CN114072923A - Perovskite optoelectronic devices with defect passivation - Google Patents
Perovskite optoelectronic devices with defect passivation Download PDFInfo
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- CN114072923A CN114072923A CN202080032884.2A CN202080032884A CN114072923A CN 114072923 A CN114072923 A CN 114072923A CN 202080032884 A CN202080032884 A CN 202080032884A CN 114072923 A CN114072923 A CN 114072923A
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- passivating
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- optoelectronic device
- perovskite
- sulfoxide
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- H—ELECTRICITY
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- 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
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- H01L31/0264—Inorganic materials
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- Inorganic Compounds Of Heavy Metals (AREA)
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- Luminescent Compositions (AREA)
Abstract
The present invention relates to optoelectronic devices based on perovskite materials comprising organic passivating agents for reducing unwanted recombination effects, and to methods of manufacturing the same. In particular, the invention relates to PeLED with abnormally high EQE up to 21.6%.
Description
Technical Field
The present invention relates to metal halide perovskite optoelectronic devices and organic passivating agents. In particular, the invention relates to metal halide perovskite optoelectronic devices in which defects have been passivated by the introduction of passivating molecules in which the ability to hydrogen bond has been reduced.
Background
Perovskites (particularly metal halide perovskites) have received increasing attention over the past decade as promising functional materials 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 wide adjustability of band gap, defect tolerance, high photoluminescence quantum efficiency and high emission color purity.
In order to realize perovskite-based high efficiency light emitting diodes (pelds), extensive attempts have been made to increase radiative recombination rates by confining electrons and holes. These limiting attempts include the use of ultra-thin emissive layers, the fabrication of nano-scale polycrystalline parts, the design of low-dimensional or multi-quantum well structures, and the synthesis of perovskite quantum dots. As a result, the EQE value of the PeLED has increased from less than 1% to about 14%.
In addition to increasing radiative recombination rates, reducing non-radiative recombination is also important to improving device performance. Unfortunately, prior art solution processed perovskite semiconductors suffer from severe trap-mediated non-radiative losses, which have been identified as the primary efficiency limiting factor for both Photovoltaics (PV) and LEDs. It is generally believed that the trap states are associated with ion defects (e.g., halide vacancies). Defect passivation by a molecular Passivating Agent (PA) that can chemically bond with defects is an attractive approach to solving this problem. Some functional groups (e.g. -NH) have been identified2P ═ O) to passivate the perovskite semiconductor for photovoltaic applications. These PAs were found to exhibit strong structure-dependent properties even though they have the same functional groups for interacting with perovskite defects. These functional groups have also been borrowed to improve the efficiency of LEDs with limited success to date. For example, treatment with trioctylphosphine oxide (TOPO) in a green PeLED has been reported to result in only moderate EQE enhancement.
A recently published article, "complete light-emitting diodes based on specific surface-scale structures" (Cao et al, 11.10.2018, Nature 249) discloses the introduction of amino acid additives into Perovskite precursor solutions and reports that the EQE of 5-aminopentanoic acid (5AVA) exceeds 18%. Similar results are claimed for even longer chain length amino acids (6-aminocaproic acid (6AcA) and 7-aminoheptanoic acid). This positive effect is attributed to the additive that promotes the formation of submicron structures, which is described as having a passivating effect.
Although improvements have been made, the negative effects of non-radiative recombination must be reduced to a considerable extent in order to make opto-electronic devices based on metal halide perovskite materials commercially attractive compared to alternative technologies such as polymer LEDs and organic LEDs.
Summary of The Invention
Although advances have been made in providing efficient perovskite material-based optoelectronic devices, non-radiative recombination losses remain a significant problem in providing commercially attractive devices.
It is an object of the present invention to provide a method and device that overcomes the disadvantages of the prior art.
This is achieved by an opto-electronic device as defined in claim 1, claim 9, claim 13 and claim 17 and a method as defined in claim 26.
According to an aspect of the present invention, there is provided an optoelectronic device based on a perovskite material comprising a passivating agent, the passivating agent comprising at least one passivating molecule. The passivating molecule is a hydrocarbon compound comprising at least one passivating group PG, at least one sensing group IG and an alkyl chain, arranged as a structural unit according to the following general formula:
wherein n is between 1 and 4. The passivating molecule can comprise at least two passivating groups and two sensing groups, wherein each passivating group has a corresponding sensing group at a distance corresponding to a value of n between 1 and 4. Alternatively, the purification molecule comprises at least two passivating groups and one sensing group associated with the two passivating groups, wherein each passivating group has a sensing group at a distance corresponding to a value of n between 1 and 4.
According to an aspect, n is between 1 and 3.
According to one aspect of the invention, the passivating molecule is an aromatic compound substituted with at least one (at least one by one) PG and at least one (at least one by one) sensing group IG arranged as a structural unit according to the following general formula:
PG-Ar-IG
wherein Ar is a substituted aryl group comprising C5-C50.
According to one aspect of the invention, the passivating molecule is an aromatic compound substituted with at least one (at least one by one) PG and at least one (at least one by one) sensing group IG arranged as a structural unit according to the following general formula:
PG-Ar-IG
wherein Ar is a substituted aryl group comprising C5-C50.
According to one aspect of the invention, the passivating agent comprises one or a combination of molecules having the general formula:
wherein n is 1 to 5,000,000.
According to one aspect of the invention, the passivating group is selected from primary amines (-NH)2) Secondary amine (-NHR), tertiary amine (-NR)2) Ethers and hydroxy (-or (h)), mercapto and thiol (-sr (h)), carbonyl (C ═ O), Phosphine (PR)3) Phosphine oxide (P ═ O), carboxyl (-coor (h)), sulfoxide (S ═ O), sulfone (O ═ S ═ O), or any lewis base functional group, where R is an alkyl chain or aryl group.
According to an aspect of the invention, the sensor group is selected from O, S, F, Cl, Br, I and N.
According to an aspect of the invention, the sensing group is selected from cyano (-CN), nitro (-NO)2) Carbonyl group ofA group (C ═ O), a carboxyl group (-coor (h)), a sulfoxide (S ═ O), a sulfone (O ═ S ═ O), an amide (-CONH)2) Acyl chloride (-COOCl), sulfoxide (S ═ O), sulfone (O ═ S ═ O).
According to an aspect of the invention, the passivating agent comprises one or a combination of EDEA, ODEA, TTTDA and DDDA.
According to aspects of the present invention, the optoelectronic device is a photovoltaic device, a laser device, a photodetector, an X-ray detector, or a light emitting diode.
The method of manufacturing a photovoltaic device according to the invention comprises the following steps:
-providing a perovskite precursor;
-providing a passivating agent or combination of passivating agents doped into the perovskite precursor;
-performing a perovskite film surface treatment;
-performing a passivating molecular vapour treatment; and
incorporation into an antisolvent.
Thanks to the invention, defect sites in the perovskite are associated with passivating functional groups (e.g., -NH)2) The interaction between them can be greatly improved. As a result, non-radiative losses in the perovskite semiconductor are greatly reduced, which allows for improved performance of the perovskite optoelectronic device. In particular, one advantage of the present invention is that it allows the preparation of perovskite LEDs with exceptionally high EQEs of up to 21.6%, which is comparable to LEDs with optimal solution processing of organic and quantum dot semiconductors.
Another advantage is that perovskite LEDs with efficient passivation result in slow current efficiency roll-off at 200mA cm-2Maintains a high EQE of 20.1% and an electro-optic conversion efficiency (wall-plug efficiency) of 11.0% at high current densities, making them more attractive than the most efficient organic and quantum dot LEDs at high excitation.
The inventors have recognized that effective passivation as invented herein 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 reference to the accompanying drawings, with respect to non-limiting embodiments of the invention.
Brief Description of Drawings
FIG. 1 is a schematic illustration of the induction effect utilized in an embodiment of the present invention;
FIG. 2 is the structure of a candidate passivating agent investigated;
FIG. 3 is a graph showing the average EQE peak value vs. Δ E from candidate passivant-treated PeLEDadA graph of dependencies of;
FIG. 4 is a schematic diagram of a PeLED according to the present invention;
FIG. 5 is a schematic view of a photovoltaic device according to the present invention;
FIGS. 6 a-h: construction, performance and perovskite film characteristics of PeLED: (a) molecular structures of HMDA and EDEA, (b) having Indium Tin Oxide (ITO)/ethoxylated Polyethyleneimine (PEIE): modified zinc oxide nanocrystals (ZnO: PEIE)/perovskites/poly (9, 9-dioctylfluorene-co-N- (4-butylphenyl) diphenylamine) (TFB)/molybdenum oxide (MoO)3) High Angle Annular Dark Field (HAADF) cross-sectional image (left, scale bar 500nm) and magnified image (right, scale bar 100nm) of EDEA-treated device of Au configuration. Representative device characteristics of the optimization control device and PA-treated (HMDA, EDEA) device: (c) EL spectrum at 2.5V; (d) EQE-J curve; (e) current density-voltage-radiance (J-V-R) characteristics. (f) TOF-SIMS measurement (25%) of EDEA treated perovskite films on ITO/ZnO: PEIE substrates showed non-fragment (fragment) molecular ions (M)+＝EDEA+) And fragment molecular ion ([ M-NH ]3]+And [ M-H]+). (g) For EDEA and PbI2ATR-FT-IR (N-H stretching) of the EDEA mixture. (h) XRD patterns for control film, EDEA (25%) treated film and HMDA (25%) treated film on ITO/ZnO: PEIE substrate. Alpha and # indicate corresponding to alpha-FAPBI, respectively3And diffraction peaks of ITO;
FIGS. 7 a-c: top view SEM images of perovskite films according to the invention, (a) control perovskite films prepared with and without anti-solvent (AS) treatment. b. c: edea (b) treated perovskite film and hmda (c) treated perovskite film, wherein PA content varies from 10% to 30%; the scale of the image is 200 nm;
FIGS. 8 a-e: (a) control device, HMDA treated deviceAnd a plot of capacitance versus frequency for the temperature dependence (320-240K) of the EDEA processed devices. (b) And (c): (ii) trap density, deduced from room temperature C-f plots of control (b) and HMDA treated (C) samples, (d) fluence (fluence) dependent PLQY. (e) PL lifetime of time-dependent single photon counting (TCSPC) detection. Excitation density for TCSPC measurement is about 1015cm-3；
FIGS. 9 a-f: dependence of EL performance on passivation effect due to hydrogen bonds, (a) molecular structure of selected PA (ODEA, TTDDA, DDDA), the letters shown in chemical structure intended to highlight the different lengths of carbon chain between N and O atoms, (b) average EQE peak to Δ E from various PA treated PeLEDadEach value is an average of 60 devices, (c) histogram of peak EQE of control and ODEA treated devices, device characteristics of best performing ODEA treated devices, (d) J-V-R characteristics, (e) EQE and electro-optic conversion efficiency as a function of current density, (f) at 25mA cm for control and ODEA treated devices-2Steady state EQE under;
FIG. 10: based on quasi-2 DPEA surface treated with EDEA and not (0.1 vol.% in chlorobenzene)2FA2Pb3I10Representative device characteristics of perovskite films, (a) EL spectra at 2.5V, (b) J-V-R, c J-EQE, where Pb is2+The concentration of (A) is 0.11M;
FIG. 11: FAPBI based on HMDA (a-c) passivation3FAPBI with membranes and EDEA (d-f) passivation3Representative device characteristics of the membrane. (a) And (d) an EL spectrum at 2.5V. (b) Chain cents, J-V-R. c. f: J-EQE, perovskite layer is prepared from precursors with a feed ratio of FAI to PbI2:PA＝2:1:x，x＝10％、20％、25％、30％)，Pb2+The concentration of (A) is 0.13M;
FIG. 12: FAPBI based on ODEA (a-c) passivation at various PA feed ratios3Film, TTDDA (d-f) passivated FAPBI3Film and DDDA (g-i) passivated FAPBI3Representative device characteristics of the membrane. (a) (d) EL spectrum at 2.5V. b. e, h: J-V-R. c. f, i: J-EQE, perovskite layer prepared from precursor with FAI to PbI feeding ratio2:PA＝2:1:x，x＝10％、20％、25％、30％)，Pb2+The concentration of (A) is 0.13M;
FIG. 13: histogram of peak EQE from 60 devices with optimized PA feed ratio. (a) HMDA 20%. (b) DDDA 25%. (c) EDEA 25%. (d) TTDDA was 20%, and the mean EQE peaks were 10.7 ± 0.67% (HMDA), 11.8 ± 0.43% (DDDA), 16.5 ± 0.67% (EDEA), and 16.4 ± 0.61% (TTDDA) for each case, all of which were prepared from the same batch of ZnO nanocrystals.
Detailed description of the invention
The present invention relates to optoelectronic devices based on perovskite materials comprising organic passivating agents for reducing unwanted recombination effects, and to methods of manufacturing the same.
Perovskites are a class of materials primarily directed at CaTiO3(XIIA2+VIB4+X2- 3) ABX described3The compound of three-dimensional structure is named perovskite structure. A and B are cations having various valences and ionic radii, and X is an anion. For metal halide hybrid perovskites, the A component is typically a monovalent organic cation, typically methylammonium (CH)3NH3 +＝MA+) Or formamidinium (HC (NH)2)2 +＝FA+) Atomic cation (usually Cs)+) Or mixtures thereof, the B component typically being a divalent metal cation (typically Pb)2 +、Sn2 +Or mixtures) and the X component is a halide anion (typically Cl)-、I-、Br-Or mixtures thereof). Examples include, but are not limited to, MAPbX3、FAPbX3、CsPbX3、MASnX3、FASnX3And CsSnX3. Or such as FA0.85MA0.1Cs0.05(Pb0.5Sn0.5)I2Br0.5Cl0.5Combinations of (a) and (b).
The B component is typically a divalent metal cation, typically Pb2+. It may also be selected from Sn2+、Ge2+、Eu2+、Cu2+、Tb2 +、Fe2+、Co2+、Zn2+、Mn2+Or with Pb2+Mixture of (e.g. Sn)2+/Pb2+) At least one of (1).
A more general description of metal halide perovskites is: a'2(ABX3)n-1BX4. Where n is the semiconductor BX in two organic insulating layers (cations A')4Number of single-layer sheets, wherein n ∞ corresponds to 3D perovskite ABX3A' is a large organic ammonium cation which cannot be incorporated into the 3D perovskite lattice but forms a layered structure or low dimensional perovskite, such as C4H9NH3 +(BA) or C8H12NH3 +(PEA)。
There are a number of options to form quasi-2D perovskites or 2D perovskites, for example:
pure 2D perovskites, e.g. BA2PbI4；
Quasi 2D perovskites (n ═ 2), e.g. BA2(FA)Pb2I7；
Quasi 2D perovskites (n ═ 3), such as BA2(FA)2Pb3I10When n ═ infinity, it is 3D FAPBI3(first part).
The present invention relates to both 3D and quasi 2D perovskites.
The perovskite may also conform to A2B1 +B2 3+X6The structural formula (1). Where A is a monovalent organic cation or alkali metal ion, including Li+、Na+、K+、Rb+、Cs+。B1 +Is a monovalent metal ion, e.g. Ag+、Cu+。B2 3+Is a trivalent metal ion selected from Bi3 +、In3+、Fe3+、Sb3+. The X component being a halide anion (usually Cl)-、I-、Br-Or mixtures thereof).
The synthesis of perovskite materials is typically carried out in solution, from which bulk, layered or micro/nanostructured perovskites can be obtained.
In the following, perovskite light emitting diodes (pelds) are discussed as illustrative examples. It will be apparent to those skilled in the art that the present invention is applicable to all optoelectronic devices in which perovskite materials are utilized, including but not limited to photovoltaic devices, such as solar cells; laser gain media in optical pump lasers or laser diodes, photodetectors and optical communication devices, X-ray detectors, luminescent down-conversion materials or luminescent up-conversion materials in any optoelectronic application, such as sensors, luminescent solar concentrators and phosphor materials.
As discussed in the background section, the primary efficiency limitation of solution processed perovskite optoelectronic devices (e.g., light emitting diodes, LEDs) is trap-mediated non-radiative loss. Defect passivation using organic molecules, molecular Passivators (PA), has been identified as an attractive approach to solving this problem. However, this approach has been practiced with only marginal success. Surprisingly, the inventors have found that weakening of the hydrogen bonds between the passivating functional moiety and the organic cations characterizing the perovskite enhances the interaction with defect sites and minimizes non-radiative recombination losses. Thus, an exceptionally high performance near-infrared perovskite led (peled) with an External Quantum Efficiency (EQE) of 21.6% can be produced. Furthermore, at 200mA cm-2The passivated PeLED maintained a high EQE of 20.1% and an electro-optic conversion efficiency of 11.0% at high current densities.
The PA utilized according to the present invention is designed to reduce hydrogen bonding capability. In particular, PA with oxygen atoms within the PA serves to polarize the inactive amino groups by inductive effects, reducing their electron donating ability and hence the associated hydrogen bonding ability. This results in enhanced coordination of the PA functional groups to the perovskite defect sites and thus improved passivation efficiency. As a result, trap-mediated non-radiative recombination is reduced and the Electroluminescence (EL) performance of the PeLED is enhanced.
Perovskite-based optoelectronic devices according to the present invention comprise perovskite materials comprising at least one Passivating Agent (PA) or a combination of Passivating Agents (PA). The one or more PAs are hydrocarbon compounds comprising at least one Passivating Group (PG), at least one sensing group (IG), and an alkyl chain. The PA molecules may be conjugated or non-conjugated small molecules, polymers, oligomers.
Suitable passivating groups are known in the art and include, but are not limited to: -NH2、-NHR、NR3-OR (H), -SR (H), phosphine oxide, sulfoxide (S ═ O), Sulfone (SO)2) Any lewis base functional group. R ═ alkyl or aromatic fused rings. Alternatively, the deactivating functional group is an aromatic fused ring containing a heteroatom (O, N, S, B), such as pyridine, pyrrole, imidazole, furan, thiophene, and thiazole.
Suitable sensor groups are known in the art and include, but are not limited to: strongly electronegative atoms, such as O, S, F, Cl, Br, I, N; functional groups exhibiting electron withdrawing/donating properties that affect the hydrogen bonding capability of the passivating functional groups, including-CN, -NO2、C＝O、COOR(H)、COO-、COONH2、COOCl、S＝O、SO2。
The sensing group (IG) affects the Passivating Group (PG) and thereby affects the hydrogen bond between the amino group and FA + of the perovskite material. Without being bound by theory, this is schematically illustrated in fig. 1, where IG is O and PG is amino (-NH)2). IG according to the invention and the distance in the carbon chain measured in number n of carbons are chosen such that the electron-withdrawing induction effect of IG (here the O atom) affects PG, thereby polarizing the PG electrons towards IG, which consequently reduces the electron-donating ability of the amino group and the associated hydrogen bonding ability.
According to one embodiment of the invention, PA has a structural unit according to the following general formula:
wherein n is chosen to be between 1 and 4. The choice of n is based on the resulting peak external quantum efficiency (peak EQE). A number of PA candidates with different distances n and different numbers of PG groups were tested: HMDA, EDEA, ODEA, TTDDA, and DDDA, the respective structures of which are illustrated in FIG. 2. Details of the experiment will be discussed below. Fig. 3 is a diagram illustrating the peak EQE of a PA candidate. All PA candidates with IG (n <4) outperformed PA candidates without IG (HMDA). As shown in the figure, significant performance enhancement was found for PAs where n becomes small, as evidenced by comparing ODEA/TTDDA or EDEA/DDDA. Increasing the number of IGs also affected the peak EQE as evidenced by comparing EDEA/ODEA and DDDA/TTDDA. The information summarized in FIG. 3 is presented in detail in FIGS. 11-13.
According to an embodiment of the present invention, the conjugation effect provided by the introduction of aryl groups is exploited in at least one passivating molecule of the PA.
According to one embodiment, the passivating molecule is an aromatic compound substituted with at least one (at least one by one) PG and at least one (at least one by one) sensing group IG, arranged as a structural unit according to the following general formula:
PG-Ar-IG
wherein Ar is a substituted aryl group comprising C5-C50.
According to one embodiment, the passivating group is a heteroaryl molecule having at least one substituent IG arranged as a structural unit according to the general formula:
HAr-IG
wherein HAr is a heteroaryl group comprising C5-C50 and at least one heteroatom selected from N, O, S.
According to one embodiment, the passivating agent comprises one or a combination of molecules having the following general structural formula:
wherein n is 1 to 5,000,000.
According to one embodiment of the present invention, a photovoltaic device is provided based on the above-described photovoltaic device comprising a perovskite material passivated with a passivating agent. Examples of photovoltaic devices include, but are not limited to, solar cells.
According to one embodiment of the present invention, a laser device or laser application is provided based on the above-described optoelectronic device comprising a perovskite material passivated with a passivating agent. Laser applications include, but are not limited to, optical pump lasers or laser gain media in laser diodes.
According to one embodiment of the present invention, an optoelectronic device based on the perovskite material passivated with a passivating agent as described above provides a photodetector or optical communication device.
According to one embodiment of the present invention, a photovoltaic device based on the above described perovskite material passivated with a passivating agent is provided comprising a luminescent down-or up-conversion material in any photovoltaic application or an optical communication device.
The structure of the PeLED according to the invention is schematically illustrated in fig. 4. The Pe Led 40 includes a substrate 41, a transparent conductive material layer 42, an electron transport/injection layer 43 (e.g., ZnO/PEIE layer), a perovskite layer 44 containing a passivating agent, a hole transport layer (TFB)45, and an electrode layer (back electrode) 46.
The structure of a photovoltaic device (e.g. a solar cell) according to the invention is schematically illustrated in fig. 5. Photovoltaic device 50 includes a substrate 51, a transparent conductive material layer 52, an electron transport layer (e.g., dense TiO)2Or compact TiO2Mesoporous TiO2Bi-layer) 53, a perovskite layer 54 containing a passivating agent, and a hole transport layer (e.g., Spiro-OMeTad)55, and an electrode layer (back electrode) 56.
A method of fabricating a perovskite-based optoelectronic device according to the present invention comprises the steps of:
(1) a perovskite precursor is provided.
(2) A passivating agent or combination of passivating agents is provided that is doped into the perovskite precursor.
(3) The perovskite film is surface treated, for example by spinning on top of the perovskite film or dipping the perovskite film into a solution containing a passivating agent.
(4) Passivating molecular vapor treatment, such as placing the perovskite film into an atmosphere with passivating molecular vapor.
(5) An anti-solvent (e.g., chlorobenzene, chloroform, ether which cannot dissolve the perovskite) (e.g., a PA-containing solution dropped onto the perovskite film during formation of the perovskite film) is incorporated.
An example of this method will be given below. As the skilled person realizes, many further steps are taken to produce a particular optoelectronic device, e.g. a PeLED, such steps following established production techniques and being well known to the skilled person.
It should be noted that elements of the different embodiments described herein may be freely combined with each other, as will be readily understood by those skilled in the art, unless such combination is explicitly stated to be inappropriate. For example, according to various embodiments, an attractive combination is to provide a PA with two or more different passivating molecules.
Results and discussion
Due to amino groups and unsaturation of PbI6-coordination bonding of octahedra, amino groups have been frequently used to passivate perovskite semiconductors. Here, we selected two similar amino-functionalized PAs, i.e., 2,2' - (ethylenedioxy) diethylamine (EDEA) and Hexamethylenediamine (HMDA) (fig. 1a), which have the same alkyl chain length; the difference is that EDEA has two additional O atoms in the chain. By adding PbI2Deposition of lead formamidine triiodide (FAPbI) by spin casting of precursors at a molar ratio of FAI: PA: 1:2: x (x: 0-30%)3) Perovskite layers in which FAI excess is used to eliminate the non-perovskite delta phase. We fabricated a PeLED with the device configuration as depicted in the high angle annular dark field cross section scanning transmission electron microscope (HAADF-STEM) image in fig. 6 b. Both the HAADF-STEM and Scanning Electron Microscope (SEM) images (fig. 7) show the formation of isolated nano-island features in the perovskite emission layer. All films were deposited on an ITO/ZnO PEIE substrate. In all cases, the Pb2+ concentration was 0.13M. All devices showed EL peak at 800nm/1.55eV (FIG. 6c) and low turn-on voltage of about 1.25V with N filled2The measurements were carried out in a glove box. Although the difference between the chemical structures of EDEA and HMDA is small, we note that there is a significant difference in the EQE values for devices treated with these two PAs (fig. 6 d). The peak EQE for the HMDA treated device was 10.9%, and the peak EQE for the EDEA treated device was 17.9%.
We performed time-of-flight secondary ion mass spectrometry (ToF-SIMS) (FIG. 6f) and X-ray photoelectron spectroscopy (XPS) characterization of perovskite films treated with EDEA, which has a lower boiling point of 105 deg.C, and thus represents the most harsh sample. Compared to the control film, we observed a distinct non-fragmenting molecular cation (C) of EDEA in the resulting perovskite film6H16N2O2 +148.1) and C1s, O1s, N1s core level spectra (core level spectra) linear changes, confirming the adsorption of EDEA molecules in perovskite films and thus providing an opportunity for passivation. Passivation by coordination bonding is first initiated by PbI2And EDEA, which results in a change in the color of the solution in its mixture, with the subsequent formation of a white precipitate. We further treated EDEA: PbI2The mixture was subjected to attenuated total reflectance fourier transform infrared (ATR-FT-IR) spectroscopy. As shown in FIG. 6g, the tensile absorption (v) band of the mixture is from-NH relative to the tensile absorption band of pure EDEA2Shift to lower wavenumbers, indicating Pb2+and-NH2Form coordinate bonds between the two.
Notably, the molecules used as potential PAs can also be used as template molecules to synthesize low-vitamin perovskite. Therefore, it is worth investigating whether these PAs affect the FAPbI3A three-dimensional (3D) crystal structure of (a). X-ray diffraction (XRD) measurements showed no difference in the treated perovskite films from 3D FAPbI3Additional diffraction peaks of those (fig. 6 h).
The samples were investigated for defective physical properties. We disclose: the significant performance improvement of the EDEA treated PeLED results from a significant reduction of defects in the perovskite emission layer. Thermal Admittance Spectroscopy (TAS) was implemented to probe the trap density and the energy depth of the trap states in the PeLED (fig. 8 a). The control and HMDA treated devices show a typical temperature dependent plot of capacitance as a function of frequency (C-f). The energy of the sub-gap derived from the temperature-dependent C-f plot shows: the trap energy depths of the control and HMDA treated devices were 0.40eV and 0.16eV, respectively. FIGS. 8b and 8C show the trap density derived from the room temperature C-f plot, giving peak trap densities of 7.8X 10 for the control and HMDA treated devices, respectively15cm-3eV-1And 5.9X 1015cm-3eV-1. These results indicate a moderate passivation effect of HMDA. In contrast, the EDEA-treated devices showed a C-f plot that was nearly temperature independent, indicating trapsThe effect of the well state is negligible and thus the passivation is excellent.
Excellent defect passivation, which leads to significantly reduced trap states in the EDEA-treated perovskite, ultimately also leads to a greatly improved external photoluminescence quantum yield (PLQY) across a large range of excitation energy densities, showing a peak PLQY of 56% (fig. 8 d). Even at 0.02mW cm-2The EDEA treated films still maintained a high PLQY of 40% at low energy densities, consistent with low defect densities. In contrast, PLQY of control and HMDA treated films showed strong intensity dependence due to trap-mediated non-radiative recombination. Low trap-mediated recombination in the EDEA-treated samples was also confirmed by time-correlated single photon counting (TCSPC) measurements (fig. 8e), which showed an extended PL lifetime of 1330ns compared to the control (130ns) and HMDA-treated (690ns) membranes.
After establishing the role of O atoms in influencing the passivation effect, we continued to explore new PAs aiming at both further validating our conclusions and improving device performance. We designed three PAs with different strengths of the inductive effect (fig. 9a), which are expected to lead to different hydrogen bonding capabilities and thus to different passivation effects. The induction effect can be increased by introducing an additional O atom compared to EDEA (e.g. 2,2' - [ oxybis (ethyleneoxy)]Diethylamine (ODEA) and to reduce the inducing effect by increasing the alkyl chain length 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 PAs with O atoms, the induction effect in DDDA is the least effective, as its N and O atoms are almost isolated from each other, resulting in the strongest hydrogen bonding ability of the amino group. FIG. 9b shows the dependence on Δ EadWhile the average EQE peak for all passivated systems varied. It clearly shows that the EL performance strongly depends on Δ EadAnd thus on the hydrogen bonding capability of the amino group. As expected, ODEA (which shows a. DELTA.E of-0.42 eV)adValues) showed the highest mean EQE peak at 19.0 ± 0.8% (fig. 9b and 9 c).
We show the characteristics of the device that performs the best ODEA treatment, giving a peak of up to 21.6%EQE (fig. 9e), near optimal organic and quantum dot LEDs. After the device is turned on, the radiance rises rapidly to reach 308W Sr at 3.3V-1m-2High radiance (fig. 9 d). High EQE and low drive voltage resulted in exceptionally high peak electro-optical conversion efficiencies of up to 15.8% (fig. 9 e). High efficiency at high current densities has been challenging in other low temperature processed LED technologies (e.g., organic LEDs) due to low carrier mobility and strong exciton-induced quenching effects. Our device is at 200mA cm-2Exhibits low efficiency roll-off, maintaining a high EQE of 20.1% and an electro-optic conversion efficiency of 11.0%, which makes them much more efficient than OLEDs and QLEDs at high excitation. In addition, we further tested the operational lifetime (T) of these devices in an unpackaged glove box50Time to half of the initial radiance). The ODEA treated device is among the PeLEDs most stable to date7-10、21Comparison device (at 25mA cm)-2Lower T501.5h) at 25mA cm-2The lower panel shows a long lifetime of 20h (fig. 9 f). This improved lifetime may be caused by reduced joule heating due to high efficiency or inhibition of ion migration due to low defect density.
We show that our passivation method is applicable to other perovskite semiconductors, such as quasi-2D perovskites with PEA as the large cation (fig. 10). In this case, we are in the PEA prepared2FA2Pb3I10The EDEA chlorobenzene solution (0.1 vol%) was rotated on top. We observed a significant EQE increase from 7% to 12%.
In summary, we have demonstrated a highly efficient near-infrared PeLED with a peak EQE of 21.6%, which represents the most efficient PeLED to date. Our device also showed low efficiency roll-off at 200mA cm-2Maintains a high EQE of 20.1% and an electro-optic conversion efficiency of 11.0% at high current densities. Our results show a unique opportunity for PeLED to achieve large-scale LEDs with efficient solution processing at high brightness.
Method
Materials: the Passivating Agent (PA) comprises hexamethyleneDiaminoethane (HMDA), 2'- (ethylenedioxy) diethylamine (EDEA), 4, 9-dioxa-1, 12-dodecane diamine (DDDA), 2' - [ oxybis (ethyleneoxy)]Diethylamine (ODEA), 4,7, 10-trioxa-1, 13-tridecanediamine (TTDDA), Ethylene Glycol Diethyl Ether (EGDE), which was purchased from Sigma-Aldrich. Formamidinium iodide (FAI) is purchased from dysol. PbI2(beads, 99.999%) were purchased from Alfa Aesar. Poly (9, 9-dioctyl-fluorene-co-N- (4-butylphenyl) diphenylamine) (TFB) was purchased from Ossila. Other materials used for device fabrication were all purchased from Sigma-Aldrich.
Preparation of perovskite solution: preparation of perovskite precursor (FAI: PbI) Using Dimethylformamide (DMF) as solvent2The PA molar ratio is 2:1: x, and x is 0-30%). First, 10mg mL of the suspension was prepared-1PA solution, then optionally mixed with Pb2+Is diluted. PbI2The optimum concentration of (3) is 0.13M. The solution precursor was stirred at 50 ℃ for 12h before spin-coating. Synthesis of colloidal ZnO nanocrystals by solution precipitation process, details of which can be found in the literature1Is found in (1).
Manufacturing of the Peled: indium Tin Oxide (ITO) glass substrates were cleaned sequentially with detergent and TL-1 (a mixture of water, ammonia (25%) and hydrogen peroxide (28%) (5: 1:1 by volume). The cleaned substrate was then treated with UV-ozone for 10 minutes. The ZnO nanocrystal solution was spin cast onto the substrate at 4,000rpm for 30 seconds in air. Then the substrate is moved into the fill N2In a glove box. Next, a layer of ethoxylated Polyethyleneimine (PEIE) (0.05 wt% in IPA) was deposited at 5,000rpm and then annealed at 100 deg.C for 10 minutes. After cooling to room temperature, spin-coated at a spin speed of 3,000rpm from a solution having various PA contents and Pb2+The precursor at concentration deposited the perovskite film and then annealed at 100 ℃ for 10 minutes. For the control perovskite film prepared by anti-solvent treatment, the spin casting rate was 5,000 rpm. Further, 150. mu.L of Chlorobenzene (CB) was added dropwise after 5 seconds of rotation. CB solution from TFB (12mg mL)-1) The TFB layer was deposited at 3,000 rpm. Finally, at about 1X10-7MoO deposition by thermal evaporation system via shadow mask at base pressure of Torrxa/Au electrode. The device area, as defined by the overlapping area of the ITO film and the top electrode, is 7.25mm-2。
And (3) PeLED characterization: all characterization of the PeLED devices was performed at room temperature in a nitrogen-filled glove box. Measurements were performed using a Keithley 2400source meter and a fiber optic integrating sphere (FOIS-1) connected to a QE Pro spectrometer (Ocean Optics). The PeLED device was tested on top of the integrating sphere and only forward emission was collected, consistent with standard OLED characterization methods. The absolute radiance was calibrated by a standard Vis-NIR light source (HL-3P-INT-CAL plus, Ocean Optics).
Perovskite film characterization: from the perspective of having an X-ray tube (Cu K alpha,
) The X-ray diffractometer (Panalytical X' Pert Pro) of (1) obtained an X-ray diffraction pattern. The steady state PL spectra of the perovskite films were recorded by using a fluorescence spectrophotometer (F-4600, HITACHI) with a 200W Xe lamp as excitation source. The absorption spectrum was measured with a Perkinelmer model Lambda 900.
Using a Scienta ESCA 200 spectrometer under ultra high vacuum (approximately 1X 10)-10mbar), a monochromatic Al (K α) X-ray source provided 1486.6eV photons. XPS experimental conditions were set so that pure Au4f was obtained7/2The full width at half maximum of the wire (at a binding energy of 84.00 eV) was 0.65 eV. All spectra were measured at a photoelectron grazing angle of 0 ° (normal emission).
Time-of-flight secondary ion mass spectrometry (TOF-SIMS) tests were performed on a ToF-SIMS.5 instrument from IONOF, Germany, using a 25keV Bi of 0.78pA ion current3 +The primary ion beam is operated in a spectral mode. A mass resolving power of about 6000 m/am is achieved. For depth profiling, 1keV Cs with a current of 39.81nA were used+The sputter beam removes material layer by layer in a staggered pattern from a 500 x 500 μm grating area. The grating region was chosen to ensure a flat pit bottom over the 100 x 100 μm region used for mass spectrometry. The position of the ITO substrate interface In the sputtering depth profile is defined by In2 +Half the maximum value of the secondary ion count rate.
H Nuclear Magnetic Resonance (NMR): in Bruker Ultra ShieRecording on Id Plus 400MHz NMR System1H NMR spectrum. All samples were prepared by dissolving 5mg of FAI in 0.4ml of dimethyl sulfoxide-d 6(DMSO-d 6). For the blend samples, 15% EDEA or HMDA (molar ratio compared to FAI) was added.
Attenuated total reflectance fourier transform infrared (ATR-FT-IR): ATR-FT-IR spectra were recorded from a PIKE MIRacle ATR accessory with diamond prim using a DLaTGS detector at room temperature in a Vertex 70 spectrometer (Bruker). Persisting measurement systems in N2In an atmosphere. At 2cm-1A sum of resolutions between 4000cm-1 and 800cm -130 scans in between to obtain spectra. The presented spectrum is baseline corrected by subtracting a linear baseline in the spectral range.
Aberration-corrected Scanning Transmission Electron Microscope (STEM): a 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 carried out at 3 kV. The STEM survey was conducted using a JEOL ARM200F TEM equipped with a spherical aberration corrector at the condenser plane. A half convergence angle of 32mrad was used. High Angle Annular Dark Field (HAADF) and Annular Bright Field (ABF) STEM were recorded, with half angles in the range of 68-280mrad and 7-18mrad, respectively.
Energy density dependent PLQY and time dependent single photon counting (TCSPC) measurements: energy density dependence of PLQY is measured by a typical three-step technique using a combination of a 445nm Continuous Wave (CW) laser, a spectrometer and an integrating sphere5. TCSPC measurements were performed on an Edinburgh Instruments spectrometer (FLS980) with a 638nm pulsed laser (less than 100ps, 0.1 MHz). The overall Instrument Response Function (IRF) is less than 130ps and the instantaneous resolution is less than 20 ps. For the optimized device, all perovskite films were deposited on an ITO/ZnO: PEIE substrate under the same spin-casting conditions and encapsulated with UV curable resin and glass slides.
Transient Absorption (TA): mounting the perovskite film sample in a dynamic vacuum (<10-5mbar). TA spectroscopy was performed in transmission geometry. Amplified Ti sapphire laser (Quantron Integra-C) generates pulses of about 130fs centered at 8 fs at a repetition rate of 1kHz00 nm. By focusing pulses into a thin CaF2A broadband white light probe is generated in the plate and pump light at 400nm is obtained via second harmonic generation in the BBO crystal. After interaction with the sample, the probe light is scattered onto a fast CCD array using a grating spectrometer, enabling broadband flash-to-shot detection.
Trap density was measured by Thermal Admittance Spectroscopy (TAS). For device capacitance measurements, we used 0.4M Pb in all cases2+To increase the signal. A sinusoidal voltage with a peak-to-peak value of 30mV generated by a Tektronix AFG 3000 function generator was applied to the device. The current signal of the device was amplified with a SR570 low noise current preamplifier (Stanford Research Systems) and then analyzed using a SR830 lock-in amplifier (Stanford Research Systems), where the amplitude and phase of the current could be measured. The capacitance of the device is calculated using a parallel equivalent circuit model based on the magnitude and phase of the current signal. The capacitance spectrum of the device was measured by scanning a sinusoidal voltage frequency from 0.01kHz to 100kHz in logarithmic steps. DE202AE closed-cycle cryocoolers (Advanced Research Systems) are used to control the temperature of the components. The capacitance-voltage curve was obtained by measuring the capacitance when a DC bias voltage was applied, which was swept from-0.5V to l.0V. Based on the capacitance spectra measured at different temperatures, the energy (E) is calculated as followsω) Trap density (N) of meterT) Distribution:
wherein VbiIs built-in potential, W is depletion layer width, VbiAnd W is obtained from a capacitance-voltage measurement, C is the capacitance measured at an angular frequency W and a temperature T, k is the Boltzmann constant, v0Is the escape attempt frequency, which can be obtained by fitting the characteristic frequency to different T based on equation (3).
Claims (26)
1. Optoelectronic device based on a perovskite material comprising a passivating agent comprising at least one passivating molecule, characterized in that said passivating molecule is a hydrocarbon compound comprising at least one passivating group PG, at least one sensing group IG and an alkyl chain, arranged as structural units according to the following general formula:
wherein n is between 1 and 4.
2. An optoelectronic device according to claim 1, wherein the passivating molecule comprises at least two passivating groups and two sensing groups, wherein each passivating group has a corresponding sensing group at a distance corresponding to a value of n between 1 and 4.
3. An optoelectronic device according to claim 1 or 2, wherein the passivating molecule comprises at least two passivating groups and one sensing group associated with the two passivating groups, wherein each passivating group has the sensing group at a distance corresponding to a value of n between 1 and 4.
4. An optoelectronic device according to claim 1, wherein n is between 1 and 3.
5. An optoelectronic device according to any one of claims 1 to 4, wherein the passivating group is selected from primary amine-NH2Secondary amine-NHR, tertiary amine-NR2Ethers and hydroxy-or (h), mercapto and thiol-sr (h), carbonyl C ═ O, phosphine PR3Phosphine oxide P ═ O, carboxy-coor (h), sulfoxide S ═ O, sulfone O ═ S ═ O, or any lewis base functional group, where R is an alkyl chain or aryl group.
6. An optoelectronic device according to any one of claims 1 to 5, wherein the sensor group is selected from O, S, F, Cl, Br, I and N.
7. An optoelectronic device according to any one of claims 1 to 5, wherein the sensing group is selected from cyano-CN, nitro-NO2Carbonyl group C ═ O, carboxyl group-coor (h), sulfoxide S ═ O, sulfone O ═ S ═ O, amide-CONH2Acyl chloride-COOCl, sulfoxide O, sulfone O, S-O.
8. An optoelectronic device according to claim 1 wherein the passivating agent comprises one or a combination of EDEA, ODEA, TTDDA and DDDA.
9. Optoelectronic device based on a perovskite material comprising a passivating agent comprising at least one passivating molecule, characterized in that said passivating molecule is an aromatic compound substituted by at least one PG and at least one sensing group IG, arranged as a structural unit according to the following general formula:
PG-Ar-IG
wherein Ar is a substituted aryl group comprising C5-C50.
10. An optoelectronic device according to claim 9, wherein the passivating group is selected from primary amine-NH2Secondary amine-NHR, tertiary amine-NR2Ethers and hydroxy-or (h), mercapto and thiol-sr (h), carbonyl C ═ O, phosphine PR3Phosphine oxide P ═ O, carboxy-coor (h), sulfoxide S ═ O, sulfone O ═ S ═ O, or any lewis base functional group, where R is an alkyl chain or aryl group.
11. An optoelectronic device according to any one of claims 9 to 10, wherein the sensor group is selected from O, S, F, Cl, Br, I and N.
12. An optoelectronic device according to any one of claims 9 to 10, wherein the sensing group is selected from cyano-CN, nitro-NO2Carbonyl group C ═ O, carboxyl group-coor (h), sulfoxide S ═ O, sulfone O ═ S ═ O, amide-CONH2Acyl chloride-COOCl, sulfoxide S ═ O, sulfone O ═ S ═ O.
13. Optoelectronic device based on a perovskite material comprising a passivating agent comprising at least one passivating molecule, characterized in that said passivating molecule is a heteroaryl molecule having at least one substituent IG arranged as a structural unit according to the following general formula:
HAr-IG
wherein HAr is a heteroaryl group comprising C5-C50 and at least one heteroatom selected from N, O, S.
14. An optoelectronic device according to claim 13, wherein the passivating group is selected from primary amine-NH2Secondary amine-NHR, tertiary amine-NR2Ethers and hydroxy-or (h), mercapto and thiol-sr (h), carbonyl C ═ O, phosphine PR3Phosphine oxide P ═ O, carboxy-coor (h), sulfoxide S ═ O, sulfone O ═ S ═ O, or any lewis base functional group, where R is an alkyl chain or aryl group.
15. An optoelectronic device according to any one of claims 13 to 14, wherein the sensor group is selected from O, S, F, Cl, Br, I and N.
16. An optoelectronic device according to any of claims 13 to 14, wherein the sensing group is selected from cyano-CN, nitro-NO2Carbonyl group C ═ O, carboxyl group-coor (h), sulfoxide S ═ O, sulfone O ═ S ═ O, amide-CONH2Acyl chloride-COOCl, sulfoxide O, sulfone O, S-O.
17. An optoelectronic device according to claim 1, wherein the passivating agent comprises one or a combination of molecules having the general structural formula:
wherein n is 1 to 5,000,000.
18. An optoelectronic device according to claim 17, wherein the passivating group is selected from primary amine-NH2Secondary amine-NHR, tertiary amine-NR2Ethers and hydroxy-or (h), mercapto and thiol-sr (h), carbonyl C ═ O, phosphine PR3Phosphine oxide P ═ O, carboxy-coor (h), sulfoxide S ═ O, sulfone O ═ S ═ O, or any lewis base functional group, where R is an alkyl chain or aryl group.
19. A photovoltaic device comprising an optoelectronic device according to any one of claims 11 to 18.
20. A laser device comprising an optoelectronic device according to any one of claims 11 to 18.
21. A photodetector comprising an optoelectronic device according to any one of claims 11 to 18.
An X-ray detector comprising an optoelectronic device according to any one of claims 11 to 18.
23. A light emitting diode comprising an optoelectronic device according to any one of claims 11 to 18.
24. The light-emitting diode (40) according to claim 23, comprising a substrate (41), a transparent conductive material layer (42), an electron transport/injection layer (43), a perovskite layer (44) comprising a passivating agent, 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 conductive material layer (52), an electron transport layer (53), a perovskite layer (54) comprising a passivating agent, and a hole transport layer (55), and an electrode layer (56).
26. A method of manufacturing an optoelectronic device according to any one of claims 1 to 16, comprising the steps of:
-providing a perovskite precursor;
-providing a passivating agent or combination of passivating agents doped into the perovskite precursor;
-performing a perovskite film surface treatment;
-performing a passivating molecular vapour treatment; and
incorporation into an antisolvent.
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| CN113013333B (en) * | 2021-02-24 | 2022-09-09 | 重庆大学 | Application of multi-active-site ligand molecules in perovskite solar cell and preparation method of device |
| CN114188488A (en) * | 2021-11-04 | 2022-03-15 | 华南师范大学 | Perovskite luminescent layer, light emitting diode, preparation method and application thereof |
| CN114220922A (en) * | 2021-11-18 | 2022-03-22 | 华中科技大学 | Method for thermally evaporating perovskite material through in-situ passivation |
| CN116096194B (en) * | 2023-04-07 | 2023-08-18 | 合肥市旭熠科技有限公司 | Novel method for preparing large-area perovskite film and application |
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| US20170283693A1 (en) * | 2016-03-31 | 2017-10-05 | Florida State University Research Foundation, Inc. | Luminescent halide perovskites, methods, compositions, and devices |
| US20180218845A1 (en) * | 2017-01-30 | 2018-08-02 | Hairen TAN | Contact passivation for perovskite optoelectronics |
| CN108493343A (en) * | 2018-04-04 | 2018-09-04 | 清华大学 | The application of a kind of perovskite thin film and preparation method thereof and the film in the opto-electronic device |
| KR101899428B1 (en) * | 2017-04-10 | 2018-09-17 | 울산과학기술원 | Passivated perovsikite light-emitting diodes and preparation method thereof |
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| US20170283693A1 (en) * | 2016-03-31 | 2017-10-05 | Florida State University Research Foundation, Inc. | Luminescent halide perovskites, methods, compositions, and devices |
| US20180218845A1 (en) * | 2017-01-30 | 2018-08-02 | Hairen TAN | Contact passivation for perovskite optoelectronics |
| KR101899428B1 (en) * | 2017-04-10 | 2018-09-17 | 울산과학기술원 | Passivated perovsikite light-emitting diodes and preparation method thereof |
| CN108493343A (en) * | 2018-04-04 | 2018-09-04 | 清华大学 | The application of a kind of perovskite thin film and preparation method thereof and the film in the opto-electronic device |
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