Nanowires of organic-inorganic perovskites
10529498 · 2020-01-07
Assignee
Inventors
Cpc classification
C01G17/006
CHEMISTRY; METALLURGY
C01G19/006
CHEMISTRY; METALLURGY
Y02P70/50
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
C01P2004/16
CHEMISTRY; METALLURGY
H10K30/00
ELECTRICITY
Y02E10/542
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
C01P2004/54
CHEMISTRY; METALLURGY
H10K85/50
ELECTRICITY
C07C211/63
CHEMISTRY; METALLURGY
H01G9/2004
ELECTRICITY
International classification
C07F7/00
CHEMISTRY; METALLURGY
Abstract
An organic-inorganic perovskite CH.sub.3NH.sub.3PbI.sub.3 nanowire showing a length-width aspect ratio from 5-400 up to 10.sup.9 and a width-height ratio of 1-100 up to 1-10000. Further, the invention is embodied as a process for making the nanowire wherein at least a polar aprotic solvents is used, the polar aprotic solvent being at least one from the list comprising DMF, DMSO, and DMAc solvents.
Claims
1. A halide perovskite nanowire comprising: a halide perovskite body having dimensions of length, wide, and height; wherein the halide perovskite body has a length-width aspect ratio between 5-400 and 5-10.sup.9 and a width-height ratio between 1-100 and 1-10000.
2. The nanowire according to claim 1, wherein the halide perovskite body is composed of methylammonium lead iodide (CH.sub.3NH.sub.3PbI.sub.3).
3. The nanowire according to claim 1, wherein the halide perovskite body is composed of ABX.sub.3 where A is an aliphatic amine and/or alkali cation, B is a transition metal and/or a noble metal, and X is a Cl, Br or I anion.
4. A mesoscopic or planar heterojunction single or tandem solar cell made of nanowires as defined in claim 1.
5. A gamma-ray, or X-ray, or visible light, or near infrared detector made of nanowires as defined in claim 1.
6. A light amplification by stimulated emission of radiation system made of nanowires as defined in claim 1.
7. A LED or OLED made of nanowires as defined in claim 1.
8. A magneto-optical data storage element made of nanowires as defined in claim 1.
Description
BRIEF DESCRIPTION OF THE FIGURES
(1) The invention will be better understood in light of the description of preferred and example embodiments and in reference to the figures, wherein
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DESCRIPTION OF PREFERRED AND EXAMPLE EMBODIMENTS OF THE INVENTION
(17) Referring to
(18) Optical microscopy was performed to confirm the crystallization of the solid. Unexpectedly, instead of a granular film composed of isotropic crystallites, a network of several micron long wire-like objects was observed, some of them pointing in the direction of sliding of the two glass plates (105,108). The filiform morphology was further confirmed using TEM (200), SEM (201, 205) and AFM (206-209) measurements as illustrated in
(19) The width of the nanowires varied between 50 and 200 nm and they had lengths up to 16 microns. The height of the crystallites was determined from AFM measurements displaying a range from ultrathin (9 nm) to several tens of nanometers thick (90 nm) scale (300-311). The formation of a small number of aggregates of 10 nm sized isotropic crystallites was also observed, as it can be seen on TEM and SEM micrographs (200, 202, 204, 206). These particles were homogeneously dispersed on the SiO.sub.2 surface and attached to the wall of larger nanowires (201). Increasing the MAPbI.sub.3 solution volume-to-surface ratio during the slip-coating process yields larger, sub-micron sized whiskers (201, 203, 205, 207). Unlike the thinner wires that have a flat surface, some of these thicker crystallites possess a U-shape void along their surface (207, 209). The size distribution of nanowires (read from optical, AFM and SEM images) prepared by two solution volumes is shown in
(20) Reference is now made to
(21) The central question is where the directionality of the perovskite growth stems from. The role of the solvent in the nanowire formation was investigated by changing the solvent. The same protocol was repeated by replacing dimethyl formamide (DMF) by gamma-butyrolactone (GBL), another commonly used solvent of organolead halide perovskites. Due to the GBL's higher boiling point the evaporation was much slower, and ca. 350 K heat treatment was required to evaporate the solvent. Clearly, no anisotropic growth was taking place during the slip-coating process from GBL solution (900-902
(22) The major interest in MAPbI.sub.3 is its high sensitivity to visible-light, its high photovoltage of about 1.1 V which are the basic ingredients for an efficient solar-to-electric energy conversion.sup.24. These advantageous characteristics will certainly be explored in other device oriented research, like photodetection and solid state lasers.sup.25. The elucidation of the morphology dependent photoconductive performance could have a consequence on the development of more efficient devices. So far, the intrinsic photoconductive properties measured by standard contact method have not even been reported for the bulk samples. Here, we demonstrate the first results showing that one can make efficient photodetector based on nanowires of MAPbI.sub.3. In addition, these findings are compared to the photodetection of a thin film of spin coated MAPbI.sub.3 frequently used in photovoltaic devices.
(23) The devices were fabricated by slip-coating nanowires of different sizes of MAPbI.sub.3 onto a highly p-doped silicon substrate with 300 nm SiO.sub.2 on top. 100 nm-thick Pt contacts were deposited by e-beam evaporation through a microfabricated hard mask. The fabricated devices have a width of 100 m and a length varying between 5 m and 50 m. The sketch of the device and the optical image of a real one are shown in
(24) We measured the current density in the device as a function of the applied source-to-drain electric field in the dark and under illumination (red laser, =633 nm). The output characteristics follow a linear behavior, indicating that the contacts are ohmic (409). The contacts show a slight asymmetric behavior probably due to fabrication asymmetries.
(25) In the dark state, the device behaves like a good insulator with currents of the order of tens of pA and resistances in the GOhm range. Under the illumination of the laser, the absorption of the light generates electron-hole pairs that are extracted by the source-to-drain electric field and cause an increase in the conductance of the material up to a factor of 300. We probed the photoresponse of the device under different incident laser powers in the 70 nW to 7 W range. The current increases parabolically with the incident power, however, under the applied experimental conditions the saturation of the photocurrent has not been reached (409).
(26) The device configuration allows to test the effect of a gate electric field on the I-V characteristics. Despite the semiconducting nature of the material, no influence of gating was noticed (1100-1103). The applicable electric field limit (break-down voltage) was determined to be 20 kV/cm. Higher electric fields risk an irreversible rupture of the filiform crystallites (1200-1203).
(27) From the photocurrent one can estimate the responsivity of the device defined as R=I.sub.ph/P.sub.in, where I.sub.ph is the photocurrent and P.sub.in is the power of the incident light, respectively. For our device R was calculated to be 5 mA/W. Although, this value is about 4 orders of magnitude smaller than the best-in-class photoelectric devices made out of graphene and monolayer MoS.sub.2.sup.26,27,28,29, it is still comparable (10 times higher) to the value that has been achieved with the first prototypes of those 2D materials.sup.30,31 (1400, 1500). Optimization of the device fabrication process and the engineering of its configuration might drastically improve the performances of the photodetectors based on filiform perovskites, similarly to how it happened for devices fabricated from graphene and MOS.sub.2 (1400, 1500).
(28) The response time of our device (410) showed that rise and decay times for the on-off current under illumination are less than 500 s, 10.sup.4 faster than the state-of-the-art photodetectors made of monolayer MoS.sub.2.sup.26,28 and graphene.sup.27,29,32. The stability of the device was also tested by performing 100 consecutive cycles measured over 1 h (1300). A slight increase of the photocurrent (5%) is presumably due to contact adjustments (1300).
(29) To compare the performance of the wire structure (500-502, 1001, 1004, 1005, 1008, 1009
(30) These results demonstrate that the morphological properties, such as the crystallite size, form and their orientation could play an essential role in the photodetection and photoconductive response of the trihalide perovskite thin films.
(31) Regarding the synthesis the Pb cation can be entirely or partially replaced by Sn, Ge, as well as transition metals cations as Mn, Fe, Co, Ni, Cu, Ag, Au etc. The organic cation can be entirely or partially replaced by other aliphatic amine molecules. The I anion can be entirely or partially replaced by F, Br or Cl anions. By applying these modifications the optoelectronic properties of the nanowires can be effectively tuned.
(32) The nanowires crystallize on porous and/or solid insulator and/or conductive polymer, metal, ceramic surfaces. Surface structuring enables growth of linear, cylindrical motives with controlled morphology (see
(33) The nanowires perpendicular to substrate can be grown by applying the perovskite DMF-DMSO solution on a porous functional surface containing parallel pores perpendicular to the surface.
(34) The relevant example, that recrystallization from solvents of different nature facilitates forming of elongated solvatomorphs of organic-inorganic perovskite (e.g. lead-methylamine iodide) is a new solution-mediated strategy with which we exerting control over crystallite characteristics. The optically active elongated form of trihalide perovskites will make it possible to explore exiting opportunities in photonics industry such as solar energy conversion, photodetectors and on-chip coherent light sources.
Details of the Sample Preparation and Characterization of the Devices
Synthesis of MAPbI3 Nanocrystallites by Slip-Coating Method (100-108)
(35) MAPbI.sub.3 single crystals and polycrystalline powder was synthesized using the method described by Poglitch and Weber..sup.33 The as-prepared polycrystalline powder was dissolved in organic solvents.
(36) Filiform crystallites: 10 microliters of saturated solution (50 w %) of MAPbI.sub.3 in dimethyl formamide (DMF, Sigma-Aldrich) was dropped onto a microscope glass slide (Thermoscientifictype, 7626 mm) and covered with a second microscope slide so that the yellow solution spreads out and forms a homogenous liquid film between the glass plates (
(37) Nanoparticle based films: were prepared by identical procedure described above applying saturated solution (40 w %) of MAPbI.sub.3 in gamma-Butyrolactone (GBL, Sigma-Alrich) solvent (
Material Characterization
(38) Energy Dispersive X-ray Spectroscopy (EDX)
(39) Scanning Electron Microscope images were taken with a MERLIN Zeiss electron microscope. The elemental composition of the fibrous crystallites was analyzed by EDX (accelerating voltage of 8 kV, working distance of 8.5 cm).
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(41) Powder X-Ray Diffraction (XRD)
(42) X-ray diffraction patterns were collected on a RIGAKU using a source of Cu K (1.54050 ). XRD results suggest that highly oriented MAPbI.sub.3 crystallites (along the (110) direction) are present on the substrate. In Fig (802-803) the low intensity wide diffraction peak centered at 2 Theta 24 degree comes from the microscope glass slides support.
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(44) Raman Spectroscopy
(45) The structure of the filiform perovskites was analyzed by Raman spectroscopy (HORIBA LabRAM HR Raman spectrometer). Spectra were taken using an 532 nm green excitation laser. Laser power was reduced in order to avoid photodegradation of the sample. Focalspot size was about 10 m using a 50 long working distance objective. The recorded Raman spectrum shows great similarities with the reported Raman modes of MAPbI.sub.3.
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(47) Fourier Transform Infrared Spectroscopy (FTIR)
(48) Measurements were performed with a Bruker Tensor FTIR spectrometer with a DTGS detector and 4 wavenumber resolution. The bulk crystal was measured in transmission mode on Si while the diffuse reflectance (DRIFT) mode was employed for the analysis of the nanowires. For the DRIFT we used an integration sphere and a flat gold surface as a reference. The vibration modes in the FT-IR spectrum of filiform crystallites shows great similarities to those obtained on bulk single crystal suggesting identical chemical composition (CH.sub.3NH.sub.3PbI.sub.3).
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Slip-Coating with GBL
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Device Fabrication
(51) The devices were fabricated by slip-coating of MAPbI.sub.3 solution (GBL-nanoparticles, DMF-filiform crystallites) onto a highly p-doped silicon substrate with 300 nm thermally grown SiO.sub.2 on top. Source and drain contacts were patterned by an e-beam evaporation (Leybold Optics LAB 600 H) of 100 nm of Pt in high vacuum (<10.sup.6 mbar, room temperature) through a microfabricated hard mask. The fabricated contact pads had a width of 100 m and a length varying between 5 m and 50 m. The sketch and an optical microscopy image of a representative device are shown in
Device Characterization
(52) Electrical Measurements
(53) If it is not otherwise specified all measurements were performed on freshly prepared samples under ambient conditions. Two-point electrical measurements (d.c.) were carried out using a National Instruments GPIB-USB-HS controller and a Keithely 2400 source meter. To minimize sources of external noise, the measurements were performed in a home-built Faraday cage. A microscope objective and a micromechanical stage were used to localize the device.
(54) Photocurrent Measurements
(55) We probed the devices and their time-dependent responsivity to laser excitation using a laser beam (COHERENT laser module, model 31-1050, =633 nm) with an illumination power from 0.1 mW to 10 mW. The spot size had a diameter of 4 mm, resulting in an estimated maximum illumination power of 0.25 Wcm.sup.2. The time response of the photocurrent was acquired by modulating the laser beam with a mechanical chopper (217 Hz) and detecting the photocurrent with a current preamplifier (
(56) Device Geometry Calculations
(57) The geometrical factors used for the performance calculations of the photodetectors were extracted from the AFM and SEM analysis of the fabricated devices (
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(59) Effect of the Gate Voltage
(60) We tested the effect of a transversal electric field applied on the semiconducting MAPbI.sub.3 nanowire channel. The device configuration is shown in
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(62) Breakdown Voltage of the Photodetector Made with Filiform Perovskites
(63) To study the performance limit and the maximum electric field applicable to the MAPbI.sub.3 nanowires under illumination we tested several devices under increasing source-to-drain electric field (an example is shown in 1200-1203).
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(65) Stability of the Photodetector Based on MAPbI.sub.3 Nanowires
(66) Referring to
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External Quantum Efficiency Calculation
(68) The external quantum efficiency (E.Q.E.) is the ratio of the number of carriers generated and collected by the photodetector to the number of photons of a given energy incident on the device. For a given incident optical power P.sub.in and a generated photocurrent I.sub.ph, it can be calculated by:
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where e is elementary charge, h is the Planck constant and v is the speed of light.
(70) The performances of the devices based on nano-perovskites were calculated by assuming that all the incident light was absorbed by the device and converted into electron-hole pairs, thus neglecting the effect of optical losses such as transmission and reflection. It is important to mention, that the transmission and reflection losses have not been determined in this work. Since the presence of these optical phenomena could highly affects the calculated EQE, in our case the reported values can be seen as characteristic lower bound values for this material.
Responsivity of State-Of-The-Art Photodetectors
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CONCLUSION
(73) The invention relates to one-dimensional elongated organic-inorganic perovskites crystallites, in particular hyper-branched and/or aligned nanoand microwires parallel or perpendicular to the substrate. The nanoand microwires can be made by solution mixing, slip-coating, spin coating, doctor blading or spraying of solution of pure solvents or solvent mixtures of polar aprotic solvents e.g. dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), dimethylacethamide (DMAc) containing Pb cations, methylamine and I anions in 1:1:3 stoichiometric ratio. The Pb cation can be entirely or partially replaced by Sn, Ge, as well as transition metals cations as Mn, Fe, Co, Ni, Cu, Ag, Au etc. The organic cation can be entirely or partially replaced by other aliphatic amine molecules or alkali cations as Na, K, Li, Cs, Rb. The I anion can be entirely or partially replaced by F, Br or Cl anions. The temperature range for anisotropic crystallization falls between 273-373 K. The time-scale of the fabrication process is between 5 and 1200 seconds. The nanowires obtained by this method have length-width aspect ratio from 5-400 and width-height ratio of 1-100. The nanowires crystallize on porous and/or solid insulator and/or conductive polymer, metal, ceramic surfaces. Surface structuring enables growth of linear, cylindrical motives with controlled morphology. The organic-inorganic nanowires can be used as Gamma-Ray, X-Ray, UV, Vis and NIR detector. It can be used in mesoscopic solar cells, LED, OLED and in systems where light amplification by stimulated emission of radiation is used. The one dimensional form of MAPbI.sub.3 could have unique optical and electrical properties. The feasibility of anisotropic growth of organolead halide perovskites opens up a new strategy towards the realization of low-temperature, solution processed films with controlled morphology.
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