ODEA, TTDDA, DDDA), the letters shown in the chemical structures aim to highlight the different length of carbon chain between N and O atoms, (b) dependence of average peak EQE values from various PAs treated PeLEDs on DEad, each value is an average of 60 devices, (c), histograms of peak EQEs for control and ODEA-treated devices, device characteristics for the best performing ODEA- treated device, (d) J-V-R characteristics, (e) EQE and Wall-plug efficiency as a function of the current density, (f) steady-state EQE for the control and ODEA-treated devices at
  • Fig.10 Representative device characteristics based on qusi-2D PEA 2 FA 2 Pb 3 I 10 perovskite films with and without EDEA surface treatment (0.1 vol% in chlorobenzene), (a) EL spectra at 2.5 V. (b), J-V-R. c, J-EQE, with the concentration of Pb2+ being 0.11 M;
  • Fig.11 Representative device characteristics based on HMDA (a-c) and EDEA (d-f) passivated FAPbI 3 films.
  • Fig.12 Representative device characteristics based on ODEA (a-c), TTDDA (d-f) and DDDA (g-i) passivated FAPbI3 films with various PA feed ratios.
  • Fig.13 Histograms of peak EQEs from 60 devices with optimized PA feed ratio.
  • HMDA 20%.
  • DDDA 25%.
  • EDEA 25%.
  • TTDDA 20%
  • the average peak EQE value for each case is 10.7 ⁇ 0.67% (HMDA), 11.8 ⁇ 0.43% (DDDA), 16.5 ⁇ 0.67% (EDEA) and 16.4 ⁇ 0.61% (TTDDA), respectively, all these devices were prepared with the same batch of ZnO nano-crystals.
  • the present invention relates to optoelectronic devices based on a perovskite material comprising organic passivation agents for reducing unwanted recombination effects and to a method of producing such.
  • Perovskites are a class of compounds that adopts the ABX3 three-dimensional structure first described for CaTiO +VI
  • a and B are cations of various valence and ionic radii and X is an anion.
  • the A component is usually a monovalent organic cation, typically
  • B component is often a divalent metal cation (usually Pb 2 + , Sn 2 + or a mixture) and X component is a halide anion (typically Cl-, I-, Br- or a mixture thereof).
  • X component is a halide anion (typically Cl-, I-, Br- or a mixture thereof). Examples include, but are not limited to MAPbX 3 , FAPbX 3 , CsPbX 3 , MASnX3, FASnX3 and CsSnX3. Or combinations like
  • the B component is often a divalent metal cation, usually Pb2+. It may also selected at least one from Sn2+, Ge2+, Eu2+, Cu2+, Tb2+, Fe2+,Co2+, Zn2+, Mn2+ or their mixture with Pb2+, like Sn2+/Pb2+.
  • a more general description of a metal halide perovskite is: A’2(ABX3)n-1BX4.
  • the present invention relates to both 3D and quasi-2D perovskites.
  • the perovskite may also match the structure formula of A +
  • A is a monovalent organic cation or alkali metal ion, including Li+, Na+, K+, Rb+, Cs+.
  • B 2 3+ is a trivalent metal ion, which may be selected from Bi3+, In3+, Fe3+, Sb3+.
  • X component is a halide anion (typically Cl-, I-, Br- or a mixture thereof).
  • perovskite material is usually performed in solution from which bulk, layered or micro/nano-structured perovskites can be obtained.
  • PeLEDs perovskite light emitting diodes
  • the invention is applicable, which is obvious for the skilled person, for all optoelectronic devices wherein a perovskite material is utilized, including, but not limited to photovoltaic devices such as solar cells, laser gain media in optical pump laser or laser diodes, photo detector and optical communication devices, X-ray detectors, luminescent down conversion or up conversion materials in any photoelectric application, like sensors, luminescent solar concentrators and phosphors material.
  • photovoltaic devices such as solar cells, laser gain media in optical pump laser or laser diodes, photo detector and optical communication devices, X-ray detectors, luminescent down conversion or up conversion materials in any photoelectric application, like sensors, luminescent solar concentrators and phosphors material.
  • the PAs utilized according to the present invention are designed to decrease the hydrogen bonding ability.
  • PAs with oxygen atoms within the PAs are used to polarize the passivating amino groups through the inductive effect, reducing their electron-donating ability and hence relevant hydrogen bonding ability.
  • the trap-mediated non-radiative recombination is reduced and the
  • the perovskite based optoelectronic device comprises a perovskite material comprising at least one or a combination of passivating agents (PAs),
  • PA or PAs
  • the PA is a hydrocarbon compound comprising at least one passivation group (PG) at least one inductive group (IG) and an alkyl chain.
  • the PA molecules can be small molecule, polymer, oligomer, conjugated or non-conjugated.
  • R alkyl or aromatic fused rings.
  • passivating function groups are aromatic fused rings containing heteroatoms (O, N, S, B), such as pyridine, pyrrole, imidazole, furan, thiophene, and thiazole.
  • Suitable inductive groups are known in the art and include, but are not limited to:
  • strong electronegative atoms e.g. O, S, F, Cl, Br, I, N
  • the inductive group (IG) affects the passivation group (PG) and thereby the hydrogen bonds between the amino groups and the FA+ of the perovskite material. Without being bound to theory, this is schematically illustrated in Fig.1, wherein the IG is O and the PG is an amino group, -NH 2 .
  • the IG according to the invention and also the distance, as measured in the number of carbons, n, in the carbon chain is selected so that the electron withdrawing inductive effect of the IG, here the O atom, affect the PG so that the PGs electrons are polarized towards the IG, which hence reduce the electron-donating ability of the amino groups and the relevant hydrogen bonding ability.
  • n is selected to be between 1 and 4.
  • the selection of n is based on the resulting peak external quantum efficiency, peak EQE.
  • a number of PA candidates with varying distance n and varying number of PG groups were tested: HMDA, EDEA, ODEA, TTDDA and DDDA, which respective structure is illustrated in Fig.2.
  • the experimental details will be discussed below.
  • Fig.3 is a graph illustrating the peak EQE for the PA candidates. All the PA candidates with IGs (n ⁇ 4) are better than the one without IGs (HMDA).
  • a significant performance enhancement is found for the PAs wherein n becomes smaller, which can demonstrated by comparing ODEA/TTDDA, or EDEA/DDDA.
  • Increasing the number of IGs also affects the peak EQE as demonstrated by comparing EDEA/ODEA and DDDA/TTDDA.
  • the information summarized in Fig.3, is in detail presented in Figs.11- 13.
  • the conjugated effect afforded by the introduction of an aryl group is utilized in at least one passivation molecule of the PA.
  • the passivation molecule is an aromatic compound which is substituted at least by one PG and at least by one inductive group, IG, arranged as a structural unit according to the general formula:
  • Ar is a substituted aryl group comprising C5 to C50.
  • the passivation group is a heteroaryl molecule with at least one substitution by IG, arranged as a structural unit according to the general formula:
  • HAr is a heteroaryl group comprising from C5 to C50, and at least one hetero atom selected from N, O, S.
  • the passivation the passivation agent comprises one of or a combination of molecules with following general structural formula: wherein n is from 1 to 5,000,000.
  • a photovoltaic device is provided based on the above described optoelectronic device comprising a perovskite material passivated with the passivation agent.
  • Example of photovoltaic device include, but is not limited to a solar cell.
  • a laser device or a laser application is provided based on the above described optoelectronic device comprising a perovskite material passivated with the passivation agent.
  • Laser applications includes but are not limited to laser gain media in optical pump laser or laser diodes.
  • a photo detector or an optical communication device is provided based on the above described optoelectronic device comprising a perovskite material passivated with the passivation agent.
  • devices comprising luminescent down conversion materials or up conversion materials in any photoelectric application or an optical communication device is provided based on the above described optoelectronic device comprising a perovskite material passivated with the passivation agent.
  • the structure of a PeLED according to the invention is schematically illustrated in Fig.4.
  • the Pe Led 40 comprises a substrate 41, a transparent conducting material layer 42, an electron transport/injection layer 43, for example a ZnO/PEIE layer, a perovskite layer comprising the passivation agent 44, a hole transport layer (TFB) 45, and an electrode layer (back electrode) 46.
  • the structure of photovoltaic device for example a solar cell, according to the invention is schematically illustrated in Fig.5.
  • the photovoltaic device 50 comprises a substrate 51, a transparent conducting material layer 52, an electron transport layer, for example a compact TiO 2 or a compact TiO 2 /mesoporous TiO2 double layer 53, a perovskite layer comprising the passivation agent 54, and a hole transport layer, for example Spiro-OMeTad 55, and an electrode layer (back electrode) 56.
  • the method of preparing a perovskite based optoelectronic device according to the invention comprises the steps of:
  • Perovskite film surface treatment e.g. spin on the top of perovskite films or immerse perovskite films into a solution with passivation agents.
  • Amino groups have been frequently employed to passivate perovskite semiconductors due to their coordination bonding to unsaturated PbI 6 -octahedral.
  • EDEA ethylenedioxy)diethylamine
  • HMDA hexamethylenediamine
  • HAADF-STEM high-angle annular dark field cross-sectional scanning transmission electron microscope
  • SEM scanning electron microscope
  • the molecules used as potential PAs could also be used as templating molecules to synthesize low dimensional perovskites.
  • these PAs affect the three-dimensional (3D) crystal structure of FAPbI 3 .
  • X-ray diffraction (XRD) measurements indicate no additional diffraction peaks other than those from 3D FAPbI3 in the treated perovskite films (Fig.6h).
  • TCSPC time-correlated single photon counting
  • the inductive effect can be increased by introducing one additional O atom (as in 2,2 ⁇ -[oxybis(ethylenoxy)]diethylamine (ODEA)), and reduced by increasing the length of alkyl chain between the N and O atoms (as in 4,9-dioxa-1,12-dodecanediamine (DDDA) and 4,7,10-trioxa-1,13-tridecanediamine (TTDDA))32.
  • ODEA 2,2 ⁇ -[oxybis(ethylenoxy)]diethylamine
  • DDDA 4,9-dioxa-1,12-dodecanediamine
  • TTDDA 4,7,10-trioxa-1,13-tridecanediamine
  • Fig.9b shows the average peak EQE values for all the passivated systems as a function of DE ad . It clearly shows that the EL performance is strongly dependent on the DE ad, and hence the hydrogen bonding ability of amino groups.
  • ODEA which shows a DEad value of -0.42 eV, delivers the highest average peak EQE of 19.0 ⁇ 0.8% (Fig.9b and 9c).
  • Our device exhibits a low efficiency roll-off, maintaining a high EQE of 20.1 % and a wall-plug efficiency of 11.0% at a high current density of 200 mA cm-2, which makes them much more efficient than OLEDs and QLEDs at high excitations.
  • the improved lifetime may result from the reduced Joule heating due to the high efficiency, or the suppression of ion migration due to the low defect density.
  • the passivation agents including hexamethylenediamine (HMDA), 2,2 ⁇ - (ethylenedioxy)diethylamine (EDEA), 4,9-dioxa-1,12-dodecanediamine (DDDA), 2,2 ⁇ - [oxybis(ethylenoxy)]diethylamine (ODEA), 4,7,10-trioxa-1,13-tridecanediamine (TTDDA), ethylene glycol diethyl ether (EGDE) were purchased from Sigma-Aldrich.
  • Formamidinium iodide (FAI) was purchased from Dyesol.
  • PbI2 (beads, 99.999%) was purchased from Alfa Aesar.
  • ITO indium tin oxide
  • TL-1 a mixture of water, ammonia (25%), and hydrogen peroxide (28%) (5:1:1 by volume)
  • the clean substrates were then treated by UV-ozone for 10 min.
  • the ZnO nanocrystal solutions were spin-casted onto the substrates at 4,000 rpm for 30 s in air. Then the substrates were moved into a N2-filled glovebox.
  • PEIE polyethylenimine ethoxylated
  • the perovskite films were deposited from the precursors with various PA contents and Pb2+ concentrations at a spin- coating speed of 3,000 rpm, followed by annealing at 100°C for 10 min.
  • the spin-casting rate is 5,000 rpm.
  • 150 mL chlorobenzene (CB) was dropped after 5 seconds spinning.
  • the TFB layer was deposited from its CB solution (12 mg mL-1) at 3,000 rpm.
  • the MoOx/Au electrode was deposited by a thermal evaporation system through a shadow mask under a base pressure of ⁇ 1 ⁇ 10-7 torr.
  • the device area was 7.25 mm-2 as defined by the overlapping area of the ITO films and top electrodes.
  • PeLEDs characterization All PeLED device characterizations were carried out at room temperature in a nitrogen-filled glovebox. A Keithley 2400 source meter and a fibre integration sphere (FOIS-1) coupled with a QE Pro spectrometer (Ocean Optics) was used for the measurements. The PeLED devices are tested on top of the integration sphere and only forward light emission can be collected, consistent with the standard OLED characterization method. The absolute radiance was calibrated by a standard Vis-NIR light source (HL-3P- INT-CAL plus, Ocean Optics).
  • F-4600, HITACHI fluorescent spectrophotometer
  • X-ray photoelectron spectroscopy (XPS) tests were carried out using a Scienta ESCA 200 spectrometer in ultrahigh vacuum ( ⁇ 1x10-10 mbar) with a monochromatic Al (K alpha) X-ray source providing photons with 1486.6 eV.
  • the XPS experimental condition was set so that the full width at half maximum of the clean Au 4f 7/2 line (at the binding energy of 84.00 eV) was 0.65 eV. All spectra were measured at a photoelectron take off angle of 0° (normal emission).
  • Time-of-flight secondary ion mass spectrometry (TOF-SIMS) tests were performed on a ToF- SIMS.5 instrument from IONTOF, Germany, operated in the spectral mode using a 25 keV Bi +
  • Attenuated total reflectance-Fourier Transform Infrared (ATR-FT-IR).
  • the ATR-FT-IR spectra were recorded from a PIKE MIRacle ATR accessory with a diamond prim in a Vertex 70 Spectrometer (Bruker) using a DLaTGS detector at room temperature. The measuring system was continuously kept in N 2 atmosphere. The spectra were acquired at 2 cm-1 resolution and 30 scans between 4000 and 800 cm-1. The presented spectra were baselined- corrected by subtracting a linear baseline over the spectral ranges.
  • STEM Aberration-corrected scanning transmission electron microscope
  • An FEI dual- beam FIB Helios workstation equipped with an in-situ micromanipulator and Pt gas injection system was used to prepare thin samples for STEM imaging. The final milling was performed at 3 kV.
  • STEM investigations were conducted using JEOL ARM200F TEM equipped with a spherical aberration corrector at the condenser plane. A semi-convergence angle of 32 mrad was used.
  • High-angle annual dark field (HAADF) and annual bright field (ABF) STEM were recorded with semi-angles in the range 68-280 mrad and 7-18 mrad, respectively.
  • HAADF high-angle annual dark field
  • ABSF annual bright field
  • Fluence-dependent PLQY and time-correlated single photon counting (TCSPC) measurements were measured by a typical three-step technique with a combination of 445 nm continuous-wave (CW) laser, spectrometer, and an integrating sphere5.
  • the TCSPC measurements were performed on an Edinburgh Instruments spectrometer (FLS980) with a 638 nm pulsed laser (less than 100 ps, 0.1 MHz).
  • the total instrument response function (IRF) was less than 130 ps, and temporal resolution was less than 20 ps. All the perovskite films were deposited on ITO/ZnO:PEIE substrates with identical spin-casting condition for the optimized devices, and encapsulated by UV curable resin and glass slides.
  • TA Transient absorption
  • the perovskite film samples were mounted in a chamber under dynamic vacuum ( ⁇ 10-5 mbar).
  • TA spectroscopy was conducted in transmission geometry.
  • An amplified Ti:sapphire laser (Quantronix Integra-C) generated ⁇ 130 fs pulses centred at 800 nm, at a repetition rate of 1 kHz.
  • a broadband white light probe was generated by focusing the pulses into a thin CaF 2 plate, and pump light at 400 nm was obtained via second harmonic generation in a BBO crystal.
  • a grating spectrometer was used to disperse the probe light on to a fast CCD array, enabling broadband shot-to-shot detection.
  • Trap density measurements by thermal admittance spectroscopy TAS.
  • TAS thermal admittance spectroscopy
  • a sinusoidal voltage with a peek-to-peak value of 30 mV generated from a Tektronix AFG 3000 function generator was applied to the device.
  • the current signal of the devices was amplified with a SR570 low noise current preamplifier (Stanford Research Systems) and then analysed using a SR830 lock-in amplifier (Stanford Research Systems), where the amplitude and phase of the current can be measured. Based on the amplitude and phase of the current signal, the capacitance of the device was calculated using the parallel equivalent circuit model.
  • the capacitance spectra of the device were measured by scanning the frequency of the sinusoidal voltage from 0.01 to 100 kHz in a logarithmic step.
  • the temperature of the device was controlled using a DE202AE closed cycle cryocooler (Advanced Research Systems).
  • the capacitance-voltage curve was obtained by measuring the capacitance when the applied DC bias voltage scanning from -0.5 to l.0 V.
  • the trap density (N T ) distribution in energy (E w ) was calculated with the following relations:
  • V bi is the built-in potential
  • W is the depletion width
  • V bi and W are derived from capacitance-voltage measurement
  • C is the capacitance measured at angular frequency of w and temperature of T
  • k is the Boltzmann constant
  • n 0 is the attempt-to-escape frequency, which can be obtained by fitting the relation of characteristic frequency with different T based on Equation (3).

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Abstract

The present invention relates to optoelectronic devices based on a perovskite material comprising organic passivation agents for reducing unwanted recombination effects and to a method of producing such.In particular the invention relates to PeLED with exceptional high EQE up to 21.6%.

Description

PEROVSKITE PHOTOELECTRONIC DEVICE WITH DEFECT PASSIVATION Field of the invention
The present invention relates to a metal halide perovskite photoelectronic device and organic passivating agents. In particular, the invention relates to a metal halide perovskite
photoelectronic device wherein defects have been passivated by the introduction of a passivation molecule wherein the hydrogen bonding ability has been decreased. Background of the invention
Perovskites, in particular metal-halide perovskites, have received growing attention over the last decade as promising functional material for optoelectronic devices such as solid-state light emitting devices and photovoltaic devices. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as broad tunability of bandgap, defect tolerance, high photoluminescence quantum efficiency and high emission color purity.
In order to achieve high-efficiency perovskite based light emitting diodes, PeLEDs, extensive efforts have been carried out to enhance radiative recombination rates by confining the electrons and holes. These confinement efforts include the use of ultra-thin emissive layers, the fabrication of nano-scaled polycrystalline features, the design of low-dimensional or multiple quantum well structures and the synthesis of perovskite quantum dots. As a result, the EQE values of PeLEDs have improved from less than 1% to ~ 14%.
In addition to enhancing radiative recombination rates, equally important is to decrease the non-radiative recombination for improving the device performance. Unfortunately, state-of- the-art solution-processed perovskite semiconductors suffer from severe trap-mediated non- radiative losses, which have been identified as a major efficiency limiting factor for both photovoltaics (PVs) and LEDs. The trap states are generally believed to be associated with ionic defects, such as halide vacancies. Defect passivation through a molecular passivation agent (PA), which can chemically bond with the defects, is an attractive methodology to tackle this issue. A few function groups (e.g.–NH2, P=O) have been identified to passivate perovskite semiconductors for photovoltaic applications. It is found that these PAs show strong structure dependent performance, even though they share identical functional groups to interact with the perovskite defects. These functional groups have also been borrowed to improve the efficiency of LEDs, resulting in limited success so far. For example, the use of trioctylphosphine oxide (TOPO) treatment in green PeLEDs has reportedly only resulted in a moderate EQE enhancement.
The recently published article“Perovskite light-emitting diodes based on spontaneously formed submicrometre-scale structures”, Cao et al, 11 October 2018, Vol 562, Nature 249, discloses introducing amino-acid additives into the perovskite precursor solution and EQE above 18% is reported for 5-aminovaleric acid (5AVA). Similar results are claimed for amino acids of even longer chain lengths; 6- aminocaproic acid (6AcA) and 7- aminoheptanoic acid. The positive effect is ascribed to the additives fascilitating the forming of submicrometre- scale structures, which is described as having a passivating effect.
Although improvements have been made the negative effect of the non-radiative
recombination must be mitigated to a considerably higher degree in order for optoelectronic devices based on metal-halide perovskite materials to be commercially attractive in comparison to alternative techniques such as polymer LEDs and organic LEDs.
Summary of the invention
Although advances have been made in providing effective optoelectronic device based on perovskite materials, the non-radiative recombination losses remains a significant problem in providing commercially attractive devices.
The object of the present invention is to provide a method and devices that overcome the drawbacks of prior art techniques.
This is achieved by the optoelectronic devices as defined in claim 1, claim 9, claim 13 and claim 17 and the method as defined in claim 26.
According to one aspect of the invention an optoelectronic device is provided based on a perovskite material comprising a passivation agent comprising at least one passivation molecule. The passivation molecule is a hydrocarbon compound comprising at least one passivation group, PG, at least one inductive group, IG, and an alkyl chain arranged as an structural unit according to the general formula:
wherein n is between 1 and 4. The passivation molecule may comprise at least two passivation groups and two inductive groups wherein each passivation group has a corresponding inductive group at a distance corresponding to a value of n between 1 and 4. Alternatively the passivation molecule comprises at least two passivation groups and one inductive groups associated with the two passivation groups wherein each passivation group has the inductive group at a distance corresponding to a value of n between 1 and 4.
According to one aspect n is between 1 and 3.
According to one aspect of the invention the passivation molecule is an aromatic compound which is substituted at least by one PG and at least by one inductive group, IG, arranged as a structural unit according to the general formula:
wherein Ar is a substituted aryl group comprising C5 to C50.
According to one aspect of the invention the passivation molecule is an aromatic compound which is substituted at least by one PG and at least by one inductive group, IG, arranged as a structural unit according to the general formula:
wherein Ar is a substituted aryl group comprising C5 to C50.
According to one aspect of the invention the passivation agent comprises one of or a combination of molecules with following general structural formula:
wherein n is from 1 to 5,000,000.
According to one aspect of the invention the passivation group is selected from primary amine, -NH2, secondary amines, -NHR, tertiarg amines,–NR2, ether and hydroxyl, -OR(H), sulfhydryl and thiol, -SR(H), carbonyl, C=O, phosphine PR3, phosphine oxides, P=O, carboxyl group, -COOR(H), sulphoxide, S=O, sulfone, O=S=O, or any Lewis Base function groups, wherein R is an alkyl chain or aryl groups.
According to one aspect of the invention the inductive group is selected from O, S, F, Cl, Br, I and N.
According to one aspect of the invention the inductive group is selected from cyano, -CN, nitro, -NO2, carbonyl, C=O, carboxyl group, -COOR(H), sulphoxide, S=O, sulfone, O=S=O, amide, -CONH2, acyl chloride, -COOCl, sulphoxide, S=O, sulfone, O=S=O.
According to one aspect of the invention passivation agent comprises one of or a combination of EDEA, ODEA, TTDDA and DDDA.
According to aspects of the invention the optoelectronic device is a photovoltaic device, a laser device, a photo detector, an X-ray detector or a light emitting diode.
The method of producing the optoelectronic device according to the invention comprises the steps of
- providing a perovskite precursor;
-providing one or a combination of passivation agent(s) doped into the perovskite precursor; -performing perovskite film surface treatment;
-performing passivation molecule vapour treatment; and
-doping into anti-solvent.
Thanks to the invention, the interaction between defect sites in perovskite and passivating function groups (e.g.–NH2) can be much improved. And hence the non-radiative losses in the perovskite semiconductors are substantially mitigated, allowing to boost the performance of perovskite optoelectronic devices. Specifically, one advantage of the present invention is that it allows to prepare perovskite LEDs with exceptional high EQE up to 21.6%, which is comparable to the best solution processed LEDs with organic and quantum dot
semiconductors.
A further advantage is that the perovskite LEDs with efficient passivation results in slow current-efficiency roll off, which maintain a high EQE of 20.1% and a Wall-plug efficiency of 11.0% at a high current density of 200 mA cm-2, making them more attractive than the most efficient organic and quantum-dot LEDs at high excitations.
The inventors have recognized that the efficient passivation invented here can improve the operational lifetime of perovskite optoelectronic devices, e.g. LEDs.
In the following, the invention will be described in more detail, by way of example only, with regard to non-limiting embodiments thereof, reference being made to the accompanying drawings.
Brief description of the drawings
Fig.1 is a schematic illustration of the inductive effect utilized in embodiments of the invention;
Fig.2 are structures of candidate passivation agents investigated;
Fig.3 is a graph showing dependence of average peak EQE values from candidate passivation agents treated PeLEDs on DEad;
Fig.4 is a schematic illustration of a PeLED according to the invention;
Fig.5 is a schematic illustration of a photovoltaic device according to the invention;
Fig.6a-h: the PeLED architecture, performance and perovskite film characteristics: (a) the molecular structures of HMDA and EDEA, (b) a high-angle annular dark field (HAADF) cross-sectional image of an EDEA-treated device (left, scale bar 500 nm) and a zoom-in image (right, scale bar 100 nm) with an architecture of indium tin oxide
(ITO)/polyethylenimine ethoxylated (PEIE): modified zinc oxide nano-crystals
(ZnO:PEIE)/perovskite/poly(9,9-dioctyl-fluorene-co-N-(4-butylphenyl)diphenyl-amine) (TFB) /molybdenum oxide (MoO3)/Au. Represented device characteristics for the optimized control and PA-treated (HMDA, EDEA) devices: (c) EL spectra at 2.5V; (d) EQE-J curves; (e) current density-voltage-radiance (J-V-R) characteristics. (f) TOF-SIMS measurements for the EDEA-treated perovskite film (25%) on the ITO/ZnO:PEIE substrate, showing
unfragment (M+= EDEA+) and fragment molecular ion ([M-NH3] + and [M-H]+). (g) ATR-FT- IR (N-H stretching) for EDEA and PbI2:EDEA mixture. (h) XRD patterns for the control, EDEA- (25%) and HMDA-treated (25%) films on the ITO/ZnO:PEIE substrates. a and # denote the diffraction peaks corresponding to a-FAPbI3 and ITO, respectively;
Fig.7a-c: top-view SEM images of the perovskite films according to the invention,( a) the control perovskite films prepared with and w/o anti-solvent (AS) treatment. b, c, EDEA- (b) and HMDA (c) -treated perovskite films with various PA contents from 10% to 30%; the scale bars for the images are 200 nm;
Fig.8a-e: (a) temperature dependence of capacitance-frequency plots for control, HMDA- treated and EDEA-treated devices (from 320 ~ 240 K). (b), (c) trap density deduced from the room temperature C-f plots for the control (b) and the HMDA-treated (c) samples, (d) fluence-dependent PLQYs. (e) time-correlated single photon counting (TCSPC) probed PL lifetime. The excitation density for the TCSPC measurement is around 1015 cm-3;
Fig.9a-f: The dependence of EL performance on passivation effects determined by the hydrogen bonds, (a) the molecular structures of selected PAs (ODEA, TTDDA, DDDA), the letters shown in the chemical structures aim to highlight the different length of carbon chain between N and O atoms, (b) dependence of average peak EQE values from various PAs treated PeLEDs on DEad, each value is an average of 60 devices, (c), histograms of peak EQEs for control and ODEA-treated devices, device characteristics for the best performing ODEA- treated device, (d) J-V-R characteristics, (e) EQE and Wall-plug efficiency as a function of the current density, (f) steady-state EQE for the control and ODEA-treated devices at
25 mA cm-2;
Fig.10: Representative device characteristics based on qusi-2D PEA2FA2Pb3I10 perovskite films with and without EDEA surface treatment (0.1 vol% in chlorobenzene), (a) EL spectra at 2.5 V. (b), J-V-R. c, J-EQE, with the concentration of Pb2+ being 0.11 M;
Fig.11: Representative device characteristics based on HMDA (a-c) and EDEA (d-f) passivated FAPbI3 films. (a), (d), EL spectra at 2.5 V. (b),€, J-V-R. c, f, J-EQE, the perovskite layers were prepared from precursor with the feed ratio of FAI: PbI2: PA = 2: 1: x, x = 10%, 20%, 25%, 30%), the concentration of Pb2+ is 0.13 M;
Fig.12: Representative device characteristics based on ODEA (a-c), TTDDA (d-f) and DDDA (g-i) passivated FAPbI3 films with various PA feed ratios. (a), (d), (g), EL spectra at 2.5 V. b, e, h, J-V-R. c, f, i, J-EQE, the perovskite layers were prepared from precursors with the feed ratio of FAI: PbI2: PA = 2: 1: x, x = 10%, 20%, 25%, 30%), the concentration of Pb2+ is 0.13 M;
Fig.13: Histograms of peak EQEs from 60 devices with optimized PA feed ratio. (a), HMDA = 20%. (b), DDDA = 25%. (c), EDEA = 25%. (d), TTDDA = 20%, the average peak EQE value for each case is 10.7 ± 0.67% (HMDA), 11.8 ± 0.43% (DDDA), 16.5 ± 0.67% (EDEA) and 16.4 ± 0.61% (TTDDA), respectively, all these devices were prepared with the same batch of ZnO nano-crystals. Detailed description
The present invention relates to optoelectronic devices based on a perovskite material comprising organic passivation agents for reducing unwanted recombination effects and to a method of producing such.
Perovskites are a class of compounds that adopts the ABX3 three-dimensional structure first described for CaTiO +VI
3 (XIIA2 B4+X2- 3), and named the perovskite structure. A and B are cations of various valence and ionic radii and X is an anion. For metal-halide hybrid perovskites, the A component is usually a monovalent organic cation, typically
methylammonium (CH3NH +
3 = MA+) or formamidinium (HC(NH2) +
2 = FA+), an atomic cation (typically Cs+) or a mixture thereof, the B component is often a divalent metal cation (usually Pb2 +, Sn2 + or a mixture) and X component is a halide anion (typically Cl-, I-, Br- or a mixture thereof). Examples include, but are not limited to MAPbX3, FAPbX3, CsPbX3, MASnX3, FASnX3 and CsSnX3. Or combinations like
FA0.85MA0.1Cs0.05(Pb0.5Sn0.5)I2Br0.5Cl0.5.
The B component is often a divalent metal cation, usually Pb2+. It may also selected at least one from Sn2+, Ge2+, Eu2+, Cu2+, Tb2+, Fe2+,Co2+, Zn2+, Mn2+ or their mixture with Pb2+, like Sn2+/Pb2+.
A more general description of a metal halide perovskite is: A’2(ABX3)n-1BX4. Here n is the number of semiconducting BX4 monolayer sheets within the two organic insulating layers (cation A’), with n = ¥ corresponding to the structure of a 3D perovskite ABX3 A’ is large organic ammonium cations that cannot be incorporated into the 3D perovskite lattice but forming layered structure or low dimensional perovskite, like C +
4H9NH3 (BA) or C8H12NH +
3 (PEA).
There are numerous choices to form quasi-2D or 2D perovskites, for example:
Pure 2D perovskite like BA2PbI4;
Quasi-2D perovskite (n=2) like BA2(FA)Pb2I7;
Quasi-2D perovskite (n=3) like BA2(FA)2Pb3I10, When n=¥, to be 3D FAPbI3 (the first part). The present invention relates to both 3D and quasi-2D perovskites.
The perovskite may also match the structure formula of A +
2B +
1 B 3
2 X6. Here, A is a monovalent organic cation or alkali metal ion, including Li+, Na+, K+, Rb+, Cs+. B +
1 is a monovalent metal ion, such as Ag+, Cu+. B2 3+ is a trivalent metal ion, which may be selected from Bi3+, In3+, Fe3+, Sb3+. X component is a halide anion (typically Cl-, I-, Br- or a mixture thereof).
The synthesis of perovskite material is usually performed in solution from which bulk, layered or micro/nano-structured perovskites can be obtained.
In the following perovskite light emitting diodes, PeLEDs, are discussed as an illustrative example. The invention is applicable, which is obvious for the skilled person, for all optoelectronic devices wherein a perovskite material is utilized, including, but not limited to photovoltaic devices such as solar cells, laser gain media in optical pump laser or laser diodes, photo detector and optical communication devices, X-ray detectors, luminescent down conversion or up conversion materials in any photoelectric application, like sensors, luminescent solar concentrators and phosphors material.
As discussed in the background section a major efficiency limit for solution-processed perovskite optoelectronic devices (e.g. light-emitting diodes, LEDs) is trap-mediated non- radiative losses. Defect passivation using organic molecules, molecular passivation agent (PA), has been identified as an attractive approach to tackle this issue. However,
implementation of this approach has been only marginally successful. Unexpectedly the inventors have found that the weakening of the hydrogen bonding between the passivating functional moieties and the organic cation featuring the perovskite, enhance the interaction with defects sites and minimize non-radiative recombination losses. Consequently, exceptionally high-performance near infrared perovskite LEDs (PeLEDs) with an external quantum efficiency (EQE) of 21.6% could be produced. In addition, the passivated PeLEDs maintain a high EQE of 20.1% and a wall-plug efficiency of 11.0% at a high current density of 200 mA cm-2.
The PAs utilized according to the present invention are designed to decrease the hydrogen bonding ability. In particular, PAs with oxygen atoms within the PAs are used to polarize the passivating amino groups through the inductive effect, reducing their electron-donating ability and hence relevant hydrogen bonding ability. This results in enhanced coordination of the PA functional groups with the perovskite defects sites and hence improved passivation efficiency. As a result, the trap-mediated non-radiative recombination is reduced and the
electroluminescence (EL) performance of PeLEDs is boosted. The perovskite based optoelectronic device according to the invention comprises a perovskite material comprising at least one or a combination of passivating agents (PAs), The PA (or PAs) is a hydrocarbon compound comprising at least one passivation group (PG) at least one inductive group (IG) and an alkyl chain. The PA molecules can be small molecule, polymer, oligomer, conjugated or non-conjugated.
Suitable passivation groups are known in the art and include, but are not limited to: -NH2, - NHR. NR3, -OR(H), -SR(H), phosphine, phosphine oxides, sulphoxide (S=O), sulfone (SO2), any Lewis Base function groups. R=alkyl or aromatic fused rings. Alternatively passivating function groups are aromatic fused rings containing heteroatoms (O, N, S, B), such as pyridine, pyrrole, imidazole, furan, thiophene, and thiazole.
Suitable inductive groups are known in the art and include, but are not limited to:
strong electronegative atoms, e.g. O, S, F, Cl, Br, I, N; function groups showing electron withdrawing/donating properties that effect on the hydrogen bonding ability of passivation function groups, including–CN, -NO2, C=O, COOR(H), COO-, COONH2, COOCl, S=O, SO2.
The inductive group (IG) affects the passivation group (PG) and thereby the hydrogen bonds between the amino groups and the FA+ of the perovskite material. Without being bound to theory, this is schematically illustrated in Fig.1, wherein the IG is O and the PG is an amino group, -NH2. The IG according to the invention and also the distance, as measured in the number of carbons, n, in the carbon chain is selected so that the electron withdrawing inductive effect of the IG, here the O atom, affect the PG so that the PGs electrons are polarized towards the IG, which hence reduce the electron-donating ability of the amino groups and the relevant hydrogen bonding ability.
According to one embodiment of the invention the PA has as a structural unit according to the general formula:
wherein n is selected to be between 1 and 4. The selection of n is based on the resulting peak external quantum efficiency, peak EQE. A number of PA candidates with varying distance n and varying number of PG groups were tested: HMDA, EDEA, ODEA, TTDDA and DDDA, which respective structure is illustrated in Fig.2. The experimental details will be discussed below. Fig.3 is a graph illustrating the peak EQE for the PA candidates. All the PA candidates with IGs (n < 4) are better than the one without IGs (HMDA). As shown in the graph, a significant performance enhancement is found for the PAs wherein n becomes smaller, which can demonstrated by comparing ODEA/TTDDA, or EDEA/DDDA. Increasing the number of IGs also affects the peak EQE as demonstrated by comparing EDEA/ODEA and DDDA/TTDDA. The information summarized in Fig.3, is in detail presented in Figs.11- 13.
According to embodiments of the invention the conjugated effect afforded by the introduction of an aryl group is utilized in at least one passivation molecule of the PA.
According to one embodiment the passivation molecule is an aromatic compound which is substituted at least by one PG and at least by one inductive group, IG, arranged as a structural unit according to the general formula:
wherein Ar is a substituted aryl group comprising C5 to C50.
According to one embodiment the passivation group is a heteroaryl molecule with at least one substitution by IG, arranged as a structural unit according to the general formula:
wherein HAr is a heteroaryl group comprising from C5 to C50, and at least one hetero atom selected from N, O, S.
According to one embodiment the passivation the passivation agent comprises one of or a combination of molecules with following general structural formula: wherein n is from 1 to 5,000,000.
According to one embodiment of the invention a photovoltaic device is provided based on the above described optoelectronic device comprising a perovskite material passivated with the passivation agent. Example of photovoltaic device include, but is not limited to a solar cell. According to one embodiment of the invention a laser device or a laser application is provided based on the above described optoelectronic device comprising a perovskite material passivated with the passivation agent. Laser applications includes but are not limited to laser gain media in optical pump laser or laser diodes.
According to one embodiment of the invention a photo detector or an optical communication device is provided based on the above described optoelectronic device comprising a perovskite material passivated with the passivation agent.
According to one embodiment of the invention devices comprising luminescent down conversion materials or up conversion materials in any photoelectric application or an optical communication device is provided based on the above described optoelectronic device comprising a perovskite material passivated with the passivation agent.
The structure of a PeLED according to the invention is schematically illustrated in Fig.4. The Pe Led 40 comprises a substrate 41, a transparent conducting material layer 42, an electron transport/injection layer 43, for example a ZnO/PEIE layer, a perovskite layer comprising the passivation agent 44, a hole transport layer (TFB) 45, and an electrode layer (back electrode) 46.
The structure of photovoltaic device, for example a solar cell, according to the invention is schematically illustrated in Fig.5. The photovoltaic device 50 comprises a substrate 51, a transparent conducting material layer 52, an electron transport layer, for example a compact TiO2 or a compact TiO2/mesoporous TiO2 double layer 53, a perovskite layer comprising the passivation agent 54, and a hole transport layer, for example Spiro-OMeTad 55, and an electrode layer (back electrode) 56.
The method of preparing a perovskite based optoelectronic device according to the invention comprises the steps of:
(1) Provide a perovskite precursor.
(2) Provide one or a combination of passivation agent(s) doped into the perovskite precursor. (3) Perovskite film surface treatment e.g. spin on the top of perovskite films or immerse perovskite films into a solution with passivation agents.
(4) Passivation molecule vapour treatment, for example place the perovskite films into an atmosphere with passivation molecule vapour. (5) Dope into anti-solvent (such as chlorobenzene, chloroform, ethyl ether which cannot dissolve perovskite) (e.g. a solution with PA, which is dropped onto perovskite films during perovskite film formation).
Examples of the method will be given below. As appreciated by the skilled person a number of further steps are taken to produce a specific optoelectronic device, for example a PeLED, such steps are follows established production technology and are well known for the skilled person.
It is to be noted that elements of different embodiments described herein may freely be combined with each other unless such a combination is expressly stated as unsuitable, as will be readily understood by the person skilled in the art. An attractive combination being providing a PA with two, or a plurality, of different passivation molecules for example according to different embodiments .
Results and discussions
Amino groups have been frequently employed to passivate perovskite semiconductors due to their coordination bonding to unsaturated PbI6-octahedral. Here, we select two similar amino- functionalized PAs, i.e.2,2¢-(ethylenedioxy)diethylamine (EDEA) and hexamethylenediamine (HMDA) (Fig.1a), which have identical length of alkyl chains; the difference is that EDEA has two additional O atoms within the chain. The formamidinium lead tri-iodide (FAPbI3) perovskite layers are deposited by spin-casting the precursors with a molar ratio of PbI2: FAI: PA = 1: 2: x (x = 0~30%), where FAI excess is used to eliminate the non-perovskite d-phase. We fabricate PeLEDs with the device architecture as depicted in the high-angle annular dark field cross-sectional scanning transmission electron microscope (HAADF-STEM) images in Fig.6b. Both HAADF-STEM and scanning electron microscope (SEM) images, Fig.7, show the formation of separated nano-island features in the perovskite emissive layer. All the films were deposited on ITO/ZnO:PEIE substrates. The Pb2+ concentration is 0.13M for all the cases. All the devices show EL peaks at 800 nm/1.55 eV (Fig.6c) and low turn on voltages around 1.25 V, where the measurements were performed in a N2-filled glovebox. In spite of the small difference between the chemical structures of EDEA and HMDA, we notice significant difference in the EQE values of the devices treated with these two PAs (Fig.6d). The peak EQE is 10.9% for the HMDA-treated devices and 17.9% for the EDEA-treated ones.
We performed time-of-flight secondary ion mass spectrometry (ToF-SIMS) (Fig.6f) and X- ray photoelectron spectroscopy (XPS) characterizations on perovskite films treated with EDEA, which has the lower boiling point of 105°C and thus represents the most critical sample. We observe obvious unfragment positive molecular ion of EDEA (C6H16N2O +
2 = 148.1) and changes in line shape of C1s, O1s, N1s core level spectra in the resulting perovskite films compared to the control ones, confirming the adsorption of EDEA molecules in the perovskite films and thus providing the opportunities for passivation. The passivation through coordination bonding is first evidenced by the strong interaction between PbI2 and EDEA, leading to a change of the solution colour in their mixture, followed by white precipitation formation. We further performed attenuated total reflectance-Fourier transform infrared (ATR-FT-IR) spectroscopy on the EDEA:PbI2 mixture. As shown in Fig.6g, the stretching absorption (n) bands from the–NH2 of the mixture shift to lower wavenumber with respect to those from the pure EDEA, indicating the formation of coordination bonds between Pb2+ and–NH2.
Notably, the molecules used as potential PAs could also be used as templating molecules to synthesize low dimensional perovskites. Thus, it is worth to investigate whether these PAs affect the three-dimensional (3D) crystal structure of FAPbI3. X-ray diffraction (XRD) measurements indicate no additional diffraction peaks other than those from 3D FAPbI3 in the treated perovskite films (Fig.6h).
The defects physics of the samples was investigated. We reveal that the remarkable performance improvement of EDEA-treated PeLEDs origins from the significantly reduced defects in the perovskite emissive layer. Thermal admittance spectroscopy (TAS) was performed to probe the trap density and the energy depth of trap states in the PeLEDs (Fig. 8a). The control and HMDA-treated devices show typical temperature dependent capacitance vs frequency (C-f) plots. The sub-gap energy deduced from the temperature dependent C-f plots shows a trap energy depth of 0.40 eV and 0.16 eV for the control and HMDA-treated devices, respectively. Fig.8b and 8c show the trap density deduced from the room
temperature C-f plots, giving a peak trap density of 7.8×1015 cm-3 eV-1 and 5.9×1015 cm-3 eV-1 for the control and HMDA-treated devices, respectively. These results indicate a moderate passivation effect of HMDA. In contrast, the EDEA-treated devices show almost temperature independent C-f plots, indicating a negligible influence from trap states and hence excellent passivation.
Excellent defects passivation, which results in significantly reduced trap states in EDEA- treated perovskites, eventually also results much enhanced external photoluminescence quantum yields (PLQYs) across a large range of excitation fluence, showing a peak PLQY of 56% (Fig.8d). Even at low fluence of 0.02 mW cm-2, the EDEA-treated films maintain a high PLQY of 40%, consistent with a low defect density. In contrast, the PLQYs of the control and HMDA-treated films show strong intensity dependence due to trap-mediated non-radiative recombination. Low trap-mediated recombination in the EDEA-treated samples is also confirmed by the time-correlated single photon counting (TCSPC) measurements (Fig.8e), which show a prolonged PL lifetime of 1330 ns compared to the control (130 ns) and HMDA- treated films (690 ns).
Having established the role that the O atom plays in affecting the passivation effects, we proceed to explore new PAs, aiming to both further validate our conclusions and improve the device performance. We designed three PAs (Fig.9a) with different strength of inductive effects, which are expected to result in different hydrogen bonding abilities and hence different passivation effectiveness. Compared with EDEA, the inductive effect can be increased by introducing one additional O atom (as in 2,2¢-[oxybis(ethylenoxy)]diethylamine (ODEA)), and reduced by increasing the length of alkyl chain between the N and O atoms (as in 4,9-dioxa-1,12-dodecanediamine (DDDA) and 4,7,10-trioxa-1,13-tridecanediamine (TTDDA))32. Among all the PAs with O atoms, the inductive effect in DDDA is the least effective since its N and O atoms are almost isolated from each other, resulting in the strongest hydrogen bonding ability of the amino groups. Fig.9b shows the average peak EQE values for all the passivated systems as a function of DEad. It clearly shows that the EL performance is strongly dependent on the DEad, and hence the hydrogen bonding ability of amino groups. As expected, ODEA, which shows a DEad value of -0.42 eV, delivers the highest average peak EQE of 19.0 ± 0.8% (Fig.9b and 9c).
We show the characteristics for the best performing ODEA-treated device, which gives a peak EQE up to 21.6% (Fig.9e), approaching the best organic and quantum dot LEDs. The radiance rapidly rises after the device turns on, reaching a high radiance of 308 W Sr-1 m-2 at 3.3 V (Fig.9d). The high EQE and low driving voltage result in an exceptionally high peak wall-plug efficiency up to 15.8% (Fig.9e). High efficiencies at high current densities have been challenging in other low-temperature processed LED techniques (e.g. organic LEDs) due to low charge carrier mobilites and strong exciton-induced quenching effects. Our device exhibits a low efficiency roll-off, maintaining a high EQE of 20.1 % and a wall-plug efficiency of 11.0% at a high current density of 200 mA cm-2, which makes them much more efficient than OLEDs and QLEDs at high excitations. Moreover, we further tested the operation lifetime (T50, time to half of the initial radiance) of these devices in the glovebox without encapsulation. The ODEA-treated devices are among the most stable PeLEDs to date7–10, 21, showing a long lifetime of 20 h at 25 mA cm-2 compared with the control devices (T50 = 1.5 h at 25 mA cm-2) (Fig.9f). The improved lifetime may result from the reduced Joule heating due to the high efficiency, or the suppression of ion migration due to the low defect density.
We show that our passivation method is applicable to other perovskite semiconductor, e.g. quasi-2D perovskite with PEA as large cation, Fig.10. In this case, we spin the EDEA chlorobenzene solution (0.1 vol%) on top of as-prepared PEA2FA2Pb3I10. We observe obvious EQE enhancement from 7% to 12%.
In summary, we have demonstrated high-efficiency near infrared PeLEDs with a peak EQE of 21.6%, which represents the most efficient PeLEDs to date. Our devices also show low efficiency roll-off, maintaining a high EQE of 20.1% and a wall-plug efficiency of 11.0% at a high current density of 200 mA cm-2. Our results indicate a unique opportunity for PeLEDs to achieve solution processed large-scaled LEDs with high efficiencies at high brightness.
Methods
Materials. The passivation agents (PAs), including hexamethylenediamine (HMDA), 2,2¢- (ethylenedioxy)diethylamine (EDEA), 4,9-dioxa-1,12-dodecanediamine (DDDA), 2,2¢- [oxybis(ethylenoxy)]diethylamine (ODEA), 4,7,10-trioxa-1,13-tridecanediamine (TTDDA), ethylene glycol diethyl ether (EGDE) were purchased from Sigma-Aldrich. Formamidinium iodide (FAI) was purchased from Dyesol. PbI2 (beads, 99.999%) was purchased from Alfa Aesar. Poly(9,9-dioctyl-fluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) was purchased from Ossila. Other materials for device fabrication were all purchased from Sigma-Aldrich. Preparation of the perovskite solution. Perovskite precursors (FAI: PbI2: PA molar ratio of 2: 1: x, x = 0 ~ 30%) were prepared with dimethylformamide (DMF) as the solvent. A 10 mg mL-1 PA solution was prepared at first, and then was diluted according to the required molar ratio to Pb2+. The optimal concentration for PbI2 was 0.13 M. The solution precursors were stirred at 50˚C for 12 h before spin-coating. Colloidal ZnO nanocrystal was synthesized by a solution–precipitation process, and the details can be found in the literature1.
PeLED fabrication. The indium tin oxide (ITO) glass substrates were sequentially cleaned by detergent and TL-1 (a mixture of water, ammonia (25%), and hydrogen peroxide (28%) (5:1:1 by volume)). The clean substrates were then treated by UV-ozone for 10 min. The ZnO nanocrystal solutions were spin-casted onto the substrates at 4,000 rpm for 30 s in air. Then the substrates were moved into a N2-filled glovebox. Next, a layer of polyethylenimine ethoxylated (PEIE) was deposited at 5,000 rpm (0.05 wt%, in IPA), followed by annealing at 100°C for 10 min. After cooling down to room temperature, the perovskite films were deposited from the precursors with various PA contents and Pb2+ concentrations at a spin- coating speed of 3,000 rpm, followed by annealing at 100°C for 10 min. For the control perovskite films prepared by anti-solvent treatment, the spin-casting rate is 5,000 rpm. In addition, 150 mL chlorobenzene (CB) was dropped after 5 seconds spinning. The TFB layer was deposited from its CB solution (12 mg mL-1) at 3,000 rpm. Finally, the MoOx/Au electrode was deposited by a thermal evaporation system through a shadow mask under a base pressure of ~1×10-7 torr. The device area was 7.25 mm-2 as defined by the overlapping area of the ITO films and top electrodes.
PeLEDs characterization. All PeLED device characterizations were carried out at room temperature in a nitrogen-filled glovebox. A Keithley 2400 source meter and a fibre integration sphere (FOIS-1) coupled with a QE Pro spectrometer (Ocean Optics) was used for the measurements. The PeLED devices are tested on top of the integration sphere and only forward light emission can be collected, consistent with the standard OLED characterization method. The absolute radiance was calibrated by a standard Vis-NIR light source (HL-3P- INT-CAL plus, Ocean Optics).
Perovskite film characterizations. X-ray diffraction patterns were obtained from an X-ray diffractometer (Panalytical X’Pert Pro) with an X-ray tube (Cu Ka, l = 1.5406 Å). Steady- state PL spectra of the perovskite films were recorded by using a fluorescent spectrophotometer (F-4600, HITACHI) with a 200 W Xe lamp as an excitation source.
Absorption spectra were measured with a PerkinElmer model Lambda 900.
X-ray photoelectron spectroscopy (XPS) tests were carried out using a Scienta ESCA 200 spectrometer in ultrahigh vacuum ( ~ 1x10-10 mbar) with a monochromatic Al (K alpha) X-ray source providing photons with 1486.6 eV. The XPS experimental condition was set so that the full width at half maximum of the clean Au 4f7/2 line (at the binding energy of 84.00 eV) was 0.65 eV. All spectra were measured at a photoelectron take off angle of 0° (normal emission). Time-of-flight secondary ion mass spectrometry (TOF-SIMS) tests were performed on a ToF- SIMS.5 instrument from IONTOF, Germany, operated in the spectral mode using a 25 keV Bi +
3 primary ion beam with an ion current of 0.78 pA. A mass resolving power of ca.6000 m/∆m was reached. For depth profiling a 1 keV Cs+ sputter beam with a current of 39.81 nA was used to remove the material layer-by-layer in interlaced mode from a raster area of 500 × 500 µm. This raster area was chosen to ensure a flat crater bottom over an area of 100 × 100 µm used for the mass-spectrometry. The position of the ITO substrate interface in the sputter depth profile was defined by half maximum of the In2 + secondary ion count rate.
H Nuclear Magnetic Resonance (NMR). The 1H NMR spectra were recorded on a Bruker Ultra Shield Plus 400 MHz NMR system. All the samples were prepared by dissolving 5 mg FAI in 0.4 ml dimethyl sulfoxide-d6 (DMSO-d6). For the blend samples, 15% EDEA or HMDA (molar ratio compared to FAI) was added.
Attenuated total reflectance-Fourier Transform Infrared (ATR-FT-IR). The ATR-FT-IR spectra were recorded from a PIKE MIRacle ATR accessory with a diamond prim in a Vertex 70 Spectrometer (Bruker) using a DLaTGS detector at room temperature. The measuring system was continuously kept in N2 atmosphere. The spectra were acquired at 2 cm-1 resolution and 30 scans between 4000 and 800 cm-1. The presented spectra were baselined- corrected by subtracting a linear baseline over the spectral ranges.
Aberration-corrected scanning transmission electron microscope (STEM). An FEI dual- beam FIB Helios workstation equipped with an in-situ micromanipulator and Pt gas injection system was used to prepare thin samples for STEM imaging. The final milling was performed at 3 kV. STEM investigations were conducted using JEOL ARM200F TEM equipped with a spherical aberration corrector at the condenser plane. A semi-convergence angle of 32 mrad was used. High-angle annual dark field (HAADF) and annual bright field (ABF) STEM were recorded with semi-angles in the range 68-280 mrad and 7-18 mrad, respectively.
Fluence-dependent PLQY and time-correlated single photon counting (TCSPC) measurements. The fluence-dependent PLQY was measured by a typical three-step technique with a combination of 445 nm continuous-wave (CW) laser, spectrometer, and an integrating sphere5. The TCSPC measurements were performed on an Edinburgh Instruments spectrometer (FLS980) with a 638 nm pulsed laser (less than 100 ps, 0.1 MHz). The total instrument response function (IRF) was less than 130 ps, and temporal resolution was less than 20 ps. All the perovskite films were deposited on ITO/ZnO:PEIE substrates with identical spin-casting condition for the optimized devices, and encapsulated by UV curable resin and glass slides.
Transient absorption (TA). The perovskite film samples were mounted in a chamber under dynamic vacuum (<10-5 mbar). TA spectroscopy was conducted in transmission geometry. An amplified Ti:sapphire laser (Quantronix Integra-C) generated ~130 fs pulses centred at 800 nm, at a repetition rate of 1 kHz. A broadband white light probe was generated by focusing the pulses into a thin CaF2 plate, and pump light at 400 nm was obtained via second harmonic generation in a BBO crystal. After interaction with the sample, a grating spectrometer was used to disperse the probe light on to a fast CCD array, enabling broadband shot-to-shot detection.
Trap density measurements by thermal admittance spectroscopy (TAS). For the device capacitance measurement, we used 0.4 M Pb2+ for all the cases to increase the signals. A sinusoidal voltage with a peek-to-peak value of 30 mV generated from a Tektronix AFG 3000 function generator was applied to the device. The current signal of the devices was amplified with a SR570 low noise current preamplifier (Stanford Research Systems) and then analysed using a SR830 lock-in amplifier (Stanford Research Systems), where the amplitude and phase of the current can be measured. Based on the amplitude and phase of the current signal, the capacitance of the device was calculated using the parallel equivalent circuit model. The capacitance spectra of the device were measured by scanning the frequency of the sinusoidal voltage from 0.01 to 100 kHz in a logarithmic step. The temperature of the device was controlled using a DE202AE closed cycle cryocooler (Advanced Research Systems). The capacitance-voltage curve was obtained by measuring the capacitance when the applied DC bias voltage scanning from -0.5 to l.0 V. Based on the capacitance spectra measured at different temperature, the trap density (NT) distribution in energy (Ew) was calculated with the following relations:
where Vbi is the built-in potential, W is the depletion width, Vbi and W are derived from capacitance-voltage measurement, C is the capacitance measured at angular frequency of w and temperature of T, k is the Boltzmann constant, n0 is the attempt-to-escape frequency, which can be obtained by fitting the relation of characteristic frequency with different T based on Equation (3).

Claims

Claims 1. An optoelectronic device based on a perovskite material comprising a passivation agent comprising at least one passivation molecule, characterized by the passivation molecule being a hydrocarbon compound comprising at least one passivation group, PG, at least one inductive group, IG, and an alkyl chain arranged as an structural unit according to the general formula:
wherein n is between 1 and 4.
2. The optoelectronic device according to claim 1, wherein the passivation molecule comprises at least two passivation groups and two inductive groups wherein each passivation group has a corresponding inductive group at a distance corresponding to a value of n between 1 and 4.
3. The optoelectronic device according to claim 1 or 2, wherein the passivation molecule comprises at least two passivation groups and one inductive groups associated with the two passivation groups wherein each passivation group has the inductive group at a distance corresponding to a value of n between 1 and 4.
4. The optoelectronic device according to claim 1, wherein n is between 1 and 3.
5. The optoelectronic device according to any of claims 1 to 4, wherein the passivation group is selected from primary amine, -NH2, secondary amines, -NHR, tertiarg amines,–NR2, ether and hydroxyl, -OR(H), sulfhydryl and thiol, -SR(H), carbonyl, C=O, phosphine PR3, phosphine oxides, P=O, carboxyl group, -COOR(H), sulphoxide, S=O, sulfone, O=S=O, or any Lewis Base function groups, wherein R is an alkyl chain or aryl groups.
6. The optoelectronic device according to any of any of claims 1 to 5, wherein the inductive group is selected from O, S, F, Cl, Br, I and N.
7. The optoelectronic device according to any of claims 1 to 5, wherein the inductive group is selected from cyano, -CN, nitro, -NO2, carbonyl, C=O, carboxyl group, - COOR(H), sulphoxide, S=O, sulfone, O=S=O, amide, -CONH2, acyl chloride, - COOCl, sulphoxide, S=O, sulfone, O=S=O.
8. The optoelectronic device according to claim 1, wherein the passivation agent
comprises one of or a combination of EDEA, ODEA, TTDDA and DDDA.
9. An optoelectronic device based on a perovskite material comprising a passivation agent comprising at least one passivation molecule, characterized by the passivation molecule is an aromatic compound which is substituted at least by one PG and at least by one inductive group, IG, arranged as a structural unit according to the general formula:
wherein Ar is a substituted aryl group comprising C5 to C50.
10. The optoelectronic device according to claim 9, wherein the passivation group is selected from primary amine, -NH2, secondary amines, -NHR, tertiarg amines,–NR2, ether and hydroxyl, -OR(H), sulfhydryl and thiol, -SR(H), carbonyl, C=O, phosphine PR3, phosphine oxides, P=O, carboxyl group, -COOR(H), sulphoxide, S=O, sulfone, O=S=O, or any Lewis Base function groups, wherein R is an alkyl chain or aryl groups.
11. The optoelectronic device according to any of claims 9 to 10, wherein the inductive group is selected from O, S, F, Cl, Br, I and N.
12. The optoelectronic device according to any of claims 9 to 10, wherein the inductive group is selected from cyano, -CN, nitro, -NO2, carbonyl, C=O, carboxyl group, - COOR(H), sulphoxide, S=O, sulfone, O=S=O, amide, -CONH2, acyl chloride, - COOCl, sulphoxide, S=O, sulfone, O=S=O.
13. An optoelectronic device based on a perovskite material comprising a passivation agent comprising at least one passivation molecule, characterized by the passivation molecule is a heteroaryl molecule with at least one substitution by IG, arranged as a structural unit according to the general formula: wherein HAr is a heteroaryl group comprising from C5 to C50, and at least one hetero atom selected from N, O, S.
14. The optoelectronic device according to claim 13, wherein the passivation group is selected from primary amine, -NH2, secondary amines, -NHR, tertiarg amines,–NR2, ether and hydroxyl, -OR(H), sulfhydryl and thiol, -SR(H), carbonyl, C=O, phosphine PR3, phosphine oxides, P=O, carboxyl group, -COOR(H), sulphoxide, S=O, sulfone, O=S=O, or any Lewis Base function groups, wherein R is an alkyl chain or aryl groups.
15. The optoelectronic device according to any of claims 13 to 14, wherein the inductive group is selected from O, S, F, Cl, Br, I and N.
16. The optoelectronic device according to any of claims 13 to 14, wherein the inductive group is selected from cyano, -CN, nitro, -NO2, carbonyl, C=O, carboxyl group, - COOR(H), sulphoxide, S=O, sulfone, O=S=O, amide, -CONH2, acyl chloride, - COOCl, sulphoxide, S=O, sulfone, O=S=O.
17. The optoelectronic device according to claim 1, wherein the passivation agent
comprises one of or a combination of molecules with following general structural formula:
wherein n is from 1 to 5,000,000.
18. The optoelectronic device according to claims 17, wherein the passivation group is selected from primary amine, -NH2, secondary amines, -NHR, tertiarg amines,–NR2, ether and hydroxyl, -OR(H), sulfhydryl and thiol, -SR(H), carbonyl, C=O, phosphine PR3, phosphine oxides, P=O, carboxyl group, -COOR(H), sulphoxide, S=O, sulfone, O=S=O, or any Lewis Base function groups, wherein R is an alkyl chain or aryl groups.
19. A photovoltaic device comprising the optoelectronic device according to any of claims 11 to 18.
20. A laser device comprising the optoelectronic device according to any of claims 11 to 18.
21. A photo detector comprising the optoelectronic device according to any of claims 11 to 18.
22. An X-ray detector comprising the optoelectronic device according to any of claims 11 to 18.
23. A light emitting diode comprising the optoelectronic device according to any of claims 11 to 18.
24. The light emitting diode (40) according to claim 23 comprising a substrate (41), a transparent conducting material layer (42), an electron transport/injection layer (43), a perovskite layer comprising the passivation agent (44), a hole transport layer (45), and an electrode layer(46).
25. The photovoltaic device (50) according to claim 20 comprising a substrate (51), a transparent conducting material layer (52), an electron transport layer (53), a perovskite layer comprising the passivation agent (54), and a hole transport layer (55), and an electrode layer (56)
26. A method of producing the optoelectronic device according to any of claims 1 to 16 comprising the steps of
- providing a perovskite precursor;
-providing one or a combination of passivation agent(s) doped into the perovskite precursor;
-performing perovskite film surface treatment;
-performing passivation molecule vapour treatment; and
-doping into anti-solvent.
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