CN118223113A - Preparation device and method of fluorescent molecule doped organic micro-nano wafer - Google Patents

Preparation device and method of fluorescent molecule doped organic micro-nano wafer Download PDF

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CN118223113A
CN118223113A CN202410162413.3A CN202410162413A CN118223113A CN 118223113 A CN118223113 A CN 118223113A CN 202410162413 A CN202410162413 A CN 202410162413A CN 118223113 A CN118223113 A CN 118223113A
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raw material
wafer
molecular
guest
molecule
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唐建伟
许淼淼
池轶瑄
金伟
黄泰临
陈学文
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
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    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract

The invention belongs to the technical field of organic fluorescent molecular materials, and particularly discloses a preparation device and a preparation method of a fluorescent molecular doped organic micro-nano wafer. The preparation device comprises an opening reaction device, a wafer collecting device and a heating device, wherein the opening reaction device comprises a guest molecule raw material region, a host molecule raw material region and a wafer growth doping region. The preparation method comprises the following steps: heating the guest molecule raw material region and the host molecule raw material region at different temperatures to enable the guest molecule raw material and the host molecule raw material to be respectively and continuously phase-changed into gaseous molecules, and mixing the gaseous host molecules and the guest molecules in the wafer growth doping region and crystallizing to form a fluorescent molecule doped organic micro-nano wafer; the wafer escapes from the opening and is collected by a wafer collection device. With the apparatus and method of the present invention, the collection of wafers is not limited by the reactor space, the wafers are easily transferred, the fluorescent molecules in the wafers have a well-defined orientation and have a spectral linewidth near the fourier transform limit at low temperatures, and the fluorescent molecules are highly doped.

Description

Preparation device and method of fluorescent molecule doped organic micro-nano wafer
Technical Field
The invention belongs to the technical field of organic fluorescent molecular materials, and particularly discloses a preparation device and a preparation method of a fluorescent molecular doped organic micro-nano wafer.
Background
The single photon source plays an important role in quantum information technology applications such as quantum computation, quantum communication, quantum precision measurement and the like. The single photon source with practicability generally meets the requirements of high single photon property, high photon homomorphism, deterministic generation, high collection efficiency and the like. Solid single quantum systems such as quantum dots, defect color centers in crystals, ions in solid matrixes, fluorescent molecules and the like have great potential in realizing deterministic high-quality single photon sources. In particular polycyclic aromatic hydrocarbon molecules doped in organic molecular crystals, which have a significant advantage in terms of fluorescence spectrum stability. For example, a tribenzo [ des, h, kl ] naphtho [1,2,3,4-rst ] pentafin (7, 8:15,16-Dibenzoterrylene; DBT) molecule doped in high quality anthracene (ANTHRACENE) crystals has a fluorescence spectrum linewidth near the Fourier transform limit at low temperature and excellent spectral stability. When the organic crystal doped with fluorescent molecules is a micro-nano wafer, the organic crystal is mixed and integrated with a photon chip prepared with a micro-nano optical waveguide to realize the efficient coupling of the fluorescent molecules and the micro-nano optical path on the chip, so that the organic crystal is a single photon source extensible integration scheme with great potential.
The single photon source has high requirement on the optical performance of fluorescent molecules, and the crystal grown by the gas phase method has high purity and good quality, so that the organic micro-nano wafer doped with fluorescent molecules is mainly prepared by the gas phase method. In the case of gas phase preparation, the host molecular material and the guest molecular (fluorescent molecular) material are heated to phase change into a gaseous state and mixed and then deposited on a relatively low temperature surface or crystallized in a relatively low temperature atmosphere. However, the existing preparation methods face the following key problems. First, prior art fabrication methods grow wafers on smooth substrate surfaces, which result in most crystals clinging to the substrate surface or being very prone to clinging to the substrate surface when mechanical transfer is attempted, resulting in transfer where only a very small number of crystals can be mechanically separated from the substrate surface. This is a very limited application of wafers, for example, it is difficult to mix and integrate wafers onto photonic chips in a position and orientation controlled manner. Moreover, current fabrication methods generally perform wafer collection inside the reactor, and thus wafer collection is limited by the reactor space. For smaller volume reactors, the substrate area for collecting wafers is small, resulting in smaller numbers of crystals being collected or wafers overlapping each other. Whereas if the reactor is increased in order to increase the crystal collection area, the concentration of gas phase molecules decreases, resulting in a low doping concentration of fluorescent molecules. In addition, even if a small-volume reactor is adopted to prepare an organic micro-nano wafer, the doping concentration of fluorescent molecules reported at present is generally low, and the requirement of high-density and expandable integration of molecules and optical chips cannot be met. The main reason is that the phase transition temperature of the fluorescent molecular material is generally significantly higher than that of the host molecular material, and if the two materials are heated in a co-melted form, the temperature of the two materials is the same, and the gas phase concentration of the fluorescent molecules is far lower than that of the host molecules; if the fluorescent molecular material and the main molecular material are heated independently, the fluorescent molecular material is generally heated in a powder state because the fluorescent molecular material cannot be melted independently, the heating efficiency is low, and even if a higher heating temperature is given, the gas phase concentration of the fluorescent molecular material is still far lower than that of the main molecular material.
Disclosure of Invention
The invention aims to provide a preparation device and a preparation method of a fluorescent molecule doped organic micro-nano wafer, so as to simultaneously meet the following technical requirements: the prepared wafer is easy to mechanically transfer, the doping concentration of fluorescent molecules is high, and the collection of the wafer is not limited by the space of a reactor.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
In a first aspect, the invention provides a preparation device of a fluorescent molecule doped organic micro-nano wafer, which comprises an opening reaction device, a wafer collecting device and a heating device, wherein the opening reaction device comprises a guest molecule raw material region, a host molecule raw material region and a wafer growth doping region;
The outlets of the guest molecule raw material region and the host molecule raw material region are respectively communicated with the lower port of the wafer growth doping region, and the top end of the wafer growth doping region is an opening;
the host molecular raw material region is loaded with a host molecular material of an organic micro-nano wafer, and the guest molecular raw material region is loaded with a fluorescent molecular material for doping; the heating device is used for heating the host molecular material of the host molecular raw material area and the fluorescent molecular material of the guest molecular raw material area respectively;
The wafer collection device is used for collecting the doped wafers escaping from the top opening of the wafer growth doped region.
Optionally, the level of the host molecular feedstock zone outlet is higher than the level of the guest molecular feedstock zone outlet.
Optionally, the guest molecule raw material area and the host molecule raw material area have different temperatures, and the shapes and the sizes of the two raw material areas can be designed according to the requirements, so that the temperatures of the guest molecule raw material and the host molecule raw material can be independently controlled, and the heating areas and the surface areas of the two raw materials can be independently controlled.
Optionally, the size of the wafer growth doped region is adjusted according to actual needs, including the length and the sectional area of the wafer growth doped region, so that the air flow of the wafer growth doped region is controlled, on one hand, enough momentum of the generated wafer is ensured to escape from the opening of the opening reaction device, and on the other hand, the wafer growth time can be adjusted, and the proper wafer size and thickness are obtained.
Optionally, the opening part of the opening reaction device and the wafer collecting device are both placed in a protective gas environment, which is helpful for improving fluorescence stability of fluorescent molecules doped in the wafer.
Optionally, the heating device is an oil bath device, the guest molecule raw material area is located at a deeper position below the oil bath liquid level, the host molecule raw material area is located near the oil bath liquid level, and the temperature of the guest molecule raw material area and the host molecule raw material area is respectively controlled by using one heating device. The oil bath heating device and the open reaction device can be freely disassembled and assembled, so that the flexible and rapid temperature control of the open reaction device can be realized, and the preparation time is shortened.
Optionally, the heating device is an electric heating device, and the guest molecule raw material region and the host molecule raw material region are respectively controlled in temperature by two independent electric heating devices.
Preferably, the opening reaction device is a special-shaped glass test tube, the special-shaped glass test tube is provided with a main tube and a branch tube, the upper part of the main tube is a wafer growth doping area, the bottom is a guest molecule raw material area, and the branch tube is a host molecule raw material area.
Optionally, the wafer collection device comprises a sheet of polymeric material having a roughened surface disposed adjacent to the opening of the open reaction device. The rough surface of the thin sheet can effectively prevent the wafers settled on the thin sheet from being clung to the surface of the thin sheet, so that the wafers can be separated from the surface of the substrate by a probe pick-up method and then transferred to other substrates or chip surfaces for specific application.
In a second aspect, the present invention provides a method for preparing a fluorescent molecule doped organic micro-nano wafer, which adopts the preparation device of the fluorescent molecule doped organic micro-nano wafer provided in the first aspect, and comprises the following steps: loading a host molecular raw material and a guest molecular raw material into the host molecular raw material zone and the guest molecular raw material zone respectively; heating the guest molecule raw material region by the heating device to enable the guest molecule raw material to continuously change phase into gaseous molecules; heating the main molecular raw material region by the heating device to enable the main molecular raw material to continuously change phase into gaseous molecules; mixing gaseous host molecules and guest molecules in the wafer growth doping area and forming an organic micro-nano wafer by cooling, wherein the organic micro-nano wafer mainly comprises the host molecules, and the guest molecules are doped in the organic micro-nano wafer; the organic micro-nano wafer moves along with the air flow to the opening of the opening reaction device and finally escapes from the opening; and collecting the wafer by using the wafer collecting device.
Optionally, the method for loading the main molecular raw materials comprises the following steps: adding a main molecular raw material into the main molecular raw material region; heating the main molecular raw material region to a temperature higher than the melting point of the main molecular raw material by using the heating device to melt the main molecular raw material; stopping heating, cooling to room temperature, and filling the main molecular raw material in the main molecular raw material area in the form of monolithic solid. Compared with the bulk molecular raw material in the form of powder, the bulk molecular raw material in the form of solid can lead the rate of the bulk molecular raw material to be more stable and controllable when the bulk molecular raw material is heated and phase-changed into gaseous molecules in the follow-up process.
Alternatively, the method for loading the guest molecule raw material comprises the following steps: adding a guest molecular raw material and a host molecular raw material into the guest molecular raw material zone, wherein the melting point of the host molecular raw material is lower than that of the guest molecular raw material, and the rate of phase change of the host molecular raw material into gaseous molecules is far higher than that of the guest molecular raw material at the same temperature; heating the guest molecular raw material region to a temperature higher than the melting point of the host molecular raw material by using the heating device, so that the guest molecular raw material is dissolved in the melted host molecular raw material; heating is continued for a period of time until the host molecular material is totally transformed into gaseous molecules, leaving only the guest molecular material in the form of a thin layer attached to the wall.
Alternatively, the method for loading the guest molecule raw material comprises the following steps: adding a guest molecular feedstock to the guest molecular feedstock zone; adding a small amount of solvent to dissolve the guest molecule raw material in the solvent; the solvent is volatilized leaving only the guest molecular material in a thin layer attached to the walls.
The two methods for loading the guest molecule raw materials can realize the guest molecule raw materials in a thin layer form which clings to the wall, and compared with the guest molecule raw materials in a powder form which are directly used, the heating area and the surface area of the guest molecule raw materials can be obviously increased when the wafer is prepared, so that the sublimation speed of the guest molecule raw materials is greatly improved, and the doping concentration is improved.
Optionally, the opening of the open-ended reaction apparatus is covered when the guest molecular feedstock is heated, so that the gaseous guest molecular concentration in the reaction apparatus is accumulated, and the open-ended reaction apparatus is not opened until the host molecular feedstock is heated and wafer generation is started. This is advantageous for further increasing the guest molecule atmosphere concentration, thereby increasing the fluorescent molecule doping concentration in the wafer.
Optionally, the step of collecting the wafer comprises the following steps: placing a polymer material sheet with a rough surface in the area near the opening; the wafer is deposited onto the sheet of polymeric material after exiting the open reaction apparatus with the gas stream.
The beneficial effects of the invention are as follows:
1. The fluorescent molecule doped micro-nano wafer prepared by the device and the method is easy to mechanically transfer. In the invention, the crystal is collected by utilizing the polymer sheet with the rough surface after escaping from the reaction device, so that the wafer can be effectively prevented from being closely attached to the surface, and the wafer is easy to be transferred after being separated from the surface of the substrate by a mechanical method. The transferable wafer has more flexible application modes, for example, the wafer can be transferred onto the photonic chip after being picked up by a probe, so that the wafer can be controllably integrated onto the photonic chip in a determined position and orientation, and the on-chip optical quantum devices such as an on-chip single-molecule single-photon source and the like are realized.
2. The invention adopts the open reaction device, the wafers are grown in the air flow in the reaction device, and the grown wafers are collected after escaping from the reaction device, so the design that the growth and the collection of the wafers are respectively arranged inside and outside the reactor can ensure higher gas-phase molecular concentration by utilizing the space limitation of the reactor when the wafers grow, and the wafers are not limited by the space of the reactor when the wafers are collected, so that a large number of wafers can be collected.
3. The fluorescent molecular doped organic micro-nano wafer prepared by the device and the method has higher fluorescent molecular doping concentration. On the one hand, the invention sets a guest molecule raw material area and a host molecule raw material area which can be controlled in temperature respectively, and can independently control the temperature of the guest molecule raw material and the host molecule raw material, thereby allowing the temperature of the host molecule raw material to be set at the optimal temperature for crystal growth, and setting the temperature of the guest molecule raw material according to the required doping concentration, wherein the higher the temperature of the guest molecule raw material is, the higher the doping concentration is; on the other hand, the invention can design the shape and the size of the two raw material areas according to the requirement, thereby independently controlling the heating area and the surface area of the two raw materials, providing another way for controlling the doping concentration, and increasing the area of the guest molecule raw material area and/or reducing the area of the host molecule raw material area can improve the doping concentration. In the preparation method, the guest molecular raw material is attached to the wall in a thin layer form, so that compared with the guest molecular raw material in a powder form, the heating area and the surface area of the guest molecular raw material in the process of preparing the wafer can be remarkably increased, the sublimation speed of the guest molecular raw material is remarkably increased, and the doping concentration is improved.
4. The organic micro-nano wafer prepared by the device and the method has regular morphology, and fluorescent molecules doped in the wafer have definite orientations and have spectral linewidths close to the Fourier transform limit at low temperature.
Drawings
The technical scheme of the invention is further specifically described below with reference to the accompanying drawings and the detailed description.
FIG. 1 is a schematic diagram of a first structure of an apparatus for preparing a fluorescent molecule doped organic micro-nano wafer according to the present invention;
FIG. 2 is an optical micrograph of an organic micronano-wafer collected on a rough sheet of polymeric material of the present invention, wherein the directions of double arrows indicate the directions of the b-axis of the crystal axis of the wafer;
FIG. 3 shows the results of the orientation test of fluorescent molecules in an organic micro-nano wafer prepared by the invention, wherein FIG. 3 (a) shows a laser scanning confocal fluorescence microscopic imaging diagram when the polarization of the laser is parallel to the b axis of the micro-nano wafer, and FIG. 3 (b) shows a laser scanning confocal fluorescence microscopic imaging diagram when the excitation polarization is perpendicular to the b axis of the micro-nano wafer;
FIG. 4 is an optical micrograph of an organic micronano-wafer prepared in accordance with the present invention as it is picked up on a tapered fiber probe;
FIG. 5 is an optical micrograph of an organic micro-nano wafer fabricated according to the present invention after being transferred onto a photonic chip and mixed with a micro-nano optical waveguide;
FIG. 6 is a second order correlation function of a single-molecule fluorescence photon sequence measured at a low temperature of 1.4K after the organic micro-nano wafer and the photon chip are mixed and integrated;
FIG. 7 shows a single-molecule resonance excitation spectrum obtained by measuring at a low temperature of 1.4K after the organic micro-nano wafer and the photon chip are mixed and integrated;
FIG. 8 is a schematic diagram of a second structure of an apparatus for preparing a fluorescent molecule doped organic micro-nano wafer according to the present invention.
Detailed Description
The technical scheme in the embodiment of the application will be further described with reference to the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. It should be noted that, the drawings provided in the specific embodiments are merely schematic, and not completely drawn according to the actual implementation, and shapes, features, dimensional proportions, spatial arrangements and the like of the components in the drawings may be different from those in the actual implementation. It should be further noted that the terms "first," "second," and the like in the description and in the claims are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order.
In all of the examples below, the guest molecule used was tribenzo [ des, h, kl ] naphtho [1,2,3,4-rst ] pentafin (7, 8:15,16-Dibenzoterrylene; DBT) of the formula I; the main molecule is anthracene (ANTHRACENE), and its structural formula is shown in formula II below.
[ Example 1]
The preparation apparatus of example 1, as shown in FIG. 1, comprises an open reaction apparatus 1, a wafer collection apparatus 2, and a heating apparatus 3. The open reaction device 1 is a special-shaped glass test tube and is provided with a main tube and branch tubes, wherein the bottom of the main tube is a guest molecule raw material region 4, the branch tubes are main molecule raw material regions 5, the upper part of the main tube is a wafer growth doping region 6, and the three regions are sequentially arranged from far to near from the opening. The wafer collection device 2 is a sheet of polymer material having a roughened surface located near the opening of the open reaction device 1. The heating device 3 is an oil bath heating device, and a lifting table is arranged below the oil bath heating device and can be used for controlling the immersion depth of the test tube in oil bath silicone oil. The opening of the open reaction apparatus 1 is located in the glove box 7, and the wafer collecting apparatus 2 is also located in the glove box 7, so that wafer growth and doping under the protection of gas can be realized.
The anthracene organic micro-nano wafer doped with DBT molecules is prepared by using the device, and the specific preparation steps are as follows:
1. Adding anthracene powder into a main molecular raw material area 5, and filling branch pipes as much as possible; covering the opening of the open reaction device 1; lifting the liquid level of the silicone oil by using a lifting table below the oil bath heating device 3 until the liquid level of the silicone oil is higher than the main molecular raw material area 5, and heating the anthracene powder to above the melting point until the anthracene powder is melted into liquid anthracene; lowering the liquid level of the silicone oil by using a lifting table to stop heating, and filling anthracene into a main molecular raw material area in a form of a whole solid after cooling to room temperature; if the entire solid form of anthracene does not fill the branch, the addition in the above steps is continued until the solid anthracene almost fills the branch.
2. Adding mixed powder of DBT and anthracene into a guest molecule raw material zone 4; the glove box 7 is filled with nitrogen; covering the opening of the open reaction device 1; lifting the liquid level of the silicone oil by using a lifting table below the oil bath heating device 3 until the liquid level of the silicone oil is higher than the guest molecule raw material area 4, heating mixed powder of DBT and anthracene to above the melting point of anthracene, and dissolving DBT in liquid anthracene; heating is continued until the anthracene has all phase changed to gaseous molecules, leaving DBT attached to the walls of the guest molecule feed zone 4 in a thin layer.
3. The anthracene wafer attached to the side wall of the open reaction apparatus 1 generated in steps 1 and 2 was scraped off.
4. Wafer generation and collection: covering the opening of the open reaction device 1; raising the liquid level of the oil bath silicone oil to enable the guest molecule raw material area 4 to be below the liquid level and the host molecule raw material area 5 to be above the liquid level of the silicone oil, so that only the guest molecule raw material area 4 is heated, DBT in the guest molecule raw material area 4 is continuously sublimated, and the concentration of gaseous DBT molecules in the opening reaction device 1 is accumulated; then raising the silicone oil level to enable the host molecule raw material area 5 to be near the silicone oil level, so that the host molecule raw material area 5 is also heated, and the guest molecule raw material area 4 is deeper below the silicone oil level at the moment, so that the two raw material areas have obvious temperature differences, and the specific temperature differences can be adjusted by changing the immersion depth of the host molecule raw material area 5 due to the fact that the temperature gradient near the silicone oil level is larger, for example, if the silicone oil level just submerges the upper end of the host molecule raw material area 5, when the temperature of anthracene in the host molecule raw material area is 215 ℃, the temperature of DBT molecules in the guest molecule raw material area can reach more than 280 ℃; the formation of wafers is seen after heating the bulk molecular feed region for several tens of seconds, at which time the lid of the open reaction apparatus 1 is opened and a large number of wafers escape from the opening and slowly settle onto a polymer material sheet 2 having a roughened surface placed in the vicinity of the open reaction apparatus and are collected.
5. After the desired number of wafers are collected, the opening of the open reaction apparatus 1 is covered, and heating is stopped.
After the organic micro-nano wafer is prepared according to the steps, the rough slice which collects the organic micro-nano wafer is taken out of the glove box and is observed under an optical microscope. Fig. 2 (a), (b), (c) and (d) show optical micrographs of four organic micronano-wafers on a rough flake, respectively, and the directions of the double arrows in fig. 2 (a), (b), (c) and (d) indicate the directions of the crystal axes b of the wafers. As can be seen from the figures of fig. 2 (a), (b), (c) and (d), the wafer shape is regular and the lateral dimensions are in the order of hundred microns. Film thickness meter tests show that the thickness of the wafer is hundred nanometers.
As shown in fig. 3 (a), laser scanning confocal fluorescence microscopic imaging is performed on a certain area of the micro-nano wafer by adopting lasers with different polarizations, and when the polarization direction of the lasers is parallel to the b-axis direction of the wafer, the fluorescence intensity is strongest; when the polarization direction of the laser light is perpendicular to the b-axis direction of the wafer, the fluorescence intensity is the weakest, as shown in fig. 3 (b). This indicates that the fluorescent molecules doped in the wafer are oriented substantially along the b-axis of the wafer. Thus, the orientation of all fluorescent molecules doped therein can be controlled collectively by controlling the orientation of the wafer, which is very advantageous for applications.
The invention improves the rate of the phase change of the guest molecules into the gaseous state by two main measures so as to improve the doping concentration of fluorescent molecules: in a first aspect, the present invention provides a guest molecular feedstock zone and a host molecular feedstock zone that are separately temperature controlled; in the prior art, the guest molecule DBT and the host molecule anthracene are heated in a eutectic melting mode, and the prepared doped wafer hardly observes fluorescence signals under the same excitation condition as that of fig. 3 (a). In a second aspect, the present invention attaches the guest molecular material to the wall in a thin layer to increase its heating efficiency; whereas the prior art adopts the partition heating of DBT molecular raw material and anthracene raw material, but the DBT molecular raw material is heated in the form of powder, the prepared doped wafer hardly observes fluorescence signal under the same excitation condition as in fig. 3 (a).
The rough surface of the polymer material sheet effectively prevents the wafer from being tightly attached to the surface, so that the wafer can be picked up from the sheet by using the probe. For example, a tapered fiber probe may be used to gently contact the wafer surface to pick up the wafer. Fig. 4 shows an optical micrograph of a micro-nano-wafer picked up on a tapered fiber probe, and the black shading in fig. 4 is the shading caused by the tapered fiber probe blocking light.
After picking up the micro-nano wafer, the wafer can be transferred for flexible application. For example, a wafer may be transferred to a photonic chip and integrated with a micro-nano optical path on the photonic chip in a defined position and orientation. Fig. 5 shows an optical micrograph of a micro-nano wafer integrated with a micro-nano optical path on a photonic chip, wherein the b-axis direction of the wafer, as indicated by the double arrow in fig. 5, is perpendicular to the propagation direction of the waveguide, i.e. the orientation of the DBT molecules doped therein is aligned with the polarization direction of the electric field of the waveguide quasi-TE conduction mode, thereby maximizing the coupling efficiency of the DBT molecules with the waveguide mode.
The hybrid integrated chip was placed in a cryostat at a temperature of 1.4K for optical characterization. A single DBT molecule in a wafer can be resonantly excited with a focused narrow linewidth laser spot. Fluorescent photons emitted by the DBT molecules are coupled into the micro-nano optical waveguide and are transmitted to two grating couplers at the far end after being split by an on-chip beam splitter, shown as BS in figure 5, namely GC1 and GC2 in figure 5 respectively. The DBT fluorescence photon signal can be detected from the grating coupler, which indicates that the DBT fluorescence molecule is successfully coupled to the micro-nano optical waveguide. Statistical analysis is performed on the arrival time difference of the photons measured at the two grating couplers, so that a second-order correlation function of the fluorescent photon sequence emitted by the DBT molecule can be obtained, as shown in fig. 6. From this second order correlation function, a pronounced anti-bunching effect can be seen, indicating that the fluorescence emitted from a single DBT molecule is a single photon sequence. Therefore, the fluorescent molecule doped organic micro-nano wafer prepared by the device and the method can be conveniently mixed and integrated with a photon chip, and can be applied to the realization of an on-chip single photon source.
Further, by scanning the frequency of the narrow linewidth laser, a resonance excitation spectrum of the DBT molecule can be obtained, and as shown in fig. 7, the linewidth is 41MHz, which is very close to the fourier transform limit (the fluorescence lifetime of the DBT molecule is about 4ns, and the corresponding fourier transform limit linewidth is about 40 MHz). Therefore, the DBT fluorescent molecules doped in the organic micro-nano wafer by using the device and the method can have excellent spectral stability even in a complex micro-nano integrated environment, and the application prospect of the device and the method in the technical field of on-chip light quantum information is shown.
[ Example 2]
Example 2 the same preparation apparatus as example 1 was used, example 2 differing from example 1 only in step 2 of the specific preparation steps:
2. Adding DBT powder and alcohol into the guest molecule raw material zone 4 to dissolve DBT in alcohol; the glove box 7 is filled with nitrogen; and lifting the liquid level of the silicone oil by using a lifting table below the oil bath heating device 3 until the liquid level of the silicone oil is higher than the guest molecule raw material area 4, heating to above 75 ℃, and leaving DBT to be attached to the wall in a thin layer form after the alcohol is completely volatilized.
[ Example 3]
The preparation apparatus of example 3, as shown in FIG. 8, comprises an open reaction apparatus 1, a wafer collection apparatus 2, a first heating apparatus 31, and a second heating apparatus 32. The open reaction device 1 is provided with a main pipe and branch pipes, wherein the bottom of the main pipe is a guest molecule raw material area 4, the branch pipes are host molecule raw material areas 5, the upper part of the main pipe is a wafer growth doping area 6, and the three areas are sequentially arranged from far to near. The wafer collection device 2 is a sheet of polymer material having a roughened surface located near the opening of the open reaction device 1. The first heating device 31 and the second heating device 32 are electric heating devices, and independently set temperatures to independently control temperatures of the guest molecule raw material region 4 and the host molecule raw material region 5, respectively. The opening of the open reaction apparatus 1 is located in the glove box 7, and the wafer collecting apparatus 2 is also located in the glove box 7, so that wafer growth and doping under the protection of gas can be realized.
The anthracene organic micro-nano wafer doped with DBT molecules is prepared by using the device, and the specific preparation steps are as follows:
1. Adding anthracene powder into a main molecular raw material area 5, and filling branch pipes as much as possible; covering the opening of the open reaction device 1; heating the bulk molecular feedstock region with a second electric heating device 32 to heat the anthracene powder above the melting point until the anthracene powder melts into liquid anthracene; stopping heating, cooling to room temperature, and filling anthracene into a main molecular raw material area in a form of monolithic solid; if the entire solid form of anthracene does not fill the branch, the addition in the above steps is continued until the solid anthracene almost fills the branch.
2. Adding mixed powder of DBT and anthracene into a guest molecule raw material zone 4; the glove box 7 is filled with nitrogen; covering the opening of the open reaction device 1; heating the mixed powder of DBT and anthracene to a temperature higher than the melting point of anthracene by using a first electric heating device 31 to dissolve DBT in liquid anthracene; heating is continued until the anthracene has all phase changed to gaseous molecules, leaving DBT attached to the walls of the guest molecule feed zone 4 in a thin layer.
3. The anthracene wafer attached to the side wall of the open reaction apparatus 1 generated in steps 1 and 2 was scraped off.
4. Wafer generation and collection: covering the opening of the open reaction device 1; heating the guest molecule raw material region 4 by using a first electric heating device 31 to continuously sublimate DBT in the guest molecule raw material region 4, and accumulating the gaseous DBT molecular concentration in the opening reaction device 1; next, the guest molecule raw material region 4 and the host molecule raw material region 5 are heated by using the first electric heating device 31 and the second electric heating device 32, respectively, the temperatures of the two electric heating devices being set independently, for example, the temperature of the first electric heating device 31 is set to 280 ℃, and the temperature of the second electric heating device 32 is set to 215 ℃; after heating for several tens of seconds, the wafer formation was observed, at which time the lid of the open reaction apparatus 1 was opened, and a large amount of the wafer was escaped from the opening and slowly settled onto the polymer material sheet 2 having a rough surface placed near the open reaction apparatus and collected.
5. After the desired number of wafers are collected, the opening of the open reaction apparatus 1 is covered, and heating is stopped.
[ Example 4]
Example 4 the same preparation apparatus as in example 3 was used, example 4 differing from example 3 only in step 2 of the specific preparation steps:
2. Adding DBT powder and alcohol into the guest molecule raw material zone 4 to dissolve DBT in alcohol; the glove box 7 is filled with nitrogen; the guest molecule material region 4 is heated by the first electric heating means 31 to a temperature of 75 ℃ or higher, and DBT remains attached to the wall as a thin layer after the alcohol is completely volatilized.
The DBT molecule-doped anthracene organic micro-nano wafers obtained in examples 2, 3, and 4 have the same microstructure and physical properties as those of the DBT molecule-doped anthracene organic micro-nano wafer obtained in example 1, and are not described in detail.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.

Claims (16)

1. The preparation device of the fluorescent molecule doped organic micro-nano wafer is characterized by comprising an opening reaction device, a wafer collecting device and a heating device, wherein the opening reaction device comprises a guest molecule raw material region, a host molecule raw material region and a wafer growth doping region;
The outlets of the guest molecule raw material region and the host molecule raw material region are respectively communicated with the lower port of the wafer growth doping region, and the top end of the wafer growth doping region is an opening;
the host molecular raw material region is loaded with a host molecular material of an organic micro-nano wafer, and the guest molecular raw material region is loaded with a fluorescent molecular material for doping; the heating device is used for heating the host molecular material of the host molecular raw material area and the fluorescent molecular material of the guest molecular raw material area respectively;
The wafer collection device is used for collecting the doped wafers escaping from the top opening of the wafer growth doped region.
2. The apparatus for preparing a fluorescent molecule doped organic micro-nano wafer according to claim 1, wherein the outlet of the host molecule raw material region is positioned at a higher level than the outlet of the guest molecule raw material region.
3. The apparatus for preparing a fluorescent molecule doped organic micro-nano wafer according to claim 1, wherein the guest molecule material region and the host molecule material region have different temperatures.
4. The apparatus for preparing a fluorescent molecule doped organic micro-nano wafer according to claim 1, wherein the guest molecule raw material region and the host molecule raw material region have different raw material surface areas after the raw materials are loaded respectively.
5. The apparatus for preparing a fluorescent molecular doped organic micro-nano wafer according to claim 1, wherein the wafer growth doped region of the open reaction device has an adjustable cross-sectional size and length.
6. The apparatus for preparing a fluorescent molecule doped organic micro-nano wafer according to claim 1, wherein the wafer collecting means comprises a polymer material sheet having a rough surface placed near the opening of the opening reaction means.
7. The apparatus for preparing a fluorescent molecular doped organic micro-nano wafer according to claim 6, wherein the opening part of the opening reaction device and the wafer collecting device are all placed in a protective gas environment.
8. The apparatus for preparing a fluorescent molecular doped organic micro-nano wafer according to claim 1, wherein the heating device is an oil bath heating device, the guest molecular raw material region is located at a deeper position below the oil bath liquid level, the host molecular raw material region is located near the oil bath liquid level, and the wafer growth doping region is located above the oil bath liquid level.
9. The apparatus for preparing a fluorescent molecule doped organic micro-nano wafer according to claim 1, wherein the heating device is an electric heating device, and the guest molecule raw material region and the host molecule raw material region are respectively controlled in temperature by two separate electric heating devices.
10. The preparation device of the fluorescent molecule doped organic micro-nano wafer according to claim 1, wherein the opening reaction device is a special-shaped glass test tube, the special-shaped glass test tube is provided with a main tube and branch tubes, the upper part of the main tube is a wafer growth doping area, the bottom is a guest molecule raw material area, and the branch tubes are host molecule raw material areas.
11. The preparation method of the fluorescent molecule doped organic micro-nano wafer is characterized by comprising the following steps of:
Loading a host molecular raw material and a guest molecular raw material into the host molecular raw material zone and the guest molecular raw material zone respectively; heating the guest molecule raw material region by the heating device to enable the guest molecule raw material to continuously change phase into gaseous molecules; heating the main molecular raw material region by the heating device to enable the main molecular raw material to continuously change phase into gaseous molecules; mixing gaseous host molecules and guest molecules in the wafer growth doping area and forming an organic micro-nano wafer by cooling, wherein the organic micro-nano wafer mainly comprises the host molecules, and the guest molecules are doped in the organic micro-nano wafer; the organic micro-nano wafer moves along with the air flow to the opening of the opening reaction device and finally escapes from the opening; and collecting the wafer by using the wafer collecting device.
12. The method for preparing a fluorescent molecule doped organic micro-nano wafer according to claim 11, wherein the step of loading the host molecule raw material comprises the following processes:
Adding a main molecular raw material into the main molecular raw material region; heating the main molecular raw material region to a temperature higher than the melting point of the main molecular raw material by using the heating device, so as to melt the main molecular raw material; after stopping heating and cooling to room temperature, the main molecular raw material is filled in the main molecular raw material area in the form of a whole solid.
13. The method of preparing a fluorescent molecule doped organic micro-nano wafer according to claim 11, wherein the step of loading guest molecule raw material comprises the following steps:
Adding a guest molecular raw material and a host molecular raw material into the guest molecular raw material zone, wherein the melting point of the host molecular raw material is lower than that of the guest molecular raw material, and the rate of phase change of the host molecular raw material into gaseous molecules is far higher than that of the guest molecular raw material at the same temperature; heating the guest molecular raw material region to a temperature higher than the melting point of the host molecular raw material by using the heating device, so that the guest molecular raw material is dissolved in the melted host molecular raw material; heating is continued for a period of time until the host molecular material is totally transformed into gaseous molecules, leaving only the guest molecular material in the form of a thin layer attached to the wall.
14. The method of preparing a fluorescent molecule doped organic micro-nano wafer according to claim 11, wherein the step of loading guest molecule raw material comprises the following steps:
adding a guest molecular feedstock to the guest molecular feedstock zone; adding a small amount of solvent to dissolve the guest molecule raw material in the solvent; the solvent is volatilized leaving only the guest molecular material in a thin layer attached to the walls.
15. The method of claim 11, wherein the opening of the open reaction device is covered when the guest molecule material is heated, so that the concentration of gaseous guest molecules in the reaction device is accumulated until the host molecule material is heated and the wafer starts to be produced, and the cover is removed, so that the opening of the open reaction device is opened.
16. The method of preparing a fluorescent molecule doped organic micro-nano wafer of claim 11, wherein the step of collecting the wafer comprises the following steps:
placing a polymer material sheet with a rough surface in the area near the opening; the wafer is deposited onto the sheet of polymeric material after exiting the open reaction apparatus with the gas stream.
CN202410162413.3A 2024-02-05 2024-02-05 Preparation device and method of fluorescent molecule doped organic micro-nano wafer Pending CN118223113A (en)

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