Method for regulating molecular assembly structure on metal surface through alkali metal salt
By co-depositing alkali metal salts and tripyridine tricarboxylic acid molecules on the metal surface and performing annealing treatment using a low-temperature scanning tunneling microscope, precise control of the molecular assembly structure on the metal surface was achieved, solving the control problem in the prior art and improving the purity and repeatability of the material.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-02-14
- Publication Date
- 2026-04-07
AI Technical Summary
Existing technologies struggle to effectively control molecular assembly structures on metal surfaces, especially lacking effective control methods without introducing strong chemical reactions.
Alkali metal salts were co-deposited with tripyridine tricarboxylic acid molecules on the surface of a metal single crystal under vacuum. The molecular assembly structure was then controlled by observing the results using a low-temperature scanning tunneling microscope and performing stepwise annealing.
It enables precise control of molecular assembly structures on metal surfaces, improves material purity and repeatability, provides atomic-level resolution characterization capabilities, and avoids the introduction of impurities and side reactions.
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Figure CN121800719A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of supramolecular structure chemistry, and in particular to a method for regulating molecular assembly structure on metal surfaces using alkali metal salts. Background Technology
[0002] In the fields of chemistry and materials science, the regulation of molecular structure is a key means to optimize the performance of functional materials and develop novel materials. Traditional regulation methods mainly rely on the reconstruction of chemical bonds, modification of functional groups, or the effects of external physical fields (such as heat, light, and electricity). However, with the development of surface and interface science, more and more studies have shown that the behavior of molecules on surfaces is not only controlled by chemical bonds, but also influenced by multiple factors such as intermolecular forces, surface geometry, and electronic interactions. In particular, the fine regulation of the surface microenvironment has become a research hotspot in areas such as molecular self-assembly, adsorption configuration regulation, and surface reaction pathway optimization on metal surfaces.
[0003] Alkali metal salts, such as sodium chloride (NaCl) and potassium chloride (KCl), are generally considered inert or highly stable inorganic salts in macroscopic chemical reactions because their low chemical reactivity under normal conditions makes them unsuitable as reactants or structure modifiers to directly participate in changes in molecular structure. However, in the field of surface science at the microscopic scale, alkali metal salts exhibit unique regulatory capabilities. Studies have shown that alkali metal salts can form ordered assembly structures on metal surfaces, thereby influencing the adsorption mode, orientation, arrangement, and intermolecular interactions of molecules through electrostatic interactions, van der Waals forces, and dipole-dipole interactions. This mechanism provides a new approach to regulating molecular structure without introducing strong chemical reactions. Summary of the Invention
[0004] The purpose of this invention is to provide a method for regulating molecular assembly structure on metal surfaces using alkali metal salts.
[0005] To achieve effective control over the molecular assembly structure on a metal surface, this invention provides a method for controlling the molecular assembly structure on a metal surface using alkali metal salts, comprising the following steps.
[0006] S1: In a vacuum environment, the precursor molecules are first placed in an organic molecule evaporation source for heating. After the precursor molecules sublimate, they are deposited on the metal single crystal surface at room temperature.
[0007] S2: Observe the self-assembly structure of precursor molecules on a metal single crystal using a low-temperature scanning tunneling microscope, and perform stepwise annealing tests until the precursor molecules form an ordered assembly structure on the surface of the metal single crystal. S3: In a vacuum environment, precursor molecules are first deposited on the surface of a metal single crystal, and then R is deposited into it. Cl molecules; S4: Observation of precursor molecules and R on metal single crystals using a low-temperature scanning tunneling microscope. The blended structure of Cl molecules was analyzed using stepwise annealing tests to observe the precursor molecules and R on the surface of the metal single crystal. The changes in the blending assembly structure of Cl molecules at annealing temperatures; it was found that on the surface of a single metal crystal, after annealing, R... Cl molecules can regulate the assembly structure of precursor molecules on metal surfaces.
[0008] Where R represents Na and K.
[0009] According to the present invention, a method for regulating the molecular assembly structure on a metal surface by means of an alkali metal salt is provided. In steps S3 and S4, R is Na. The structure regulation of precursor molecules can be achieved by observing the annealed metal surface in a low-temperature scanning tunneling microscope.
[0010] According to the present invention, a method for regulating the molecular assembly structure on a metal surface by means of alkali metal salts is provided. In steps S3 and S4, R is K. The structure regulation of precursor molecules can be achieved by observing the annealed metal surface in a low-temperature scanning tunneling microscope.
[0011] According to the present invention, a method for regulating molecular assembly structure on a metal surface by means of alkali metal salt is provided, wherein the precursor molecule is a tripyridine tricarboxylic acid molecule.
[0012] According to the present invention, a method for regulating molecular assembly structure on a metal surface by means of alkali metal salt is provided, wherein the metal single crystal surface is a gold Au(111) surface, a silver Ag(111) surface, or a copper Cu(111) surface.
[0013] According to the present invention, a method for regulating the molecular assembly structure on a metal surface by means of alkali metal salts is provided, wherein the temperature of the stepwise annealing is controlled at around 200 ℃ to 300 ℃.
[0014] According to the present invention, a method for regulating molecular assembly structure on a metal surface by means of alkali metal salt is provided, wherein the self-assembled structure of the precursor molecules and the coverage of the precursor molecules and alkali metal salt co-deposited on the metal single crystal surface are both greater than 0.5 monolayers.
[0015] According to the present invention, a method for regulating molecular assembly structure on a metal surface using alkali metal salts is provided, wherein the vacuum degree of the vacuum environment is less than or equal to 5 × 10⁻⁶. -10 mbar.
[0016] According to the method for regulating molecular assembly structure on a metal surface by means of alkali metal salt provided by the present invention, the scanning temperature of the low-temperature scanning tunneling microscope in steps S2 and S4 is 78 ~ 79 K.
[0017] The above-described one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects: This invention provides an innovative method for controlling the molecular assembly structure on a metal surface using alkali metal salts. The method involves depositing tripyridine tricarboxylic acid molecules onto a metal single-crystal surface using thermal evaporation under ultra-vacuum conditions. Subsequently, an alkali metal salt is deposited onto the metal single-crystal surface. Through further annealing, the alkali metal salt molecules on the metal surface achieve control over the organic molecular structure through intermolecular forces. This structure is characterized at atomic resolution using low-temperature scanning tunneling microscopy (LT-STM), revealing an ordered molecular structure arrangement that differs from the self-assembled structure of pure organic molecules.
[0018] Compared with the prior art, the beneficial effects of the present invention are as follows: The synthesis environment of this invention is reliable, employing ultra-vacuum and low-temperature environments, which avoids impurities and side reactions that may be introduced in traditional chemical reactions, thereby improving the purity and performance of the materials.
[0019] This invention offers strong controllability in depositing terpyridine tricarboxylic acid molecules and alkali metal salts. By controlling the thermal evaporation deposition time and annealing temperature and time, the deposition amount and reaction rate of terpyridine tricarboxylic acid molecules and alkali metal salts on the surface of a metal single crystal can be precisely controlled, achieving accurate control over the molecular structure.
[0020] This invention achieves structural control of the tripyridine tricarboxylic acid molecule by selectively using alkali metal salts and metal single crystal surfaces, and has strong reproducibility. This invention offers high observability, enabling visualization studies of changes in molecular structure regulation by alkali metal salts at the atomic level using a low-temperature scanning tunneling microscope, providing theoretical support for the subsequent fine-tuning of the surface microenvironment.
[0021] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description
[0022] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0023] Figure 1This is an image of the self-assembled structure of TATP tripyridine tricarboxylic acid molecules deposited on the surface of an Au(111) single crystal and annealed at 300 °C, in a method for regulating molecular assembly structure on a metal surface by alkali metal salts provided by the present invention.
[0024] Figure 2 This is an image of the assembly structure of terpyridine tricarboxylic acid molecules and alkali metal NaCl co-deposited onto the surface of Au(111) single crystal and annealed at 320 ℃ and 340 ℃, in a method for regulating molecular assembly structure on a metal surface by alkali metal salts provided by the present invention.
[0025] Figure 3 This is an image of the assembly structure of terpyridine tricarboxylic acid molecules and alkali metal KCl co-deposited onto the surface of an Au(111) single crystal and annealed at 230 °C, in a method for regulating molecular assembly structure on a metal surface by alkali metal salts provided by the present invention.
[0026] Figure 4 This is an image of the self-assembled structure of terpyridine tricarboxylic acid molecules deposited on the surface of an Ag(111) single crystal and annealed at 200 °C, as provided in this invention, in a method for regulating molecular assembly structure on a metal surface by using alkali metal salts.
[0027] Figure 5 This is an image of the assembly structure of terpyridine tricarboxylic acid molecules and alkali metal NaCl co-deposited onto the surface of Ag(111) single crystal and annealed at 300 °C, in a method for regulating molecular assembly structure on a metal surface by means of alkali metal salts provided by the present invention.
[0028] Figure 6 This is an image of the assembly structure of terpyridine tricarboxylic acid molecules and alkali metal KCl co-deposited onto the surface of Ag(111) single crystal and annealed at 300 ℃ and 350 ℃, in a method for controlling molecular assembly structure on a metal surface by alkali metal salts provided by the present invention.
[0029] Figure 7 This is an image of the self-assembled structure of terpyridine tricarboxylic acid molecules deposited on a Cu(111) single crystal surface and annealed at 200 °C, in a method for regulating molecular assembly structure on a metal surface by alkali metal salts provided by the present invention.
[0030] Figure 8 This is an image of the assembly structure of terpyridine tricarboxylic acid molecules and alkali metal NaCl co-deposited onto the surface of a Cu(111) single crystal and annealed at 200 °C, in a method for regulating molecular assembly structure on a metal surface by means of alkali metal salts provided by the present invention.
[0031] Figure 9This is an image of the assembly structure of terpyridine tricarboxylic acid molecules and alkali metal KCl co-deposited onto the surface of Cu(111) single crystal and annealed at 200 °C, in a method for regulating molecular assembly structure on a metal surface by alkali metal salts provided by the present invention.
[0032] Figure 10 This is a schematic diagram of the TATP assembly process. Detailed Implementation
[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. The following embodiments are used to illustrate this invention but should not be used to limit its scope.
[0034] In the description of the embodiments of the present invention, it should be noted that the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing the embodiments of the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the embodiments of the present invention. In addition, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.
[0035] In the description of the embodiments of the present invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "connected" and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in the embodiments of the present invention based on the specific circumstances.
[0036] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms are not limited to the same embodiment or example, and the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Furthermore, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.
[0037] The following is in conjunction with the accompanying drawings. Figures 1 to 9 The embodiments further illustrate the method provided by the present invention for regulating molecular assembly structure on metal surfaces by means of alkali metal salts. Figure 10 This is a schematic diagram of the TATP assembly process.
[0038] Example 1 S1: In a vacuum environment, the precursor molecules are first placed in an organic molecule evaporation source for heating. After the precursor molecules sublimate, they are deposited on the metal single crystal surface at room temperature. Tripyridine tricarboxylic acid molecules were placed in a crucible, and then the crucible was placed in an organic molecule evaporation source. Au(111) single crystal and organic molecule evaporation source were placed in an ultra-high vacuum chamber. The organic molecule evaporation source was heated, and the tripyridine tricarboxylic acid molecules underwent thermal sublimation at 155 °C and were deposited on the surface of Au(111) single crystal at room temperature for 5 minutes.
[0039] S2: Observe the self-assembly structure of precursor molecules on a metal single crystal using a low-temperature scanning tunneling microscope, and perform stepwise annealing tests until the precursor molecules form an ordered assembly structure on the surface of the metal single crystal. The self-assembled structure of terpyridine tricarboxylic acid molecules on Au(111) single crystals was observed using a low-temperature scanning tunneling microscope. The molecules deposited on the surface of Au(111) single crystals at room temperature did not form an ordered assembly structure. Stepwise annealing of the Au(111) single crystals with deposited terpyridine tricarboxylic acid molecules at 100 °C, 200 °C, 300 °C, and 350 °C revealed that annealing at 300 °C yielded an ordered molecular structure, with the molecules arranged in a face-to-face dimer, such as... Figure 1 As shown.
[0040] S3: In a vacuum environment, precursor molecules are first deposited on the surface of a metal single crystal, and then R is deposited into it. Cl molecules; Where R is Na.
[0041] Tripyridine tricarboxylic acid (TPCA) molecules and NaCl molecules were placed in separate crucibles, which were then positioned at different locations within an organic molecular evaporation source. An Au(111) single crystal and the organic molecular evaporation source were placed in an ultra-high vacuum chamber. The crucible containing the TPCA molecules in the organic molecular evaporation source was heated, causing the TPCA molecules to sublimate at 155 °C and deposit onto the room-temperature Au(111) single crystal surface for 5 minutes. The crucible containing the NaCl molecules in the organic molecular evaporation source was then heated, causing the NaCl molecules to sublimate at 450 °C and deposit onto the already deposited TPCA molecules on the room-temperature Au(111) single crystal surface for 1 minute and 30 seconds.
[0042] S4: Observation of precursor molecules and R on metal single crystals using a low-temperature scanning tunneling microscope. The blended structure of Cl molecules was analyzed using stepwise annealing tests to observe the precursor molecules and R on the surface of the metal single crystal. The changes in the blending assembly structure of Cl molecules at annealing temperatures; it was found that on the surface of a single metal crystal, after annealing, R... Cl molecules can regulate the assembly structure of precursor molecules on metal surfaces.
[0043] Where R is Na.
[0044] Observation of the blended structure of terpyridine tricarboxylic acid molecules and NaCl molecules on Au(111) single crystals using low-temperature scanning tunneling microscopy revealed that no ordered assembly structure was formed. Stepwise annealing of Au(111) single crystals co-deposited with terpyridine tricarboxylic acid and NaCl molecules at 100 ℃, 200 ℃, 300 ℃, 320 ℃, and 340 ℃ showed that annealing at 320 ℃ and 340 ℃ yielded ordered supramolecular nanonetwork structures, such as... Figure 2 As shown.
[0045] Example 2 S3: In a vacuum environment, precursor molecules are first deposited on the surface of a metal single crystal, and then R is deposited into it. Cl molecules; Where R is K.
[0046] Tripyridine tricarboxylic acid (TPCA) molecules and KCl molecules were placed in separate crucibles, which were then positioned at different locations within an organic molecular evaporation source. An Au(111) single crystal and the organic molecular evaporation source were placed in an ultra-high vacuum chamber. The crucible containing the TPCA molecules in the organic molecular evaporation source was heated, causing the TPCA molecules to sublimate at 155 °C and deposit onto the room-temperature Au(111) single crystal surface for 5 minutes. The crucible containing the KCl molecules in the organic molecular evaporation source was then heated, causing the KCl molecules to sublimate at 310 °C and deposit onto the already deposited TPCA molecules on the room-temperature Au(111) single crystal surface for 3 minutes.
[0047] S4: Observation of precursor molecules and R on metal single crystals using a low-temperature scanning tunneling microscope. The blended structure of Cl molecules was analyzed using stepwise annealing tests to observe the precursor molecules and R on the surface of the metal single crystal. The changes in the blending assembly structure of Cl molecules at annealing temperatures; it was found that on the surface of a single metal crystal, after annealing, R... Cl molecules can regulate the assembly structure of precursor molecules on metal surfaces.
[0048] Where R is K.
[0049] Observation of the blended structure of terpyridine tricarboxylic acid (TATP) and KCl molecules on Au(111) single crystals using a low-temperature scanning tunneling microscope revealed that no ordered assembly structure was formed. Stepwise annealing of the Au(111) single crystals co-deposited with TATP and KCl molecules at 100 °C, 200 °C, 230 °C, 250 °C, and 300 °C showed that annealing at 230 °C yielded an ordered TATP-KCl assembly structure, as shown in the figure. Figure 3 As shown.
[0050] Example 3 S1: In a vacuum environment, the precursor molecules are first placed in an organic molecule evaporation source for heating. After the precursor molecules sublimate, they are deposited on the metal single crystal surface at room temperature. Tripyridine tricarboxylic acid molecules were placed in a crucible, and then the crucible was placed in an organic molecule evaporation source. The Ag(111) single crystal and the organic molecule evaporation source were placed in an ultra-high vacuum chamber. The organic molecule evaporation source was heated, and the tripyridine tricarboxylic acid molecules underwent thermal sublimation at 155 °C and were deposited on the surface of the Ag(111) single crystal at room temperature for 5 minutes.
[0051] S2: Observe the self-assembly structure of precursor molecules on a metal single crystal using a low-temperature scanning tunneling microscope, and perform stepwise annealing tests until the precursor molecules form an ordered assembly structure on the surface of the metal single crystal. The self-assembled structure of terpyridine tricarboxylic acid molecules on Ag(111) single crystals was observed using a low-temperature scanning tunneling microscope. The molecules, deposited on the surface of Ag(111) single crystals at room temperature, did not form an ordered assembly structure. Stepwise annealing of the Ag(111) single crystals with deposited terpyridine tricarboxylic acid molecules at 100 °C, 200 °C, 300 °C, and 350 °C revealed that annealing at 200 °C yielded an ordered molecular structure, with the molecules arranged back-to-back as dimers, such as... Figure 4 As shown.
[0052] S3: In a vacuum environment, precursor molecules are first deposited on the surface of a metal single crystal, and then R is deposited into it. Cl molecules; Where R is Na.
[0053] Tripyridine tricarboxylic acid (TPCA) molecules and NaCl molecules were placed in separate crucibles, which were then positioned at different locations within an organic molecular evaporation source. An Ag(111) single crystal and the organic molecular evaporation source were placed in an ultra-high vacuum chamber. The crucible containing the TPCA molecules in the organic molecular evaporation source was heated, causing the TPCA molecules to sublimate at 155 °C and deposit onto the room-temperature Ag(111) single crystal surface for 5 minutes. The crucible containing the NaCl molecules in the organic molecular evaporation source was then heated, causing the NaCl molecules to sublimate at 450 °C and deposit onto the room-temperature Ag(111) single crystal surface where the TPCA molecules had already been deposited for 1 minute and 30 seconds.
[0054] S4: Observation of precursor molecules and R on metal single crystals using a low-temperature scanning tunneling microscope. The blended structure of Cl molecules was analyzed using stepwise annealing tests to observe the precursor molecules and R on the surface of the metal single crystal. The changes in the blending assembly structure of Cl molecules at annealing temperatures; it was found that on the surface of a single metal crystal, after annealing, R... Cl molecules can regulate the assembly structure of precursor molecules on metal surfaces.
[0055] Where R is Na.
[0056] Observation of the blended structure of terpyridine tricarboxylic acid (TPAT) and NaCl molecules on Ag(111) single crystals using a low-temperature scanning tunneling microscope revealed that no ordered assembly structure was formed. Stepwise annealing of the Ag(111) single crystals co-deposited with TPAT and NaCl molecules at 100 °C, 200 °C, 300 °C, 350 °C, and 400 °C showed that annealing at 300 °C yielded an ordered TATP-NaCl zigzag chain structure, such as... Figure 5 As shown.
[0057] Example 4 S3: In a vacuum environment, precursor molecules are first deposited on the surface of a metal single crystal, and then R is deposited into it. Cl molecules; Where R is K.
[0058] Tripyridine tricarboxylic acid (TPCA) molecules and KCl molecules were placed in separate crucibles, which were then positioned at different locations within an organic molecular evaporation source. An Ag(111) single crystal and the organic molecular evaporation source were placed in an ultra-high vacuum chamber. The crucible containing the TPCA molecules in the organic molecular evaporation source was heated, causing the TPCA molecules to sublimate at 155 °C and deposit onto the room-temperature Ag(111) single crystal surface for 5 minutes. The crucible containing the KCl molecules in the organic molecular evaporation source was then heated, causing the KCl molecules to sublimate at 310 °C and deposit onto the room-temperature Ag(111) single crystal surface where the TPCA molecules had already been deposited for 3 minutes.
[0059] S4: Observation of precursor molecules and R on metal single crystals using a low-temperature scanning tunneling microscope. The blended structure of Cl molecules was analyzed using stepwise annealing tests to observe the precursor molecules and R on the surface of the metal single crystal. The changes in the blending assembly structure of Cl molecules at annealing temperatures; it was found that on the surface of a single metal crystal, after annealing, R... Cl molecules can regulate the assembly structure of precursor molecules on metal surfaces.
[0060] Where R is K.
[0061] Observation of the blended structure of terpyridine tricarboxylic acid (TATP) and KCl molecules on Ag(111) single crystals using a low-temperature scanning tunneling microscope revealed that no ordered assembly structure was formed. Stepwise annealing of the Ag(111) single crystals co-deposited with TATP and KCl molecules at 100 °C, 200 °C, 300 °C, 350 °C, and 400 °C showed that at 300 °C, an ordered TATP-KCl zigzag chain assembly structure was obtained, and at 350 °C, a Sierpinski triangular structure was obtained, such as... Figure 6 As shown.
[0062] Example 5 S1: In a vacuum environment, the precursor molecules are first placed in an organic molecule evaporation source for heating. After the precursor molecules sublimate, they are deposited on the metal single crystal surface at room temperature. Tripyridine tricarboxylic acid molecules were placed in a crucible, and then the crucible was placed in an organic molecular evaporation source. The Cu(111) single crystal and the organic molecular evaporation source were placed in an ultra-high vacuum chamber. The organic molecular evaporation source was heated, and the tripyridine tricarboxylic acid molecules underwent thermal sublimation at 155 °C and were deposited on the surface of the Cu(111) single crystal at room temperature for 5 minutes.
[0063] S2: Observe the self-assembly structure of precursor molecules on a metal single crystal using a low-temperature scanning tunneling microscope, and perform stepwise annealing tests until the precursor molecules form an ordered assembly structure on the surface of the metal single crystal. The self-assembled structure of terpyridine tricarboxylic acid molecules on Cu(111) single crystals was observed using a low-temperature scanning tunneling microscope. The molecules deposited on the surface of Cu(111) single crystals at room temperature did not form an ordered assembly structure. Stepwise annealing of the Cu(111) single crystals with deposited terpyridine tricarboxylic acid molecules at 100 °C, 200 °C, 300 °C, and 350 °C revealed that annealing at 200 °C yielded an ordered molecular structure, with the molecules forming a chiral trimer structure, such as... Figure 7 As shown.
[0064] S3: In a vacuum environment, precursor molecules are first deposited on the surface of a metal single crystal, and then R is deposited into it. Cl molecules; Where R is Na.
[0065] Tripyridine tricarboxylic acid (TPCA) molecules and NaCl molecules were placed in separate crucibles, which were then positioned at different locations within an organic molecular evaporation source. A Cu(111) single crystal and the organic molecular evaporation source were placed in an ultra-high vacuum chamber. The crucible containing the TPCA molecules in the organic molecular evaporation source was heated, causing the TPCA molecules to sublimate at 155 °C and deposit onto the room-temperature Cu(111) single crystal surface for 5 minutes. The crucible containing the NaCl molecules in the organic molecular evaporation source was then heated, causing the NaCl molecules to sublimate at 450 °C and deposit onto the room-temperature Cu(111) single crystal surface where the TPCA molecules had already been deposited for 1 minute and 30 seconds.
[0066] S4: Observation of precursor molecules and R on metal single crystals using a low-temperature scanning tunneling microscope. The blended structure of Cl molecules was analyzed using stepwise annealing tests to observe the precursor molecules and R on the surface of the metal single crystal. The changes in the blending assembly structure of Cl molecules at annealing temperatures; it was found that on the surface of a single metal crystal, after annealing, R... Cl molecules can regulate the assembly structure of precursor molecules on metal surfaces.
[0067] Where R is Na.
[0068] Observation of the blended structure of terpyridine tricarboxylic acid (TATP) and NaCl molecules on Cu(111) single crystals using a low-temperature scanning tunneling microscope revealed that no ordered assembly structure was formed. Stepwise annealing of Cu(111) single crystals co-deposited with TATP and NaCl molecules at 100 °C, 200 °C, 300 °C, and 350 °C showed that annealing at 200 °C yielded ordered TATP-NaCl honeycomb network structures, rectangular structures, and yin-yang fish-shaped structures, such as... Figure 8 As shown.
[0069] Example 6 S3: In a vacuum environment, precursor molecules are first deposited on the surface of a metal single crystal, and then R is deposited into it. Cl molecules; Where R is K.
[0070] Tripyridine tricarboxylic acid (TPCA) molecules and KCl molecules were placed in separate crucibles, which were then positioned at different locations within an organic molecular evaporation source. A Cu(111) single crystal and the organic molecular evaporation source were placed in an ultra-high vacuum chamber. The crucible containing the TPCA molecules in the organic molecular evaporation source was heated, causing the TPCA molecules to sublimate at 155 °C and deposit onto the room-temperature Cu(111) single crystal surface for 5 minutes. The crucible containing the KCl molecules in the organic molecular evaporation source was then heated, causing the KCl molecules to sublimate at 310 °C and deposit onto the room-temperature Cu(111) single crystal surface where the TPCA molecules had already been deposited for 3 minutes.
[0071] S4: Observation of precursor molecules and R on metal single crystals using a low-temperature scanning tunneling microscope. The blended structure of Cl molecules was analyzed using stepwise annealing tests to observe the precursor molecules and R on the surface of the metal single crystal. The changes in the blending assembly structure of Cl molecules at annealing temperatures; it was found that on the surface of a single metal crystal, after annealing, R... Cl molecules can regulate the assembly structure of precursor molecules on metal surfaces.
[0072] Where R is K.
[0073] Observation of the blended structure of terpyridine tricarboxylic acid (TATP) and KCl molecules on Cu(111) single crystals using a low-temperature scanning tunneling microscope revealed that no ordered assembly structure was formed. Stepwise annealing of the Cu(111) single crystals co-deposited with TATP and KCl molecules at 100 °C, 200 °C, 300 °C, and 350 °C showed that an ordered TATP-KCl windmill-like structure could be obtained at 200 °C, as shown in the image. Figure 9As shown.
[0074] In summary, this invention protects a method for controlling the molecular assembly structure on a metal surface using alkali metal salts. Under ultra-high vacuum, terpyridine tricarboxylic acid molecules are deposited onto different metal single-crystal surfaces via thermal evaporation. Alkali metal salt molecules are then deposited on top of this, achieving co-deposition of the two types of molecules. Stepwise annealing allows the alkali metal salt molecules to form different, regularly occurring structures on each single crystal through intermolecular interactions, thereby enabling the control of the terpyridine tricarboxylic acid molecular assembly structure and achieving atomic-level resolution characterization.
[0075] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for regulating molecular assembly structure on a metal surface using alkali metal salts, characterized in that, Structure regulation is achieved by depositing alkali metal salts onto the surface of a metal single crystal on which precursor molecules have already been deposited, followed by annealing. The process includes the following steps: S1: In a vacuum environment, the precursor molecules are first placed in an organic molecule evaporation source for heating. After the precursor molecules sublimate, they are deposited on the metal single crystal surface at room temperature. S2: Observe the self-assembly structure of precursor molecules on a metal single crystal using a low-temperature scanning tunneling microscope, and perform stepwise annealing tests until the precursor molecules form an ordered assembly structure on the surface of the metal single crystal. S3: In a vacuum environment, precursor molecules are first deposited on the surface of a metal single crystal, and then R is deposited into it. Cl molecules; S4: Observation of precursor molecules and R on metal single crystals using a low-temperature scanning tunneling microscope. The blended structure of Cl molecules was analyzed using stepwise annealing tests to observe the precursor molecules and R on the surface of the metal single crystal. The changes in the blending assembly structure of Cl molecules at annealing temperatures; it was found that on the surface of a single metal crystal, after annealing, R... Cl molecules regulate the assembly structure of precursor molecules on metal surfaces; Where R represents Na and K.
2. The method for regulating molecular assembly structure on a metal surface using alkali metal salts according to claim 1, characterized in that, In steps S3 and S4, R is Na, and the structure of precursor molecules can be regulated by observing the annealed metal surface in a low-temperature scanning tunneling microscope.
3. The method for regulating molecular assembly structure on a metal surface using alkali metal salts according to claim 1, characterized in that, In steps S3 and S4, R is K, and the structure of precursor molecules can be controlled by observing the annealed metal surface in a low-temperature scanning tunneling microscope.
4. The method for regulating molecular assembly structure on a metal surface using alkali metal salts according to claim 1, characterized in that, The precursor molecule is a tripyridine tricarboxylic acid molecule.
5. The method for regulating molecular assembly structure on a metal surface using alkali metal salts according to claim 1, characterized in that, The surface of the metal single crystal is a gold Au(111) surface, a silver Ag(111) surface, or a copper Cu(111) surface.
6. The method for regulating molecular assembly structure on a metal surface using alkali metal salts according to claim 1, characterized in that, The temperature for gradual annealing is controlled between 200 ℃ and 300 ℃.
7. The method for regulating molecular assembly structure on a metal surface using alkali metal salts according to claim 1, characterized in that, The self-assembled structure of the precursor molecules and the coverage of the precursor molecules and alkali metal salt co-deposited on the surface of the metal single crystal are both greater than 0.5 monolayers.
8. The method for regulating molecular assembly structure on a metal surface using alkali metal salts according to claim 1, characterized in that, The vacuum level of the vacuum environment is less than or equal to 5 × 10⁻⁶. -10 mbar.
9. The method for regulating molecular assembly structure on a metal surface using alkali metal salts according to claim 1, characterized in that, The scanning temperature of the low-temperature scanning tunneling microscope described in steps S2 and S4 is 78 ~ 79 K.