CN111647948B - Organic semiconductor micro-nano crystal with improved exciton-photon coupling strength and preparation method and application thereof - Google Patents

Organic semiconductor micro-nano crystal with improved exciton-photon coupling strength and preparation method and application thereof Download PDF

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CN111647948B
CN111647948B CN201910161795.7A CN201910161795A CN111647948B CN 111647948 B CN111647948 B CN 111647948B CN 201910161795 A CN201910161795 A CN 201910161795A CN 111647948 B CN111647948 B CN 111647948B
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CN111647948A (en
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李金彪
付红兵
吴义室
姚建年
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Abstract

The invention belongs to the field of application characterization of photoelectric materials, and particularly relates to an organic semiconductor micro-nano crystal with improved exciton-photon coupling strength, and a preparation method and application thereof. The invention provides an organic semiconductor micro-nano crystal with ultrahigh exciton-photon coupling strength, which is obtained by self-assembly of DPAVBi molecules, can effectively carry out exciton-photon strong coupling, and the coupling strength can be as high as 1.2 eV; meanwhile, the micro-nano crystal can realize stimulated emission. The method lays a foundation for finally realizing the bose-Einstein condensation and the polarization excimer laser in the organic micro-nano crystal, and can be used as an effective material in the aspect of polarization excimer devices. The invention also provides a preparation method of the micro-nano crystal, which can be prepared by a simple solvent exchange method.

Description

Organic semiconductor micro-nano crystal with improved exciton-photon coupling strength and preparation method and application thereof
Technical Field
The invention belongs to the field of application characterization of photoelectric materials, and particularly relates to an organic semiconductor micro-nano crystal with improved exciton-photon coupling strength, and a preparation method and application thereof.
Background
Strong coupling of photons and excitons in the limited domain in a semiconductor quantum microcavity can generate exciton polaritons of a semi-optical semi-substance, so that bose-einstein condensation, low-threshold laser and strong polarized excimer solitons can be observed. The exciton binding energy of inorganic materials is typically less than 0.1eV, and exciton polaritons are typically observed at low temperatures, e.g., temperatures below 100K. Frenkel excitons in organic materials have stronger bonding energy than Wannier-Mott excitons in inorganic materials, and thus exciton polaritons of organic materials have higher stability at room temperature. The organic semiconductor material is an important advanced material in the field of micro-nano photonics based on the advantages of low cost, easiness in processing, adjustable chemical properties and the like. However, since the study of exciton polaritons needs to be implemented in a microcavity, a Fabry-Perot cavity (FP cavity) composed of a pair of parallel highly reflective mirror surfaces is generally used, which is not favorable for the integration of the optoelectronic circuit. Therefore, there is still a need to improve the properties of these materials and develop new, efficient and stable organic opto-electronic devices.
Disclosure of Invention
The present invention provides a DPAVBi crystal having an XRD spectrum substantially as shown in figure 2 (c).
According to the present invention, the DPAVBi crystal has an SEM image substantially as shown in fig. 2 (a).
According to the present invention, the DPAVBi crystal has a SAED diagram substantially as shown in fig. 2(b) except for the inset.
According to the invention, the DPAVBi crystal has a TEM image substantially as shown in the inset portion of fig. 2 (b).
According to the present invention, DPAVBi refers to 4,4' -bis [4- (di-p-tolylamino) styryl ] biphenyl having a chemical structure represented by the following formula:
Figure BDA0001984904370000021
according to the invention, the crystal is a micro-nano crystal, preferably a micro-ribbon-shaped single crystal, such as a micro-ribbon.
According to the invention, the crystal is obtained by self-assembly of DPAVBi molecules.
According to an embodiment of the present invention, the thickness of the crystal may be 0.1 to 0.2 times the width.
According to exemplary embodiments of the invention, the width of the crystals may be, for example, about 0.5 to 20 μm, preferably about 0.5 to 10 μm, such as about 0.8 to 4 μm, 3 to 8 μm, 6 to 10 μm, such as 0.80 μm, 1.77 μm, 8.04 μm; the thickness of the crystals may be, for example, about 0.05 to 4 μm, preferably about 0.1 to 1.5 μm, e.g., 0.1 μm, 0.2 μm, 0.5 μm;
according to embodiments of the present invention, the length of the crystal may be 5 to 200 times the width.
According to exemplary embodiments of the invention, the length of the crystals may be, for example, about 10 to 200. mu.m, preferably about 20 to 100. mu.m, such as 20 to 50 μm, 50 to 80 μm, 70 to 100. mu.m.
According to the invention, the crystal may present exciton-photon coupling, the group refractive index may be 3-10, and the exciton-photon coupling intensity may be 0.6-1.2 eV.
The invention also provides a DPAVBi micron belt which comprises the crystal. Preferably, said micro-strip consists of said crystals.
The invention also provides a preparation method of the DPAVBi crystal, which comprises the step of obtaining the crystal by self-assembling the DPAVBi molecule through a solvent exchange method.
According to an embodiment of the invention, the preparation method comprises the steps of: mixing the DPAVBi solution with a poor solvent, standing to obtain a suspension, and carrying out solid-liquid separation on the suspension to obtain the crystal.
According to an embodiment of the invention, the DPAVBi solution comprises DPAVBi and a solvent, such as a good solvent.
According to an embodiment of the present invention, the good solvent may be any one of tetrahydrofuran, dichloromethane, chloroform, acetonitrile or a combination thereof, preferably tetrahydrofuran.
According to an embodiment of the invention, the concentration of the DPAVBi solution is 1 to 50mmol/L, preferably 5 to 20mmol/L, such as 10 mmol/L.
According to an embodiment of the present invention, the poor solvent may be any one of n-hexane, n-heptane, methanol, ethanol, or a combination thereof, preferably any one of n-hexane, methanol.
According to an embodiment of the invention, the volume ratio of the DPAVBi solution to the poor solvent is 1 (1-100), preferably 1 (2-25), such as 1:5,1:10,1: 20.
According to an embodiment of the invention, the time of standing is 0.1 to 5 hours, such as 0.5 hour.
According to an embodiment of the invention, the preparation method further comprises the steps of: and washing the crystal by using a poor solvent, dispersing to obtain a dispersion system, transferring the dispersion system to a substrate, and volatilizing the poor solvent to obtain the crystal. Wherein the poor solvent has the above-mentioned definition.
According to an embodiment of the present invention, the ratio of the crystals to the poor solvent in the dispersion system may be (1-6) mg (2-30) mL, preferably (1-3) mg (2-10) mL, for example 1mg:5 mL.
According to an embodiment of the present invention, the substrate may be any one of a quartz substrate, a glass substrate, and a silicon substrate.
The invention also provides a method for measuring the exciton-photon coupling strength, which comprises the following steps:
1) collecting the micro-area luminescence spectrum of the crystal under continuous optical pumping, and determining the position of a mode peak by using a Lorentz fitting mode;
2) and (3) putting the mode peak wavelength band into the following calculation formula to obtain the group refractive index of the crystal at each wavelength:
Δλm＝λ2/2wng
wherein, Δ λmDenotes a mode peak pitch, λ denotes a light emission wavelength, w denotes a width of a micro band, ngThe refractive index of the group at each wavelength is shown.
Preferably, the assay method further comprises: the effect of exciton polarization excimer is researched by analyzing the relation between energy and wave vector, and the final exciton-photon coupling potential energy is obtained by a finite element analysis method and the following formula simulation calculation:
Figure BDA0001984904370000041
wherein E isphAnd EexRespectively representing uncoupled cavity photons and pure excitonsThe energy of (a); v represents the exciton-photon coupling potential; e represents the energy of the coupled exciton polarized excimer state; | alpha | non-2And | β | |)2Respectively the mixing coefficients of photons and excitons in the polariton;
cavity photon EphBy the formula
Figure BDA0001984904370000042
To obtain wherein
Figure BDA0001984904370000043
Is a reduced Planck constant, k is the polariton wave vector, c is the speed of light in vacuum, ε0Is the relative dielectric constant.
Further, the invention also provides application of the DPAVBi crystal or the micro-strip, which is used for Bose-Einstein condensation, polaritons (such as a polariton device) and laser devices.
The invention has the beneficial effects that:
the invention provides an organic semiconductor micro-nano crystal with ultrahigh exciton-photon coupling strength, which is obtained by self-assembly of DPAVBi molecules, can effectively carry out exciton-photon strong coupling, and the coupling strength can be as high as 1.2 eV; meanwhile, the micro-nano crystal can realize stimulated emission and is used as a laser device. The method lays a foundation for finally realizing the bose-Einstein condensation and the low-threshold polarization excimer laser in the organic micro-nano crystal, and can be used as an effective material in the aspect of polarization excimer devices. The invention also provides a preparation method of the micro-nano crystal, which can be prepared by a simple solvent exchange method.
Drawings
FIG. 1 is a schematic diagram of a preparation method for preparing a micro-nano crystal in example 1.
FIG. 2(a) is an SEM picture of a micro-nano crystal prepared in example 2;
fig. 2(b) is a combined view of a SAED (selected area electron diffraction) image and a TEM image of the micro-nano crystal prepared in example 2, wherein the part of the insert in the lower right corner of fig. 2(b) is the TEM image, and the part except the insert in the lower right corner is the SAED image;
FIG. 2(c) is an XRD pattern of the micro-nano crystal prepared in example 2.
FIG. 3 is a schematic diagram of a method for collecting photoluminescence spectra of a micro-nano crystal under continuous optical pumping.
FIG. 4(a) is photoluminescence spectra of micro-nano crystals with widths of 4.96 μm, 6.36 μm and 8.04 μm prepared in examples, and FIG. 4(b) is group refractive index at different wavelengths.
FIG. 5 shows the energy-wave vector distribution and the exciton-photon mixing coefficient distribution in the polariton obtained by simulating DPAVBi micro-nano crystal with the width of 0.80 μm, 1.77 μm and 8.04 μm prepared in the example.
FIG. 6 is a distribution diagram of exciton-photon coupling intensity along with the change of the width of the micro-nano crystal.
FIG. 7(a) is photoluminescence spectra of the micro-nano crystal prepared in the example under different pumping energies, wherein the spectral lines correspond to pumping energies of 4.00, 3.44 and 2.80 muJ/cm from top to bottom respectively2The spectral line of (1); fig. 7(b) is the distribution of integrated intensity of its photoluminescence spectrum with pump energy.
FIG. 8 shows fluorescence spectra of micro-nano crystals with widths of 4.96 μm, 6.36 μm and 8.04 μm under continuous laser irradiation and laser spectra when the pumping energy is higher than a threshold value, which are obtained in example.
FIG. 9 shows the test results of the device of the present embodiment under the angle-resolved spectroscopy test system.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; in the examples, SEM photograph acquisition was performed using a field emission scanning electron microscope (FESEM, Hitachi S-4300, acceleration voltage 10-15KV), TEM and SAED photograph acquisition was performed using a transmission electron microscope (JEOL JEM-2011), and XRD photograph was performed using D/max2400X-ray diffractometer with Cu target radiation angle of 3-40 degree
Figure BDA0001984904370000051
Figure BDA0001984904370000052
The optical microscope optical path system is used for collecting various spectrums of the micro-nano crystal at room temperature in the air. Laser beams are focused on the micro-nano crystal through a 50X 0.9NA objective lens on a microscope, PL spectrum signals of the micro-nano crystal are collected through the 50X 0.9NA objective lens which can move in a 3-dimensional mode below a sample stage, and exciting light is filtered through a long-wave filter with the wavelength of 420 nanometers. The collected PL spectral signals were finally directed through fiber optics into a CCD (SPECC-10-400B/LbN, Roper Scientific) in a multicolor apparatus (Spectropro-550i, Acton). Spatially resolved PL spectroscopy was performed by introducing a hexagonal aperture in front of the fiber to collect only the PL spectrum in a selected region. The angle-resolved spectral acquisition uses an optical path system in a fourier imaging configuration, and the angular coverage of the test is ± 70 °.
Reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Referring to the method shown in fig. 1, the preparation of the DPAVBi micro-nano crystal comprises the following steps:
adding 100 μ L10 mmol/L DPAVBi tetrahydrofuran solution into 2mL n-hexane, standing for 30min to obtain suspension with green precipitate, and centrifuging to obtain DPAVBi crystal.
Preparing a DPAVBi micro-nano crystal test sample:
washing the obtained crystal precipitate twice by using a poor solvent n-hexane, taking 1mg of crystal, dispersing the crystal in 5mL of n-hexane to obtain a dispersion system of the DPAVBi crystal in the n-hexane, spraying about 0.5mL of the dispersion system on a quartz substrate, and volatilizing the n-hexane in a natural environment to obtain a sample for testing. The obtained DPAVBi crystal is in a micron belt shape, the length of the DPAVBi crystal is 20-50 mu m, the width of the DPAVBi crystal is 0.8-4 mu m, and the thickness of the DPAVBi crystal is 0.1-0.5 mu m through observation tests such as image acquisition. The crystals with the width of 0.80 μm and 1.77 μm in the test sample were selected for subsequent testing.
Example 2
Referring to the method shown in fig. 1, the preparation of the DPAVBi micro-nano crystal comprises the following steps:
200 mu L of 10mmol/L DPAVBi tetrahydrofuran solution is dripped into 2mL of n-hexane and stands for 20min to obtain suspension with green precipitate, then the suspension is centrifugally separated to obtain DPAVBi crystals, the obtained crystal precipitate is washed twice by poor solvent n-hexane, 1mg of crystals is dispersed in 5mL of n-hexane to obtain a dispersion system of the DPAVBi crystals in the n-hexane, about 0.5mL of the dispersion system is sprayed on a quartz substrate, and the n-hexane is volatilized in a natural environment to obtain a sample for testing. The obtained DPAVBi crystal is in a micron belt shape, the length of the DPAVBi crystal is 50-80 mu m, the width of the DPAVBi crystal is 3-8 mu m, and the thickness of the DPAVBi crystal is 0.3-0.8 mu m through observation tests such as image acquisition. Crystals with a width of 4.96 μm and 6.36 μm in the test sample were selected for subsequent testing.
Example 3
Referring to the method shown in fig. 1, the preparation of the DPAVBi micro-nano crystal comprises the following steps:
adding 400 mu L of 10mmol/L DPAVBi tetrahydrofuran solution into 2mL of n-hexane, standing for 15min to obtain suspension with green precipitate, centrifuging to obtain DPAVBi crystal, washing the obtained crystal precipitate twice with poor solvent n-hexane, dispersing 1mg of crystal in 5mL of n-hexane to obtain a dispersion system of the DPAVBi crystal in n-hexane, spraying about 0.5mL of the dispersion system on a quartz substrate, and volatilizing n-hexane in natural environment to obtain a sample for testing. The obtained DPAVBi crystal is in a micron belt shape, the length of the DPAVBi crystal is 70-100 mu m, the width of the DPAVBi crystal is 6-10 mu m, and the thickness of the DPAVBi crystal is 0.5-1.2 mu m through observation tests such as image acquisition. Crystals having a width of 8.04 μm in the test sample were selected for subsequent testing.
Test examples
1. SEM, TEM, XRD and SAED tests were performed on the micro-nano crystal prepared in example 2, and the spectrogram is shown in fig. 2, wherein fig. 2(a) is an SEM picture, and fig. 2(b) is a combined picture of SAED (selected area electron diffraction) and TEM pictures (bottom right corner is bottom right corner)TEM picture), fig. 2(c) is an XRD data pattern. The crystal cell parameters of the micro-nano crystal single crystal structure obtained by self-assembling DPAVBi molecules are as follows:
Figure BDA0001984904370000071
Figure BDA0001984904370000072
α is 78.676(4) °, β is 75.229(5) °, and γ is 84.165(4) °. Analyzing the spectrogram to obtain the dominant growth direction of the micro-nano crystal [010 ]]Crystal orientation, followed by width [100 ]]And (4) crystal orientation. The XRD diffraction peak can be assigned to the (001) series of peaks, indicating that the crystal plane parallel to the substrate is the (001) crystal plane.
2. Photoluminescence spectra of the micro-nano crystals with widths of 4.96 μm, 6.36 μm and 8.04 μm prepared in examples 2 and 3 respectively were collected under continuous optical pumping by referring to the method shown in fig. 3 (fig. 4(a)), and the mode peak positions were determined by lorentz fitting. Substituting the mode peak position obtained by fitting into a formula: delta lambdam＝λ2/2wng(ii) a Wherein Δ λmRepresenting the mode peak distance, lambda represents the light-emitting wavelength, w represents the width of the micro-nano crystal, and the refractive index n of the group at each wavelength is obtainedgThe size of (2). As shown in fig. 4(b), this ultra-high group refractive index and its gradual decrease with increasing wavelength indicate that intense exciton-photon coupling occurs and exciton-polariton quasiparticles are formed in these micro-nano crystals.
3. And (4) performing analog calculation on the exciton-photon coupling strength of the micro-nano crystal.
The effect of exciton polaritons is studied by analyzing the relationship between energy and wave vector. In wave vector space, the spacing of distributed Feedback (FP) cavity oscillation modes is integral multiple pi/Lz(LzFP cavity length). For singlet exciton to photon coupling, this energy-wavevector dispersion relationship can be modeled with the following coupled-oscillator modes:
Figure BDA0001984904370000081
wherein EphAnd EexRespectively representing uncoupled cavity photons and pureThe energy of the exciton; v represents the exciton-photon coupling strength; e represents the energy of the coupled exciton polarized excimer state; | alpha | non-2And | β | |)2The mixing coefficients of photons and excitons in the polariton, respectively. Cavity photon EphBy the formula
Figure BDA0001984904370000082
To obtain wherein
Figure BDA0001984904370000083
Is a reduced Planck constant, k is the polariton wave vector, c is the speed of light in vacuum, ε0Is the relative dielectric constant.
The final exciton-photon coupling intensity can be obtained through finite element analysis method simulation calculation.
FIG. 5 shows the energy-wavevector distribution and the exciton-photon mixing coefficient distribution in the polarization excimer obtained by simulating the DPAVBi micro-nano crystal with the width of 0.80 μm, 1.77 μm and 8.04 μm prepared in examples 1 and 3. The distribution of exciton-photon coupling intensity along with the change of the width of the micro-nano crystal is shown in figure 6. When the width dimension of the micro-nano crystal is less than about 3 micrometers, the exciton photon coupling intensity is increased sharply along with the reduction of the width, and when the width is reduced to 0.8 micrometers, the exciton-photon coupling intensity obtained by simulation can reach 1.2 eV.
4. And (4) testing and representing stimulated emission of the micro-nano crystal.
Photoluminescence spectra of a single micro-nano crystal under different pumping energy are collected by taking 400-nanometer femtosecond laser as a light source, and whether the micro-nano crystal can realize stimulated emission can be determined.
Fig. 7(a) is a photoluminescence spectrum of the micro-nano crystal prepared in example 2 under different pumping energies, and an obvious mode peak indicates the occurrence of a stimulated emission phenomenon. From the distribution of integrated intensity of photoluminescence spectrum with pumping energy shown in FIG. 7(b), it can be seen that the data distribution is composed of two parts, linear region and super-linear region, and the laser threshold P can be determined by the intersection point position of the two partsthThe position of (a).
Fig. 8 is a comparison of fluorescence spectra of the micro-nano crystals prepared in examples 2 and 3 under excitation of continuous laser and 400 nm femtosecond laser, and it can be seen that mode peak positions of the micro-nano crystals and the nano crystals have high coincidence, indicating that laser of the micro-nano crystals has exciton polariton components.
Application examples
Referring to the preparation method of the crystal in the embodiment 1-3, in the dispersion system of the obtained crystal in n-hexane, 0.5mL of the crystal is sprayed on a quartz glass substrate with a surface plated with an 80-nanometer silver film, and after the natural volatilization of the solvent is completed, a silver film with a thickness of 35-50 nanometers is evaporated on the substrate, so that a device structure with the upper and lower surfaces of the micro-nano crystal in parallel silver mirrors is obtained. The device is used for testing, and by means of an angle-resolved spectrum testing system under femtosecond laser pumping, the test result is shown in fig. 9, so that the phenomena of bose-einstein condensation and polarization excimer laser can be observed, and the crystal can be well applied to a polarization excimer device.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (3)

1. A DPAVBi crystal, wherein DPAVBi is 4,4' -bis [4- (di-p-tolylamino) styryl ] biphenyl having a chemical structure represented by the following formula:
Figure 773724DEST_PATH_IMAGE001
；
the crystal has the unit cell parameters as follows: a = 12.5329(6) a, b = 19.8454(9) a, c = 20.7968(12) a;
the crystal is a micron ribbon single crystal;
the width dimension of the crystal is 0.8-8.04 μm;
the preparation method of the DPAVBi crystal comprises the following steps: mixing 5-20 mmol/L of DPAVBi tetrahydrofuran solution with a poor solvent, standing to obtain a suspension, and carrying out solid-liquid separation on the suspension to obtain the crystal; washing the crystal with a poor solvent and dispersing to obtain a dispersion system, transferring the dispersion system to a substrate, and volatilizing the poor solvent to obtain the crystal;
the poor solvent is n-hexane;
the volume ratio of the DPAVBi solution to the poor solvent is 1 (5-20);
in the dispersion system, the ratio of the crystal to the poor solvent is (1-3) mg (2-10) mL.
2. The crystal of claim 1, wherein the crystal exhibits exciton-photon coupling, a group refractive index of 3-10, and an exciton-photon coupling intensity of 0.6-1.2 eV.
3. The crystal of claim 1, wherein the crystal has a thickness of 0.1 to 0.2 times the width; the length of the crystal is 5-200 times of the width.
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