CN113529015B - Method for producing metal organic material - Google Patents
Method for producing metal organic material Download PDFInfo
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- CN113529015B CN113529015B CN202110751617.7A CN202110751617A CN113529015B CN 113529015 B CN113529015 B CN 113529015B CN 202110751617 A CN202110751617 A CN 202110751617A CN 113529015 B CN113529015 B CN 113529015B
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention relates to a preparation method of metal organic material, under the vacuum condition, put metal substrate, basic group metal salt and organic material that the atomic level is smooth into the thermal evaporator separately, degas, heat, deposit and grow homogeneous alkali metal film and organic material film; and carrying out annealing treatment on the base metal salt film and the organic material film deposited on the metal substrate to finish the preparation. According to the preparation method provided by the invention, the base metal salt is used for replacing base metal to serve as a donor of base ions and atoms, so that the technical problems that strong-metal base atoms are not easy to separate and alkali metal atoms are unstable in air in the prior art are solved, the base metal atoms can be uniformly diffused on a substrate, the doping difficulty of organic base elements is reduced, a base metal-organic material film material with accurate doping proportion is prepared, and the safety and controllability of base element doping are effectively improved.
Description
Technical Field
The invention relates to the technical field of organic semiconductor material preparation, in particular to a preparation method of a metal organic material.
Background
Organic semiconductor materials have many new characteristics different from inorganic semiconductor materials, the organic semiconductor materials have the characteristics of light weight, flexibility, easy processability, low-temperature large-area film forming and the like, and the research on applying the low-cost organic semiconductor materials to microelectronic and optoelectronic devices and wearable equipment is highly emphasized in recent years. Ultrafast spectrum technology and ultrastructure characterization methods established in recent years provide means for researching the excited state of an organic semiconductor, so that basic research and application research of the excited state property and the excited state structure of the organic semiconductor are rapidly developed, and the method becomes one of the most active research fields internationally at present.
Perylene tetracarboxylic dianhydride (PTCDA) is widely reported as a common organic semiconductor material with a few electron systems and good photoelectric properties for testing the growth process, electronics and optical properties of semiconductor films. In particular, the organic material itself is a semiconductor having a band gap, which makes it possible to easily control the intrinsic P — N characteristics of the semiconductor by donor doping. For example, after doping of metal ions serving as charge donor bases, the photoelectric properties of the material can be regulated through the change of P-N characteristics of the material. Meanwhile, the conductivity of the donor is obviously improved due to the increase of the charge density of the donor, and even the superconducting performance is realized. In addition, doping of base metals in different proportions can also affect the crystal structure of the film, and further affect the optical-electrical-magnetic properties of the film. This will certainly help to expand the potential practical application area and range of the material itself. Such as wearable optoelectronic devices, sensors, sodium storage cells, single photon light sources required in quantum communication technology, etc.
The existing mature method for doping base metal in the organic semiconductor film preparation process is to dope the organic film by usually adopting an alkali metal adsorbent as an alkali metal donor, so as to prepare the doped film with a metal organic covalent structure. The base metals in the prior art generally have lower melting points (such as Na =97.72 ℃ and K =63.38 ℃), and for the base metal atoms deposited on the substrate, the atoms are easier to leave the growth substrate rather than uniformly diffuse on the substrate during the high-temperature annealing treatment of the sample, so that the technical route of depositing the base metal first, then depositing molecular materials such as PTCDA and then performing the subsequent annealing treatment in the preparation process of the organic film is difficult. In addition, alkali metals, as group 1 elements in the periodic table of elements, are abnormally activated, so that the safety during and after the preparation of the material is also an important consideration.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a preparation method of a metal organic material.
The preparation method of the metal organic material comprises the following steps:
s1, respectively putting an atomically flat metal substrate, basic metal salt and an organic material into a thermal evaporator under a vacuum condition, degassing and heating, respectively and uniformly diffusing the basic metal salt and the organic material on the metal substrate in sequence, and depositing and growing a uniform film;
s2, annealing the base metal salt film and the organic material film deposited on the metal substrate to finish the preparation of the metal organic material.
Further, in the step S1, an atomic-level flat metal substrate is obtained by carrying out sputtering and annealing treatment on the metal substrate; in the sputtering process, an ion gun is vertical to the metal substrate, the distance is 80mm, the high voltage of the ion gun is 3000V, the exciting current is 3mA, and the substrate current is 7 muA; in the annealing process, the annealing temperature is 300-60 ℃, the heating rate is 1 ℃/s, and the cooling rate is 0.5 ℃/s.
Further, the annealing temperature in step S3 is: 50 to 350 ℃.
Further, the dosage of the raw material is more than or equal to the deposition growth rate in the annealing process and the deposition growth time in the annealing process.
Further, the coverage rate of the dosage of the alkali metal salt is less than or equal to 50 percent, namely the dosage of the alkali metal salt is less than or equal to 0.5ML; the coverage rate of the organic material dosage is less than or equal to 80 percent, namely the organic material dosage is less than or equal to 0.8ML.
Further, the alkali metal salt is one or a mixture of more of lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt and francium salt, and the organic material is an organic small molecule material having one or more of anhydride group, carboxyl group, carbonyl group and halogen functional group.
According to the preparation method of the metal organic material, the base metal-containing salts are used for replacing base metals to serve as donors of base ions and atoms, the technical problems that strong-metal base atoms are easy to separate and alkali metal atoms are unstable in air in the prior art are solved, the base metal atoms can be uniformly diffused on a substrate, the doping difficulty of organic base elements is reduced, the base metal-organic material thin film material with accurate doping proportion is prepared, and meanwhile, the safety and controllability of base element doping are effectively improved.
Drawings
FIG. 1 is a flow chart of a method of preparing a metal-organic material according to an embodiment of the present invention;
FIG. 2 is a diagram of a method for preparing a metal-organic material and for switching between structures according to an embodiment of the present invention;
FIG. 3 shows Na in example 1 of the present invention 0.25 PTCDA scanning tunnel microscope topography;
FIG. 4 shows Na in example 2 of the present invention 0.5 PTCDA scanning tunnel microscope topography;
FIG. 5 is a topographic map of a NaPTCDA scanning tunneling microscope in example 3 of the present invention;
FIG. 6 shows Na in example 4 of the present invention 2 PTCDA scanning tunneling microscope topography.
Detailed Description
Embodiments of the present invention will be described in further detail with reference to the drawings and examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a metal organic material, which comprises the following steps:
s1, air pressure of 3 x 10 -5 Under the argon condition of Torr, carrying out sputtering and annealing treatment on the metal substrate by using argon ions, and repeatedly carrying out sputtering and annealing treatment on the metal substrate until obtaining the metal substrate with flat atomic level; at an air pressure of 5X 10 -10 Under the condition of Torr, respectively putting an atomically flat metal substrate, naCl and PTCDA into a thermal evaporator, degassing and heating, respectively and uniformly diffusing the NaCl and the PTCDA on the metal substrate in sequence, and depositing and growing a uniform NaCl film and a uniform PTCDA film;
s2, annealing the NaCl film and the PTCDA film deposited on the metal substrate to finish the preparation of the metal organic material.
According to the preparation method provided by the invention, base metal is replaced by base metal salt to be used as base ions, and the technical scheme of the invention can not only improve the safety coefficient in the material preparation process, but also enable base metal atoms to be uniformly diffused on a metal substrate, so that the technical problem that the base metal-PTCDA nanostructure can only be prepared by depositing and growing PTCDA molecules first and then depositing and growing alkali metal, and the doping of the base metal and organic materials can be effectively and accurately controlled is solved.
The invention provides a preferred embodiment, in step S1, an atomic-level flat metal substrate is obtained by sputtering a metal substrate and then annealing; in the sputtering process, the argon ion gun and the metal substrate are kept vertical, the distance is 80mm, the argon ion gun has high voltage of 3000V, the exciting current is 3mA, and the substrate current is 7 muA. In the annealing process, the annealing temperature is 500 ℃, the heating rate is 1 ℃/s, and the cooling rate is 0.5 ℃/s.
The invention provides a preferred embodiment, the annealing temperature in step S2 is: 50-350 ℃.
The invention provides a preferred embodiment, the dosage of the raw material is more than or equal to the deposition growth rate in the annealing process and the deposition growth time in the annealing process.
The metal organic materials of NaCl and PTCDA with different proportions can be prepared by adjusting the dosages of NaCl and PTCDA with different proportions and annealing at different temperatures.
The invention provides a preferable embodiment, the coverage rate of NaCl dosage is less than or equal to 50 percent, namely the NaCl dosage is less than or equal to 0.5ML; the coverage of the PTCDA dose is less than or equal to 80 percent, i.e. the PTCDA dose is less than or equal to 0.8ML.
In a preferred embodiment, the alkali metal salt is one or a mixture of lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, and francium salt. The organic material is an organic micromolecular material with one or more of anhydride group, carboxyl group, carbonyl group and halogen functional group.
Example 1
s1, at the air pressure of 5 multiplied by 10 -10 And (2) carrying out NaCl deposition growth on an atomically flat Au substrate by using a thermal evaporator under the condition of Torr, wherein in the deposition growth process, the Au substrate is vertical to a window of the thermal evaporator, the temperature of a crucible is 450 ℃, the deposition growth rate is 0.03ML/min, and the deposition growth time is 20s. Under the same air pressure condition, the thermal evaporator is used for carrying out PTCDA deposition growth on the Au substrate with NaCl, the Au substrate with NaCl is deposited and grown vertically to the window of the thermal evaporator, the crucible temperature is 350 ℃, the deposition growth rate is 0.04ML/min, and the deposition growth time is 10min.
S2, annealing the Au substrate deposited with the NaCl thin film and the PTCDA thin film to complete the preparation of the metal organic material.
The present invention provides a preferred embodiment, in step S1, the air pressure is 3 × 10 -5 Under the argon condition of Torr, carrying out sputtering-first and annealing-later treatment on the Au substrate by using argon ions, repeating sputtering and annealing treatment for three times on the Au substrate, and characterizing the Au substrate by using a low-energy electron diffractometer, an Auger electron spectrometer and a scanning tunnel microscope to obtain the Au substrate with smooth atomic level, no impurities and few defects. In the sputtering process, the argon ion gun is vertical to the Au substrate, the distance is 80mm, the high voltage of the argon ion gun is 3000V, the excitation current is 3mA, and the Au substrate current is 7 muA. In the annealing process, the annealing temperature is 500 ℃, the heating rate is 1 ℃/s, and the cooling rate is 0.5 ℃/s.
In step S2, the annealing temperature is 200 ℃, the annealing temperature is maintained for 10min after 200 ℃, the temperature rising rate is 1 ℃/S, and the temperature reduction rate is 0.5 ℃/S, so as to complete the preparation of the metal organic material.
The invention provides a preferred embodiment, the dosage of NaCl is more than or equal to 0.0125ML and the dosage of PTCDA is more than or equal to 0.4ML.
The invention provides a preferable embodiment, when the metal organic material is prepared by the preparation method, the maximum coverage rate of NaCl is 50 percent when annealing treatment is carried out for 1 time, namely the maximum dosage of NaCl is 0.5ML; the maximum coverage of PTCDA was 80%, i.e. the maximum dose of PTCDA was 0.8ML.
The structure of the prepared metal organic material is shown in figure 3, and comparison with the result of the first principle calculation proves that the unit cell of the metal organic material comprises 1 Na atom and 4 PTCDA molecules, namely Na 0.25 PTCDA。
Example 2
s1, at a pressure of 5X 10 -10 And under the Torr condition, performing NaCl deposition growth on an atomically flat Au substrate by using a thermal evaporator, wherein in the deposition growth process, the Au substrate is vertical to a window of the thermal evaporator, the crucible temperature is 450 ℃, the deposition growth rate is 0.03ML/min, and the deposition growth time is 40s. Under the same air pressure condition, the thermal evaporator is used for carrying out PTCDA deposition growth on the Au substrate with NaCl, the Au substrate with NaCl is deposited and grown vertically to the window of the thermal evaporator, the crucible temperature is 350 ℃, the deposition growth rate is 0.04ML/min, and the deposition growth time is 10min.
S2, annealing the Au substrate deposited with the NaCl film and the PTCDA film to finish the preparation of the metal organic material.
The present invention provides a preferred embodiment, in step S1, the air pressure is 3 × 10 -5 Under the argon condition of Torr, carrying out sputtering-first and annealing-later treatment on the Au substrate by using argon ions, repeating sputtering and annealing treatment for three times on the Au substrate, and characterizing the Au substrate by using a low-energy electron diffractometer, an Auger electron spectrometer and a scanning tunnel microscope to obtain the Au substrate with smooth atomic level, no impurities and few defects. In the sputtering process, the argon ion gun and the Au substrate are kept vertical at a distance of 80mm, the argon ion gun has high voltage of 3000V, the excitation current is 3mA, and the Au substrate current is 7 muA. In the annealing process, the annealing temperature is 500 ℃, the heating rate is 1 ℃/s, and the cooling rate is 0.5 ℃/s.
In step S2, the annealing temperature is 50 ℃, the annealing temperature is maintained for 10min after reaching 50 ℃, the temperature rise rate is 1 ℃/S, and the temperature drop rate is 0.5 ℃/S, so as to complete the preparation of the metal organic material.
The invention provides a preferred embodiment, the dosage of NaCl is more than or equal to 0.025ML and the dosage of PTCDA is more than or equal to 0.4ML.
The invention provides a preferable embodiment, when the metal organic material is prepared by the preparation method, the maximum coverage rate of NaCl is 50 percent when annealing treatment is carried out for 1 time, namely the maximum dosage of NaCl is 0.5ML; the maximum coverage of PTCDA was 80%, i.e. the maximum dose of PTCDA was 0.8ML.
The structure of the prepared metal organic material is shown in figure 4 by measuring the metal organic material by using a scanning tunneling microscope, and the comparison of the structure with the result of the calculation of the first principle proves that the unit cell of the metal organic material comprises 1 Na atom and 2 PTCDA molecules, namely Na 0.5 PTCDA。
Example 3
Embodiment 3 of the present invention provides a method for preparing a metal organic material, as shown in fig. 1, including the following steps:
s1, at a pressure of 5X 10 -10 And under the Torr condition, performing NaCl deposition growth on an atomically flat Au substrate by using a thermal evaporator, wherein in the deposition growth process, the Au substrate is vertical to a window of the thermal evaporator, the crucible temperature is 500 ℃, the deposition growth rate is 0.15ML/min, and the deposition growth time is 20s. Under the same air pressure condition, the thermal evaporator is used for carrying out PTCDA deposition growth on the Au substrate with NaCl, the Au substrate with NaCl is deposited and grown vertically to the window of the thermal evaporator, the crucible temperature is 350 ℃, the deposition growth rate is 0.04ML/min, and the deposition growth time is 10min.
S2, annealing the Au substrate deposited with the NaCl film and the PTCDA film to finish the preparation of the metal organic material.
The present invention provides a preferred embodiment, in step S1, the air pressure is 3 × 10 -5 Under the argon condition of Torr, carrying out sputtering and annealing treatment on an Au substrate by using argon ions, repeating sputtering and annealing treatment on the Au substrate for three times, and representing the Au substrate by using a low-energy electron diffractometer, an Auger electron energy spectrometer and a scanning tunnel microscope to obtain the Au substrate with smooth atomic level, no impurities and few defects. In the sputtering process, the argon ion gun is perpendicular to the Au substrate and is at a distance80mm, high pressure of an argon ion gun of 3000V, excitation current of 3mA, and Au substrate current of 7 muA. In the annealing process, the annealing temperature is 500 ℃, the heating rate is 1 ℃/s, and the cooling rate is 0.5 ℃/s.
In step S2, the annealing temperature is 200 ℃, the annealing temperature is maintained for 10min after reaching 200 ℃, the temperature rise rate is 1 ℃/S, and the temperature drop rate is 0.5 ℃/S, thereby completing the preparation of the metal organic material.
The present invention provides a preferred embodiment, the dosage of NaCl is 0.05ML or more and the dosage of PTCDA is 0.4ML or more.
The invention provides a preferable embodiment, when the metal organic material is prepared by the preparation method, the maximum coverage rate of NaCl is 50 percent when annealing treatment is carried out for 1 time, namely the maximum dosage of NaCl is 0.5ML; the maximum coverage of PTCDA was 80%, i.e. the maximum dose of PTCDA was 0.8ML.
The metal organic material is measured by using a scanning tunnel microscope, the structure of the prepared metal organic material is shown in fig. 5, and comparison with the result of the first principle calculation proves that the unit cell of the metal organic material comprises 1 Na atom and 1 PTCDA molecule, namely NaPTCDA.
Example 4
s1, at the air pressure of 5 multiplied by 10 -10 And under the Torr condition, performing NaCl deposition growth on an atomically flat Au substrate by using a thermal evaporator, wherein in the deposition growth process, the Au substrate is vertical to a window of the thermal evaporator, the crucible temperature is 500 ℃, the deposition growth rate is 0.15ML/min, and the deposition growth time is 40s. Under the same air pressure condition, the thermal evaporator is used for carrying out PTCDA deposition growth on the Au substrate with NaCl, the Au substrate with NaCl is deposited and grown vertically to the window of the thermal evaporator, the crucible temperature is 350 ℃, the deposition growth rate is 0.04ML/min, and the deposition growth time is 10min.
S2, annealing the Au substrate deposited with the NaCl thin film and the PTCDA thin film to complete the preparation of the metal organic material.
The invention provides a preferable exampleExample, in step S1, the gas pressure is 3X 10 -5 Under the argon condition of Torr, carrying out sputtering and annealing treatment on an Au substrate by using argon ions, repeating sputtering and annealing treatment on the Au substrate for three times, and representing the Au substrate by using a low-energy electron diffractometer, an Auger electron energy spectrometer and a scanning tunnel microscope to obtain the Au substrate with smooth atomic level, no impurities and few defects. In the sputtering process, the argon ion gun is vertical to the Au substrate, the distance is 80mm, the high voltage of the argon ion gun is 3000V, the excitation current is 3mA, and the Au substrate current is 7 muA. In the annealing process, the annealing temperature is 500 ℃, the heating rate is 1 ℃/s, and the cooling rate is 0.5 ℃/s.
In step S2, the annealing temperature is 300 ℃, the annealing temperature is maintained for 10min after reaching 300 ℃, the temperature rising rate is 1 ℃/S, and the temperature reduction rate is 0.5 ℃/S, so as to complete the preparation of the metal organic material.
The present invention provides a preferred embodiment, the dosage of NaCl is 0.1ML or more and the dosage of PTCDA is 0.4ML or more.
The invention provides a preferable embodiment, when the metal organic material is prepared by the preparation method, the maximum coverage rate of NaCl is 50 percent when annealing treatment is carried out for 1 time, namely the maximum dosage of NaCl is 0.5ML; the maximum coverage of PTCDA was 80%, i.e. the maximum dose of PTCDA was 0.8ML.
The structure of the prepared metal organic material is shown in fig. 6, and comparison with the result of the first principle calculation proves that the unit cell of the metal organic material comprises 2 Na atoms and 1 PTCDA molecule, namely Na 2 PTCDA。
Example 5
Embodiment 5 of the present invention provides a method for preparing a metal organic material, as shown in fig. 1, including the following steps:
s1, at the air pressure of 5 multiplied by 10 -10 And under the Torr condition, performing NaCl deposition growth on an atomically flat Au substrate by using a thermal evaporator, wherein in the deposition growth process, the Au substrate is vertical to a window of the thermal evaporator, the crucible temperature is 450 ℃, the deposition growth rate is 0.03ML/min, and the deposition growth time is 20s. Under the same air pressure condition, using a thermal evaporator to produceAnd carrying out the deposition growth of the PTCDA on the Au substrate with the NaCl, wherein the Au substrate with the NaCl is vertical to a window of the thermal evaporator, the crucible temperature is 350 ℃, the deposition growth rate is 0.04ML/min, and the deposition growth time is 10min.
S2, annealing the Au substrate deposited with the NaCl thin film and the PTCDA thin film to complete the preparation of the metal organic material.
The present invention provides a preferred embodiment, in step S1, the air pressure is 3 × 10 -5 Under the argon condition of Torr, carrying out sputtering-first and annealing-later treatment on the Au substrate by using argon ions, repeating sputtering and annealing treatment for three times on the Au substrate, and characterizing the Au substrate by using a low-energy electron diffractometer, an Auger electron spectrometer and a scanning tunnel microscope to obtain the Au substrate with smooth atomic level, no impurities and few defects. In the sputtering process, the argon ion gun is vertical to the Au substrate, the distance is 80mm, the high voltage of the argon ion gun is 3000V, the excitation current is 3mA, and the Au substrate current is 7 muA. In the annealing process, the annealing temperature is 500 ℃, the heating rate is 1 ℃/s, and the cooling rate is 0.5 ℃/s.
In step S2, the annealing temperature is 200 ℃, the annealing temperature is maintained for 10min after 200 ℃, the temperature rising rate is 1 ℃/S, and the temperature reduction rate is 0.5 ℃/S, so as to complete the preparation of the metal organic material.
The metal organic material is measured by using a scanning tunnel microscope, and the comparison of the result with the first principle calculation proves that the unit cell of the metal organic material comprises 1 Na atom and 4 PTCDA molecules.
The invention provides a preferred embodiment, as shown in fig. 2, at least 0.0125ML of NaCl and a prepared metal organic material whose unit cell comprises 1 Na atom and 4 PTCDA molecules are annealed, the annealing temperature is 200 ℃, after reaching 200 ℃, the annealing temperature is maintained for 20s, the temperature rising rate is 1 ℃/s, the temperature reducing rate is 0.5 ℃/s, the conversion between metal organic material structures is completed, the metal organic material is measured by using a scanning tunneling microscope, and the comparison with the result of the first principle calculation proves that the unit cell comprises 1 Na atom and 2 PTCDA molecules. Then Na is completed 0.25 PTCDA to Na 0.5 And (5) PTCDA conversion.
The invention provides aIn a preferred embodiment, as shown in fig. 2, at least 0.025ML of NaCl and a prepared metal-organic material whose unit cell contains 1 Na atom and 2 PTCDA molecules are annealed at 200 ℃, and then maintained at 200 ℃ for 20s, at a temperature rising rate of 1 ℃/s and a temperature falling rate of 0.5 ℃/s, thereby completing the structural transformation between the metal-organic materials, and the metal-organic material is measured by using a scanning tunneling microscope, and the comparison with the calculation result of the first principle proves that the unit cell contains 1 Na atom and 1 PTCDA molecule. Then Na is completed 0.5 PTCDA to NaPTCDA conversion.
The present invention provides a preferred embodiment, as shown in fig. 2, at least 0.05ML of NaCl and a prepared metal organic material whose unit cell includes 1 Na atom and 1 PTCDA molecule are annealed at 300 ℃, and after reaching 300 ℃, the annealing temperature is maintained for 20s, the temperature rising rate is 1 ℃/s, the temperature decreasing rate is 0.5 ℃/s, thereby completing the conversion between the metal organic material structures, and the metal organic material is measured by using a scanning tunneling microscope, and the comparison with the first principle calculation result proves that the unit cell includes 2 Na atoms and 1 PTCDA molecule. I.e., complete NaPTCDA to Na 2 PTCDA conversion.
The preparation method can adjust the dosages of NaCl and PTCDA with different proportions, and carry out annealing at different temperatures, so as to prepare the metal organic materials of NaCl and PTCDA with different proportions.
Example 6
Embodiment 6 of the present invention provides a method for preparing a metal organic material, as shown in fig. 1, including the following steps:
s1, at the air pressure of 5 multiplied by 10 -10 And under the Torr condition, performing NaCl deposition growth on an atomically flat Au substrate by using a thermal evaporator, wherein in the deposition growth process, the Au substrate is vertical to a window of the thermal evaporator, the crucible temperature is 500 ℃, the deposition growth rate is 0.15ML/min, and the deposition growth time is 20s. Under the same air pressure condition, the thermal evaporator is used for carrying out PTCDA deposition growth on the Au substrate with NaCl, the Au substrate with NaCl is vertical to the window of the thermal evaporator, the crucible temperature is 350 ℃, the deposition growth rate is 0.04ML/min, and the deposition growth time is 5min.
S2, annealing the Au substrate deposited with the NaCl film and the PTCDA film to finish the preparation of the metal organic material.
The present invention provides a preferred embodiment, in step S1, the air pressure is 3 × 10 -5 Under the argon condition of Torr, carrying out sputtering and annealing treatment on an Au substrate by using argon ions, repeating sputtering and annealing treatment on the Au substrate for three times, and representing the Au substrate by using a low-energy electron diffractometer, an Auger electron energy spectrometer and a scanning tunnel microscope to obtain the Au substrate with smooth atomic level, no impurities and few defects. In the sputtering process, the argon ion gun is vertical to the Au substrate, the distance is 80mm, the high voltage of the argon ion gun is 3000V, the excitation current is 3mA, and the Au substrate current is 7 muA. In the annealing process, the annealing temperature is 500 ℃, the heating rate is 1 ℃/s, and the cooling rate is 0.5 ℃/s.
In step S2, the annealing temperature is 300 ℃, the annealing temperature is maintained for 5min after reaching 300 ℃, the temperature rising rate is 1 ℃/S, and the temperature reduction rate is 0.5 ℃/S, so as to complete the preparation of the metal organic material.
The metal organic material is measured by using a scanning tunnel microscope, and the comparison of the result with the first principle calculation proves that the unit cell of the metal organic material comprises 2 Na atoms and 1 PTCDA molecule.
The invention provides a preferred embodiment, as shown in fig. 2, at least 0.2ML PTCDA and a prepared metal organic material with unit cell containing 2 Na atoms and 1 PTCDA molecule are annealed, the annealing temperature is 200 ℃, the temperature is maintained for 5min after reaching 200 ℃, the temperature rise rate is 1 ℃/s, the temperature decrease rate is 0.5 ℃/s, the conversion between metal organic material structures is completed, the metal organic material is measured by using a scanning tunneling microscope, and the comparison with the result of the first principle calculation proves that the unit cell contains 1 Na atom and 1 PTCDA molecule. Then Na is completed 2 PTCDA to NaPTCDA conversion.
The present invention provides a preferred embodiment, as shown in FIG. 2, at least 0.4ML of PTCDA and the prepared metal organic material with unit cell containing 1 Na atom and 1 PTCDA molecule are annealed at 200 deg.C for 5min after reaching 200 deg.C, and the heating rate is increasedThe temperature reduction rate is 0.5 ℃/s at 1 ℃/s, the conversion between the metal organic material structures is completed, a scanning tunnel microscope is used for measuring the metal organic material, and the comparison with the calculation result of the first principle proves that the unit cell of the metal organic material comprises 1 Na atom and 2 PTCDA molecules. I.e., complete NaPTCDA to Na 0.5 And (5) PTCDA conversion.
The invention provides a preferred embodiment, as shown in fig. 2, 0.8ML PTCDA and a prepared metal organic material of which unit cell comprises 1 Na atom and 2 PTCDA molecules are annealed, the annealing temperature is 200 ℃, the temperature is maintained for 5min after reaching 200 ℃, the temperature rise rate is 1 ℃/s, the temperature decrease rate is 0.5 ℃/s, the conversion between metal organic material structures is completed, the metal organic material is measured by using a scanning tunneling microscope, and the comparison with the result of the first principle calculation proves that the unit cell comprises 1 Na atom and 4 PTCDA molecules. Then Na is completed 0.5 PTCDA to Na 0.25 PTCDA conversion.
According to the preparation method of the metal organic material, the base metal-containing salts are used for replacing base metals to serve as donors of base ions and atoms, the technical problem that the base atoms are not easy to separate in the prior art is solved, the base metal atoms can be uniformly diffused on the Au substrate, the doping difficulty of organic base elements is reduced, the base metal-perylene tetracarboxylic acid dianhydride film material with accurate doping proportion is prepared, and meanwhile, the safety and controllability of base element doping are effectively improved. The preparation method of the metal organic material provided by the invention has the advantages of simple synthetic route, good repeatability and capability of large-scale industrialization. Meanwhile, the metal organic material prepared by the preparation method effectively regulates and controls the energy band structure of the molecular crystal, and greatly improves the photoelectric property of the molecular crystal.
In the description of the specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are exemplary and should not be taken as limiting the invention. Variations, modifications, substitutions and alterations of the above-described embodiments may be made by those of ordinary skill in the art without departing from the scope of the present invention.
The above embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (5)
1. The preparation method of the metal organic material is characterized by comprising the following steps:
s1, respectively putting an atomically flat metal substrate, basic metal salt and an organic material into a thermal evaporator under a vacuum condition, degassing and heating, respectively and uniformly diffusing the basic metal salt and the organic material on the metal substrate in sequence, and depositing and growing a uniform film;
s2, annealing the base metal salt film and the organic material film deposited on the metal substrate to finish the preparation of the metal organic material;
adjusting the dosages of NaCl and PTCDA in different proportions, and performing annealing treatment at different temperatures to prepare the metal organic materials of the PTCDA in different Na ion doping proportions; the doping ratio of Na ions to PTCDA included: 1:1, 1:2, 1:4, 2:1;
when annealing treatment is carried out each time, the coverage rate of the dosage of the basic group metal salt is less than or equal to 50 percent, namely the dosage of the basic group metal salt is less than or equal to 0.5ML; the coverage rate of the organic material dosage is less than or equal to 80 percent, namely the organic material dosage is less than or equal to 0.8ML.
2. The method for producing a metal-organic material according to claim 1, wherein in step S1,
sputtering a metal substrate and then annealing to obtain an atomic-level flat metal substrate;
in the sputtering process, an ion gun is vertical to the metal substrate, the distance is 80mm, the high voltage of the ion gun is 3000V, the exciting current is 3mA, and the substrate current is 7 muA;
in the annealing process, the annealing temperature is 300-600 ℃, the heating rate is 1 ℃/s, and the cooling rate is 0.5 ℃/s.
3. The method for preparing a metal-organic material according to claim 1, wherein the annealing temperature in step S2 is: 50-350 ℃.
4. The method of claim 1, wherein the amount of the raw material is not less than the deposition growth rate during the annealing process and the deposition growth time during the annealing process.
5. The method according to any one of claims 1 to 4, wherein the alkali metal salt is one or a mixture of lithium, sodium, potassium, rubidium, cesium and francium salts, and the organic material is a small organic molecule material having one or more of acid anhydride, carboxyl, carbonyl and halogen functions.
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| EP0826434A1 (en) * | 1996-07-31 | 1998-03-04 | Istituto Nazionale Di Fisica Nucleare | Process and apparatus for preparing thin films of polymers and composite materials on different kind of substrates |
| CN110679008A (en) * | 2017-06-02 | 2020-01-10 | 纳米技术仪器公司 | Shape conforming alkali metal-sulfur battery |
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