CN113265240B - Efficient blue light-emitting Cd-based perovskite material and preparation method and application thereof - Google Patents
Efficient blue light-emitting Cd-based perovskite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-efficiency blue light-emitting Cd-based perovskite material, a preparation method and application thereof, and a compound [ (Me) 2 ‑Pipz]CdBr 3 (COO) belongs to the P2/c space group and has a cell parameter of
α = γ =90 °, β =101.819 (8) °, Z =2, unit cell volume
The material has a one-dimensional framework structure, a simple preparation method and high yield, has high-efficiency blue-violet light emission under the excitation of ultraviolet light, has a photoluminescence quantum yield as high as 52.27 percent, has a color purity as high as 95.6 percent, is a blue-violet light emission perovskite material with the highest light quantum yield and the highest color purity at present, and has important application prospects in the fields of solid-state lighting, display and the like.
Description
Technical Field
The invention relates to the technical field of photoluminescence materials, and particularly relates to a high-efficiency blue-light-emitting Cd-based perovskite material and a preparation method and application thereof.
Background
The organic-inorganic hybrid halide is a novel excellent photoelectronic material and has wide application prospect in the fields of light-emitting diodes, photoelectric detectors, photovoltaic solar cells, lasers and the like. In particular perovskite APbX 3 (＝Cs,CH 3 NH 3 X = Cl, br, I) is of great interest due to its excellent photoluminescent properties, tunable composition, tunable band gap to cover the entire visible region, narrow emission band, high quantum yield and mild synthesis process. Among them, the blue, green and red three primary color leds play a crucial role in the field of illumination and display. However, quantum yields close to 100% with the green and red regionsIn contrast, APbCl 3 The quantum yield of blue emission is less than 1%, and blue emission still needs to be improved in consideration of the balanced development of three primary colors in high resolution display.
At present, two structural design strategies are proposed for realizing efficient blue light emission. The first method is to consider APbBr 3 The green emitter has high quantum yield, and chlorine is added into the bromine-based perovskite to enlarge the band gap and realize high-energy blue-violet light emission. However, almost all halogen-mixed perovskites undergo halide migration under illumination, have inherent phase separation, form Cl-and Br-rich phases, and photoluminescence spontaneously changes from blue-violet to green, which greatly hinders the operation of the device. A second approach to achieving blue light emission is to combine three-dimensional APbX 3 The perovskite is reduced to the nano-scale such as quantum dots, quasi-two-dimensional nanosheets and the like. Although blue-violet light emission was successfully achieved, the quantum yield dropped dramatically, with the narrow emission peak splitting into broad multiple peaks at the same time. Furthermore, nanostructures are primarily based on colloidal chemistry, and the inherent instability of nanocrystals leads to severe optical instability. Thus, while the above design strategy effectively achieves blue-violet light emission, phase separation and spectral instability still present difficulties in the operation of blue-violet light emitting devices. Therefore, the development of new single-component violet-blue luminescent materials that are efficient and stable remains a challenging and attractive task.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, provides a high-efficiency blue light-emitting Cd-based perovskite material, a preparation method and application thereof, and synthesizes a novel one-dimensional organic-inorganic hybrid photoluminescent material [ (Me) 2 -Pipz]CdBr 3 (COO), solves the problem of CsPbX of the traditional three-dimensional perovskite material 3 The light quantum yield is low, and the structure and the luminescence property are unstable.
In a first aspect, the present invention provides a high efficiency blue light emitting Cd-based perovskite material having a molecular formula of [ (Me) 2 -Pipz]CdBr 3 (COO) wherein (Me) 2 -Pipz is 1,4 dimethylpiperazine.
In a second aspect, the invention also provides a preparation method of the high-efficiency blue-light-emitting Cd-based perovskite material, which comprises the following steps:
s1: weighing CdBr 2 ·4H 2 O、PbBr 2 And 1, 4-dimethylpiperazine, which is dissolved in hydrobromic acid, N-dimethylformamide, ethylene glycol and H 2 In the mixed solution of O, the mixture is put into a stainless steel hydrothermal kettle and sealed;
s2: putting the sealed hydrothermal kettle into an electrothermal blowing dry box for reaction;
s3: and opening the hydrothermal kettle, carrying out suction filtration on the solid-liquid mixture, airing the mixture obtained by suction filtration to obtain a colorless flaky crystal material, washing with ethanol, and naturally airing to obtain the colorless flaky crystal material.
Preferably, in step S1, cdBr 2 ·4H 2 O、PbBr 2 And 1, 4-dimethylpiperazine in a molar ratio of (2.5-3.5) to (0.8-1.2) to (7-9).
Preferably, in step S1, hydrobromic acid, N-dimethylformamide, ethylene glycol and H 2 The volume ratio of O is (0.8-1.2): (0.9-1.1): (2.5-3.5): (2.8-3.2).
Preferably, in step S2, the reaction temperature is 80-120 ℃ and the reaction time is 5-8 days.
In a third aspect, the invention also provides an application of the high-efficiency blue light-emitting Cd-based perovskite material, and the high-efficiency blue light-emitting Cd-based perovskite material is used for a photoluminescence material.
Compared with the prior art, the invention has the following beneficial effects:
the invention aims at the traditional three-dimensional perovskite material CsPbX 3 The key technical problems of low light quantum yield, unstable structure and luminous performance and the like are solved by adopting a hydrothermal synthesis method, selecting IIB group metal Cd as an optical active center and 1, 4-dimethylpiperazine as a structural template agent to synthesize a novel one-dimensional organic-inorganic hybrid photoluminescent material [ (Me) 2 -Pipz]CdBr 3 (COO) which effectively isolates a one-dimensional inorganic skeleton by using a larger band gap of 1, 4-dimethylpiperazine, and exhibits inherent characteristics of the inorganic skeleton, thereby having high-efficiency blue-violet light emissionThe photoluminescence quantum yield is as high as 52.27%, and the color purity can reach 95.6%, which is the blue-violet light emitting perovskite material with the highest light quantum yield and the highest color purity at present; and further researches the photoluminescence performance and stability of the metal halide, and lays a foundation for the research of novel low-dimensional organic-inorganic hybrid metal halide high-efficiency blue-violet light luminescent materials.
Drawings
FIG. 1 shows Compound [ (Me) 2 -Pipz]CdBr 3 (COO) 1D chain scheme along b-axis.
FIG. 2 is compound [ (Me) 2 -Pipz]CdBr 3 (COO) Stacking Structure diagram along the a-axis.
FIG. 3 shows [ (Me) compound obtained in example 1 2 -Pipz]CdBr 3 Powder diffraction pattern of (COO).
FIG. 4 shows the compound [ (Me) obtained in example 2 2 -Pipz]CdBr 3 Powder diffraction pattern of (COO).
FIG. 5 shows [ (Me) compound obtained in example 3 2 -Pipz]CdBr 3 Powder diffraction pattern of (COO).
FIG. 6 is compound [ (Me) 2 -Pipz]CdBr 3 (COO) in the ultraviolet-visible absorption spectrum.
FIG. 7 is compound [ (Me) 2 -Pipz]CdBr 3 Thermogravimetric analysis of (COO).
FIG. 8 is compound [ (Me) 2 -Pipz]CdBr 3 (COO) excitation spectrum (left) and emission spectrum (right) at room temperature.
Fig. 9 is a commission internationale de l' eclairage (CIE) 1931 color coordinate diagram.
FIG. 10 shows the excitation spectrum of a reference substance collected by an integrating sphere and the compound [ (Me) 2 -Pipz]CdBr 3 Emission spectrum of (COO).
FIG. 11 is compound [ (Me) 2 -Pipz]CdBr 3 (COO) photoluminescence decay pattern at room temperature and fitted curve.
FIG. 12 is compound [ (Me) 2 -Pipz]CdBr 3 (COO) emission spectrum, emission spectrum after 30 days in a humid environment and 48 hours of UV irradiation.
Fig. 13 is an emission spectrum of a white-light WLED at 80mA drive current, with the top right corner of the figure being a photograph of an assembled WLED.
Fig. 14 is an emission spectrum of WLED as a function of device current.
FIG. 15 is the 1931CIE color coordinates for an NTSC standard color space (black lines) and a WLED device (grey).
Fig. 16 is a normalized peak intensity variation for WLED systems at different drive currents.
Fig. 17 is the luminescence spectrum of the WLED system over time at 80mA operating current.
Fig. 18 is the change in light efficiency after 5 hours of energizing the WLED system at 80mA operating current.
Detailed Description
The preparation method of the high-efficiency blue light-emitting Cd-based perovskite material comprises the following steps:
s1: weighing CdBr as raw material 2 ·4H 2 O、PbBr 2 And 1, 4-dimethylpiperazine, which is dissolved in hydrobromic acid, N-dimethylformamide, ethylene glycol and H 2 In the mixed solution of O, the mixture is put into a stainless steel hydrothermal kettle and sealed;
s2: putting the sealed hydrothermal kettle into an electrothermal blowing dry box with a program temperature control function for reaction;
s3: and opening the hydrothermal kettle, carrying out suction filtration on the solid-liquid mixture, airing the mixture obtained by suction filtration to obtain a colorless flaky crystal material, washing with ethanol, and naturally airing to obtain the colorless flaky crystal material.
Wherein, in the solvent thermal reaction process of step S2, N, N-dimethylformamide (DMF, C) 3 H 7 NO) hydrolysis first takes place under acidic conditions:
the generated HCOOH further reacts with inorganic metal salt, and the molecular formula of coordination generation is [ (Me) 2 -Pipz]CdBr 3 (COO) compound.
Adopted by the inventionThe raw materials are all provided by Aladdin reagent company: cdbr 2 ·4H 2 O (purity 98%), pbBr 2 (purity 99%), 1, 4-dimethylpiperazine (purity 98%), hydrobromic acid (concentration 48%), ethylene glycol (purity 99.5%), N, N-dimethylformamide (purity 99.5%), H 2 O (purity 100%). The hydrothermal kettle is provided by Jinan science and technology company and has the capacity of 15mL. The electric heating air blowing drying box is provided for Shanghai-Hengchang scientific instruments, and is DHG-9240 (A). The crystal structure was measured by an X-ray single crystal diffractometer (Bruker, germany, SMARTAPEXII), the powder diffraction was measured by an X-ray powder diffractometer (Bruker D8 ADVANCE), the ultraviolet-visible absorption spectrum was measured by an ultraviolet-visible spectrophotometer (PE Lambda 900), and the thermogravimetric analysis was measured by a thermogravimetric analyzer (TAQ 500). Photoluminescence (PL) spectra were tested by the Edinburgh FLS920 fluorescence spectrometer. The photoluminescence quantum efficiency (PLQE) was tested by FLS920 fluorescence spectrometer equipped with an integrating sphere. The time-resolved attenuation data was collected into 10000 counts using the time-dependent single photon counting capability of the Edinburgh FLS920 fluorescence spectrometer, the Edinburgh EPL-360 picosecond pulse diode laser provided excitation, and the mean lifetime was obtained by exponential fitting. Chromaticity coordinates were calculated using commission international de l illumination (CIE) color coordinate calculation software based on emission spectra. The testing of the white light diode is completed on a remote PCE-2000B photoelectric system tester.
Example 1
The preparation method of the high-efficiency blue light-emitting Cd-based perovskite material comprises the following steps:
1) 0.08607g (0.25 mmol) of CdBr 2 ·4H 2 O，0.02936g(0.08mmol)PbBr 2 0.07993g (0.7 mmol) of 1, 4-dimethylpiperazine was dissolved in 0.8mL of hydrobromic acid, 0.9mLN, N-dimethylformamide, 2.5mL of ethylene glycol and 2.8mLH 2 In the mixed solution of O, the mixture is stirred for 5 minutes by magnetic force to be fully mixed; putting the mixture into a stainless steel hot kettle made of polytetrafluoroethylene and sealing;
2) Placing the hydrothermal kettle in a blast drying oven at a speed of 10 ℃/h -1 Heating to 80 deg.C at heating rate, heating at constant temperature for 120 hr, and cooling in airAt room temperature, finishing the synthesis reaction;
3) Opening the hydrothermal kettle, carrying out suction filtration on the solid-liquid mixture, and airing the mixture obtained by suction filtration to obtain a colorless flaky crystal material, namely the target product [ (Me) 2 -Pipz]CdBr 3 (COO), washing with ethanol, and naturally drying to obtain the product with yield of 80mg.
Example 2
The preparation method of the high-efficiency blue light-emitting Cd-based perovskite material comprises the following steps:
1) 0.1033g (0.3 mmol) of CdBr 2 ·4H 2 O，0.03670g(0.1mmol)PbBr 2 0.09135g (0.8 mmol) of 1, 4-dimethylpiperazine are dissolved in 1mL of hydrobromic acid, 1mL of LN, 3mL of N-dimethylformamide, 3mL of ethylene glycol and 3mL of LH 2 In the mixed solution of O, the mixture is stirred for 5 minutes by magnetic force to be fully mixed; putting the mixture into a stainless steel hot kettle made of polytetrafluoroethylene and sealing;
2) Placing the hydrothermal kettle in a blast drying oven at a speed of 10 ℃/h -1 The temperature is raised to 100 ℃ at the heating rate, the constant temperature heating is continuously carried out for 156h, the reaction is cooled to the room temperature in the air, and the synthesis reaction is finished.
3) Opening the hydrothermal kettle, carrying out suction filtration on the solid-liquid mixture, and airing the mixture obtained by suction filtration to obtain a colorless flaky crystal material, namely the target product [ (Me) 2 -Pipz]CdBr 3 (COO), washing with ethanol, and naturally drying to obtain the product with yield of 87mg.
Example 3
The preparation method of the high-efficiency blue light-emitting Cd-based perovskite material comprises the following steps:
1) 0.1205g (0.35 mmol) of CdBr 2 ·4H 2 O，0.04404g(0.12mmol)PbBr 2 0.10277g (0.9 mmol) of 1, 4-dimethylpiperazine was dissolved in 1.2mL of hydrobromic acid, 1.1mL of LN, N-dimethylformamide, 3.5mL of ethylene glycol and 3.2mL of LH 2 In the mixed solution of O, the mixture is stirred for 5 minutes by magnetic force to be fully mixed; putting the mixture into a stainless steel hot kettle of polytetrafluoroethylene and sealing;
2) Placing the hydrothermal kettle in a blast drying oven at a speed of 10 ℃/h -1 The temperature is raised to 120 ℃ at the heating rate, constant temperature heating is continuously carried out for 192h, the reaction is cooled to room temperature in the air, and the synthesis reaction is finished.
3) Opening the hydrothermal kettle, carrying out suction filtration on the solid-liquid mixture, and airing the mixture obtained by suction filtration to obtain a colorless flaky crystal material, namely the target product [ (Me) 2 -Pipz]CdBr 3 (COO), washing with ethanol, and naturally drying to obtain the product with yield of 98mg.
Examples 1 to 3 preparation of the obtained Compound [ (Me) 2 -Pipz]CdBr 3 The structure and performance experiments of (COO) are as follows:
(1) Compound [ (Me) 2 -Pipz]CdBr 3 (COO) Crystal Structure
As shown in FIGS. 1-2, the compound [ (Me) 2 -Pipz]CdBr 3 (COO) belongs to the monoclinic system, P2/c space group, and has a unit cell parameter of
α = γ =90 °, β =101.819 (8) °, Z =2, unit cell volume
In its asymmetric unit, there are 1 independent Cd 2+ Ion, 3 Br-ions, one HCOO-ion. All Cd 2+ The ion is coordinated and connected with three Br-ions and one HCOO-ion to form CdBr 3 (COO), cd-Br bonding distances from shorter
To a longer
Different CdBr 3 (COO) are connected through a shared Br atom to form a one-dimensional chain, wherein the one-dimensional chain is formed by organic cations [ (Me) with larger band gaps 2 -Pipz] 2+ Separated, [ (Me) 2 -Pipz]The isolation therebetween allows the crystal to exhibit the inherent characteristics of an inorganic skeleton.
(2)[(Me) 2 -Pipz]CdBr 3 (COO) powder diffraction Structure
As shown in the figure3-5, compound [ (Me) 2 -Pipz]CdBr 3 The diffraction pattern of the polycrystalline powder of (COO) was the same as the data of the single crystal structure simulation, indicating that the polycrystalline powder was pure [ (Me) 2 -Pipz]CdBr 3 (COO), color purity close to 100%.
(3) Compound [ (Me) 2 -Pipz]CdBr 3 (COO) absorption spectrum
As shown in FIG. 6, for compound [ (Me) 2 -Pipz]CdBr 3 (COO) powder samples after grinding are subjected to solid-state ultraviolet-visible optical absorption spectrum tests, obvious absorption peaks are shown at about 220nm, 290nm and 360nm, the optical band gap is 2.64eV, and the compound is proved to have strong optical absorption and belongs to semiconductor materials.
(4) Compound [ (Me) 2 -Pipz]CdBr 3 Thermogravimetric analysis of (COO)
As shown in FIG. 7, at N 2 To compound [ (Me) under ambient conditions 2 -Pipz]CdBr 3 (COO) A thermal stability test was carried out at temperatures ranging from room temperature to 800 ℃ and showed that the compound remained stable until 140 ℃ and gradually decomposed as the temperature increased. This illustrates Compound [ (Me) 2 -Pipz]CdBr 3 (COO) is very thermally stable and can be chemically stable up to 140 ℃.
(5) Compound [ (Me) 2 -Pipz]CdBr 3 Photoluminescence properties of (COO)
As shown in FIGS. 8-9, compound [ (Me) 2 -Pipz]CdBr 3 (COO) under excitation of 329nm ultraviolet light, a narrow-band high-frequency emission is generated, the peak value of the emission is 432nm, the narrow half-peak width is 41nm, and the minimum Stokes shift is 103nm. The corresponding international commission on illumination (CIE) chromaticity coordinates (x, y) are (0.16, 0.03), very close to the national committee on television standards international standard, blue-violet light CIE color coordinates (0.14, 0.08). The color purity is 95.6 percent, and the blue light emitting material belongs to the blue light emitting material with the highest color purity at present.
As shown in FIG. 10, the calculation of PLQE is based on the equation η QE ＝I S /(E R -E S )，I S Fluorescence emission spectra of representative samples, E R Of light excited by an empty integrating sphereSpectrum (without sample), E S Is an excitation spectrum for exciting the sample. Measurement of Compound [ (Me) 2 -Pipz]CdBr 3 The PLQE of the (COO) bulk crystals was about 52.27%. The compound has very high quantum yield, and is the highest quantum yield in the Cd-based compounds with blue-violet light emission found at present.
(6) Compound [ (Me) 2 -Pipz]CdBr 3 Luminescent lifetime of (COO)
As shown in FIG. 11, compound [ (Me) 2 -Pipz]CdBr 3 (COO) time-resolved emission spectroscopy was monitored at 432nm using a bi-exponential function I (t) = A 1 exp(-t/τ 1 )+A 2 exp(-t/τ 2 ) Fitting was performed, I (t) represents the luminescence intensity, t is the time after excitation, a is a constant, and τ is the luminescence lifetime. Compound [ (Me) 2 -Pipz]CdBr 3 (COO) has an average life of 16.6274. Mu.s, and Compound [ (Me) 2 -Pipz]CdBr 3 (COO) has a longer emission peak lifetime, indicating fluorescent properties.
(7) Compound [ (Me) 2 -Pipz]CdBr 3 (COO) stability
As shown in FIG. 12, the crystals were exposed to strong UV light from a 300W xenon lamp for 48 hours in a humid environment for 30 days (humidity 90% -95%), respectively. The results of luminescence tests on the compounds respectively show that the emission intensity is only slightly reduced, and the positions of emission peaks are not changed, which indicates that the compounds [ (Me) 2 -Pipz]CdBr 3 (COO) has good photochemistry and environmental stability, and is expected to be applied to aspects of solid state lighting, display and the like.
(8) Compound [ (Me) 2 -Pipz]CdBr 3 (COO) application to LED
Mixing the compound [ (Me) 2 -Pipz]CdBr 3 (COO) and commercial Red phosphor (K) 2 SiF 6 :Mn 4+ ) Green phosphor ((Ba, sr) 2 SiO 4 :Eu 2+ ) According to a ratio of 3.5:1.5:1 was uniformly coated on a 365nm ultraviolet chip to successfully produce a white light LED, and as shown in fig. 13, the Electroluminescence (EL) emission spectrum can cover the entire visible light region(ii) a EL emission spectra were tested at various currents of 20-120mA and showed a monotonic increase in emission intensity and with the most ideal CIE chromaticity coordinates (0.332, 0.354), color coordinate positions very close to that of white, 0.33, high Color Rendering Index (CRI) of 95.4 and approximate "warm" white Correlated Color Temperature (CCT) of 4933K, when the current was as high as 80 mA.
As shown in the emission spectrum of the WLED with device current variation of fig. 14, the emission spectrum profile does not change significantly with the increase of the driving current, and the emission intensity of the WLED increases monotonically, showing excellent stability.
Fig. 15 shows the 1931CIE color coordinates of the leds, NTSC standard color space and WLED device, making a WLED that exhibits an ultra-wide color gamut.
Fig. 16 is a graph of normalized peak intensity variation for the WLED system at different drive currents: the spectral stability is good, the emission intensity is monotonously increased in the current range of 120mA, the method has potential application prospect in high-power photoelectric devices.
Fig. 17 is the luminescence spectrum of the WLED system over time at 80mA operating current: the EL emission spectrum intensity and the luminous efficiency of the prepared WLED device are slightly reduced, and the thermal and light stability of the compound is proved.
The stable emission spectrum with the change of the electrified time under the working current of 80mA is subsequently tested, and as shown in figure 18, after the electrification for 5 hours, the stability can be kept high, the emission intensity can not be obviously weakened, and the compound [ (Me) is further proved 2 -Pipz]CdBr 3 Thermal and optical stability of (COO).
Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions should be within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present disclosure and the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. The high-efficiency blue light-emitting Cd-based perovskite material is characterized in that the molecular formula is [ (Me) 2 -Pipz]CdBr 3 (COO) belonging to the monoclinic system, P2/c space group, cell parameter ofa =6.1199(15) Å，b = 7.3541(18) Å，c = 15.855(4) Å，α =γ = 90 º，β = 101.819(8) º，ZUnit cell volume =2V = 698.4(3) Å 3 。
2. The method for preparing a high-efficiency blue-light-emitting Cd-based perovskite material as claimed in claim 1, wherein the method comprises the following steps:
s1: weighing CdBr 2 •4H 2 O、PbBr 2 And 1, 4-dimethylpiperazine, which is dissolved in hydrobromic acid, N-dimethylformamide, ethylene glycol and H 2 In the mixed solution of O, the mixture is put into a stainless steel hydrothermal kettle and sealed;
s2: putting the sealed hydrothermal kettle into an electrothermal blowing dry box for reaction;
s3: and opening the hydrothermal kettle, carrying out suction filtration on the solid-liquid mixture, airing the mixture obtained by suction filtration to obtain a colorless flaky crystal material, washing with ethanol, and naturally airing to obtain the colorless flaky crystal material.
3. The method of claim 2, wherein in step S1, cdBr 2 •4H 2 O、PbBr 2 And 1, 4-dimethylpiperazine in a molar ratio of (2.5-3.5) to (0.8-1.2) to (7-9).
4. The method of claim 2, wherein in step S1, hydrobromic acid, N-dimethylformamide, ethylene glycol and H 2 The volume ratio of O is (0.8-1.2): (0.9-1.1): (2.5-3.5): (2.8-3.2).
5. The method according to claim 2, wherein the reaction temperature in step S2 is 80 to 120 ℃ and the reaction time is 5 to 8 days.
6. The use of a high efficiency blue light-emitting Cd-based perovskite material as claimed in claim 1, wherein the high efficiency blue light-emitting Cd-based perovskite material is used in a photoluminescent material.
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