Nanometer geometric quantity standard template and preparation method and application thereof

Abstract

The invention belongs to the technical field of nanometer testing, and provides a nanometer geometric quantity standard sample plate and a preparation method and application thereof. The nanometer geometric quantity standard sample plate comprises a substrate and a nanometer periodic structure two-dimensional supramolecular film attached to the substrate, and the nanometer periodic structure two-dimensional supramolecular film is obtained by self-assembly of 5, 5 '-(9H-fluorene-2, 7-diyl) diphthalic acid and 1, 2-bis (4-pyridyl) ethane. The nanometer geometric quantity standard sample plate provided by the invention has excellent precision. The invention also provides a preparation method of the nanometer geometric quantity standard sample plate, self-assembly is to prepare the nanometer periodic structure two-dimensional supramolecular film from bottom to top, and the morphology, size and performance of the nanometer structure can be more accurately controlled from bottom to top, so that the nanometer periodic structure two-dimensional supramolecular film has high precision and high performance; the length, the line width and the duty ratio of the nanometer geometric quantity structure can be modulated by regulating and controlling the self-assembly condition.

Description

Technical Field

[0001] The present invention relates to the field of nanometer testing technology, and in particular to a nanometer geometric quantity standard sample plate and a preparation method and application thereof. Background Art

[0002] As the process nodes of integrated circuits continue to shrink, chip performance is increasingly affected by the size of nano-geometric quantities, which puts forward new requirements for the high precision and high stability of nano-measurement. Traditional nano-measurement technology is mainly laser interferometry, which measures the changes in interference fringes to infer the tiny displacement or length change of the measured object. In laser interferometry, due to the influence of various factors (such as errors in optical components, signal distortion, etc.), nonlinear errors may occur, affecting the accuracy and stability of the measurement. In addition, laser interferometry is sensitive to environmental conditions (such as temperature, humidity, vibration, etc.), and it is necessary to measure under relatively stable environmental conditions and take corresponding measures to reduce the impact of environmental factors, and the maintenance cost is high. Therefore, laser interferometry does not have advantages in the accuracy and stability of nano-measurement and the measurement cost.

[0003] In 2018, the International Bureau of Weights and Measures stipulated a method for reproducing the definition of the silicon lattice constant as the international unit meter. In addition to being traced back to the laser wavelength, the nano-geometric standard sample can also be traced back to the atomic-scale silicon lattice constant, which improves the accuracy of the value of the nano-geometric standard sample and gives it a huge advantage in nano-metrology traceability calibration. At present, the main methods for preparing nano-geometric standard samples include photolithography technology, electron beam exposure technology, deposition and etching technology, etc. The precision of the nano-geometric standard samples prepared by the above methods needs to be further improved. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a nano-geometric quantity standard sample and its preparation method and application. The nano-geometric quantity standard sample provided by the present invention has high precision.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The invention provides a nano-geometric quantity standard sample, comprising a substrate and a nano-periodic structure two-dimensional supramolecular film attached to the substrate, wherein the nano-periodic structure two-dimensional supramolecular film is obtained by self-assembly of 5,5'-(9H-fluorene-2,7-diyl)diisophthalic acid and 1,2-bis(4-pyridyl)ethane.

[0007] Preferably, the substrate is made of highly oriented pyrolysis graphite, gold or copper.

[0008] The present invention also provides a method for preparing the nano-geometric quantity standard sample described in the above technical solution, comprising the following steps:

[0009] providing a substrate;

[0010] 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane are self-assembled on the substrate to obtain the nano-geometric quantity standard sample.

[0011] Preferably, the self-assembly of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane on the substrate comprises the following steps: sequentially dropping a 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution and a 1,2-bis(4-pyridyl)ethane solution on the substrate for self-assembly.

[0012] Preferably, the self-assembly of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane on the substrate comprises the following steps: sequentially dropping 1,2-bis(4-pyridyl)ethane solution and 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution on the substrate for self-assembly.

[0013] Preferably, the self-assembly of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane on the substrate comprises the following steps: dropwise adding a 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid / 1,2-bis(4-pyridyl)ethane mixed solution on the substrate for self-assembly.

[0014] Preferably, in the mixed system formed by the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution and the 1,2-bis(4-pyridyl)ethane solution, the molar ratio of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid to 1,2-bis(4-pyridyl)ethane is 1 to 1.5:1, the concentration of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid is 0.0005 to 0.002 mol / mL, and the pH value is 6 to 7.5.

[0015] Preferably, in the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid / 1,2-bis(4-pyridyl)ethane mixed solution, the molar ratio of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid to 1,2-bis(4-pyridyl)ethane is 1-1.5:1, the concentration of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid is 0.0005-0.002 mol / mL, and the pH value is 6-7.5.

[0016] Preferably, the substrate is mechanically peeled off before use.

[0017] The present invention also provides the use of the nano-geometric quantity standard sample described in the above technical solution or the nano-geometric quantity standard sample prepared by the preparation method described in the above technical solution in nano-measurement.

[0018] The invention provides a nano-geometric quantity standard sample.

[0019] The invention forms a nano-periodic structure two-dimensional supramolecular film on a substrate by self-assembly of 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid and 1,2-bis(4-pyridyl) ethane. The nano-periodic structure two-dimensional supramolecular film formed by self-assembly has excellent precision.

[0020] The present invention also provides a method for preparing the nano-geometric standard template described in the above technical solution. The self-assembly is a bottom-up preparation of a two-dimensional supramolecular film with a nano-periodic structure. The bottom-up method can more accurately control the morphology, size and performance of the nano-structure, so that the two-dimensional supramolecular film with a nano-periodic structure has high precision and high performance. By regulating the conditions of self-assembly, the length, line width and duty cycle of the nano-geometric structure can be modulated. In addition, the preparation method of the present invention obtains a cross-scale nano-geometric structure. In addition, the preparation method of the present invention has the advantages of simple operation, low cost and easy scale-up, and is suitable for large-scale production applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 A flowchart of the first self-assembly provided by the present invention;

[0022] Figure 2 The nano-grid STM image of the nano-periodic structure two-dimensional supramolecular film obtained in Example 1;

[0023] In the figure, 1-substrate, 2-disordered structure two-dimensional supramolecular film, 3-nano-periodic structure two-dimensional supramolecular film. DETAILED DESCRIPTION

[0024] The invention provides a nano-geometric quantity standard sample, comprising a substrate and a nano-periodic structure two-dimensional supramolecular film attached to the substrate, wherein the nano-periodic structure two-dimensional supramolecular film is obtained by self-assembly of 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid and 1,2-bis(4-pyridyl)ethane.

[0025] Unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.

[0026] The nano-geometric quantity standard sample provided by the present invention comprises a substrate, and the material of the substrate preferably comprises highly oriented pyrolysis graphite, gold or copper, and more preferably is highly oriented pyrolysis graphite.

[0027] The nano-geometric standard template provided by the present invention comprises a nano-periodic structure two-dimensional supramolecular film attached to the substrate, wherein the nano-periodic structure two-dimensional supramolecular film is obtained by self-assembly of 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid and 1,2-bis(4-pyridyl)ethane. In the present invention, the thickness of the nano-periodic structure two-dimensional supramolecular film is preferably 0.3 to 1 nm. In the present invention, the molar ratio of 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid and 1,2-bis(4-pyridyl)ethane in the nano-periodic structure two-dimensional supramolecular film is preferably 1 to 1.5:1, and specifically preferably 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1 or 1.5:1.

[0028] In the present invention, the nanoperiodic structure two-dimensional supramolecular film is preferably attached to any surface of the substrate. In the present invention, the nanoperiodic structure two-dimensional supramolecular film is attached to any surface of the substrate, so that any position of the nanogeometric standard sample can be used without positioning.

[0029] In the present invention, the nanoperiodic structure of the two-dimensional supramolecular film preferably includes a nanowire width structure or a nanogrid structure.

[0030] In the present invention, the nano-periodic structure two-dimensional supramolecular film preferably has a nano-geometric structure across a large range of scales; the nano-geometric structure preferably includes step height, length, pitch and line width.

[0031] The invention forms a nano-periodic structure two-dimensional supramolecular film on a substrate by self-assembly of 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid and 1,2-bis(4-pyridyl) ethane. The nano-periodic structure two-dimensional supramolecular film formed by self-assembly has excellent precision.

[0032] The present invention also provides a method for preparing the nano-geometric quantity standard sample described in the above technical solution, comprising the following steps:

[0033] providing a substrate;

[0034] 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane are self-assembled on the substrate to obtain the nano-geometric quantity standard sample.

[0035] The present invention provides a substrate. In the present invention, the material of the substrate is preferably consistent with the above technical solution, which will not be repeated here. Before using the substrate, the present invention preferably also includes mechanical peeling, and the present invention does not specifically limit the parameters of the mechanical peeling.

[0036] After providing the substrate, the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane of the present invention are self-assembled on the substrate to obtain the nano-geometric quantity standard sample.

[0037] In the present invention, the self-assembly of 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid and 1,2-bis(4-pyridyl)ethane on the substrate preferably comprises the following steps: sequentially dropping a 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid solution and a 1,2-bis(4-pyridyl)ethane solution on the substrate to perform self-assembly (referred to as the first self-assembly). In the present invention, the solvent of the 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid solution is preferably a polar solvent, and the polar solvent preferably includes one or more of heptanoic acid, octylbenzene and furan, and more preferably heptanoic acid. In the present invention, the concentration of the 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid solution is preferably 0.001 to 0.002 mol / mL, and specifically preferably 0.001 mol / mL, 0.0015 mol / mL or 0.002 mol / mL. In the present invention, the amount of the 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid solution added is preferably 1 to 2 μL / cm 2 , preferably 1 μL / cm 2 After the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution is added dropwise, the 1,2-bis(4-pyridyl)ethane solution is preferably added dropwise directly.

[0038] In the present invention, the solvent of the 1,2-bis(4-pyridyl)ethane solution is preferably consistent with the solvent of the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution, which will not be repeated here. In the present invention, the concentration of the 1,2-bis(4-pyridyl)ethane solution is preferably 0.001 to 0.002 mol / mL, specifically preferably 0.001 mol / mL, 0.0015 mol / mL or 0.002 mol / mL. In the present invention, the amount of the 1,2-bis(4-pyridyl)ethane solution added is preferably 1 to 2 μL / cm 2 , preferably 1 μL / cm 2 .

[0039] In the present invention, in the mixed system formed by the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution and the 1,2-bis(4-pyridyl)ethane solution, the molar ratio of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid to 1,2-bis(4-pyridyl)ethane is preferably 1 to 1.5:1, specifically preferably 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1 or 1.5:1; the concentration of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid is preferably 0.0005 to 0.002 mol / mL, specifically preferably 0.0005 mol / mL, 0.00075 mol / mL or 0.001 mol / mL, and the pH value is preferably 6.0 to 7.5.

[0040] In the present invention, the temperature of the first self-assembly is preferably room temperature, the time is preferably 8 to 15 minutes, and more preferably 10 minutes. After the first self-assembly, the present invention preferably further comprises evaporating the solvent, and the temperature of the evaporating solvent is preferably 50 to 70°C, and more preferably 60°C; the present invention does not specifically limit the time of evaporating the solvent, as long as the solvent can be completely removed.

[0041] In the present invention, the flowchart of the first self-assembly is as follows Figure 1 As shown, specifically: first prepare 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution and 1,2-bis(4-pyridyl)ethane solution, and then mechanically peel off the substrate 1; drip 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution on the surface of the substrate 1 to form a disordered two-dimensional supramolecular film 2, and then drip 1,2-bis(4-pyridyl)ethane solution for self-assembly to obtain a nano-periodic structure two-dimensional supramolecular film 3.

[0042] In the present invention, the self-assembly of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane on the substrate preferably includes the following steps: sequentially dropping 1,2-bis(4-pyridyl)ethane solution and 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution on the substrate to perform self-assembly (referred to as the second self-assembly).

[0043] In the present invention, the solvent, concentration and drop amount of the 1,2-bis(4-pyridyl)ethane solution and the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution are preferably consistent with the above technical solution, and are not repeated here. In the present invention, in the mixed system formed by the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution and the 1,2-bis(4-pyridyl)ethane solution, the molar ratio of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane, the concentration and pH value of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid are preferably consistent with the above technical solution, and are not repeated here.

[0044] In the present invention, the temperature, time and post-treatment of the second self-assembly are preferably consistent with the above technical solution, which will not be described in detail here.

[0045] In the present invention, the self-assembly of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane on the substrate preferably includes the following steps: dropping a 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid / 1,2-bis(4-pyridyl)ethane mixed solution on the substrate to perform self-assembly (referred to as the third self-assembly). In the present invention, in the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid / 1,2-bis(4-pyridyl)ethane mixed solution, the molar ratio of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid to 1,2-bis(4-pyridyl)ethane is preferably 1 to 1.5:1, specifically preferably 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1 or 1.5:1; the concentration of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid is preferably 0.0005 to 0.002 mol / mL, specifically preferably 0.0005 mol / mL, 0.00075 mol / mL or 0.001 mol / mL; and the pH value is preferably 6.0 to 7.5.

[0046] In the present invention, the temperature, time and post-treatment of the third self-assembly are preferably consistent with the above technical solution, which will not be described in detail here.

[0047] In the present invention, self-assembly is to prepare a nanoperiodic structure two-dimensional supramolecular film from bottom to top, which can more accurately control the morphology, size and performance of the nanostructure, so that the nanoperiodic structure two-dimensional supramolecular film has high precision and high performance; by regulating the conditions of self-assembly, the length, line width and duty cycle of the nano-geometric structure can be modulated; in addition, the preparation method of the present invention obtains a cross-scale nano-geometric structure. In addition, the preparation method of the present invention has the advantages of simple operation, low cost and easy amplification, and is suitable for large-scale production and application.

[0048] The present invention also provides the use of the nano-geometric quantity standard sample described in the above technical solution or the nano-geometric quantity standard sample prepared by the preparation method described in the above technical solution in nano-measurement.

[0049] In the present invention, the application devices of the nano-geometric quantity standard sample preferably include a scanning tunneling microscope and an atomic force microscope; the nano-geometric quantity standard sample can be used for the calibration and traceability of the scanning tunneling microscope and the atomic force microscope.

[0050] The nano-geometric quantity standard sample provided by the present invention and its preparation method and application are described in detail below in conjunction with the embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0051] Example 1

[0052] 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid was dissolved in heptanoic acid to obtain a 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution having a concentration of 0.001 mol / mL.

[0053] 1,2-bis(4-pyridyl)ethane was dissolved in heptanoic acid to obtain a 1,2-bis(4-pyridyl)ethane solution with a concentration of 0.001 mol / mL.

[0054] The highly oriented cracked graphite substrate is mechanically exfoliated to prepare a clean substrate surface.

[0055] On the clean substrate surface, the 2 The 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid solution is added dropwise to cover the surface of the substrate, thereby forming a large-scale disordered structure two-dimensional supramolecular film.

[0056] On the surface of a large-scale disordered two-dimensional supramolecular film, the 21,2-bis(4-pyridyl)ethane solution was added dropwise, and self-assembly was performed for 10 minutes. After the 1,2-bis(4-pyridyl)ethane solution was added dropwise, in the obtained mixed system, the concentration of 1,2-bis(4-pyridyl)ethane was 0.0005 mol / mL, the concentration of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid was 0.0005 mol / mL, the pH value of the mixed system was 6.5, and the ambient temperature was 25°C. The solvent was removed to obtain a nano-geometric standard sample.

[0057] Figure 2 The nanogrid STM image of the nanoperiodic structure two-dimensional supramolecular film in the obtained nanogeometric standard sample is shown in Figure 2 As shown, the line width a of the grid structure in direction A is 4.55 nanometers, and the line width b in direction B is 1.90 nanometers. The line width is uniform, the structure is neat, and the periodicity is good.

[0058] Through the preparation method of the present invention, a high-precision, stable-performance, cross-scale nano one-dimensional or two-dimensional grid standard sample can be prepared on the surface of a substrate. By controlling the self-assembly, the periodicity of the geometric structure and the duty cycle can be regulated to achieve precise control of the nano one-dimensional or two-dimensional grid, which is a supplement to the existing nano one-dimensional or two-dimensional grid standard sample and promotes the rapid development of related disciplines and industries. The nano geometric standard sample prepared by the present invention is suitable for calibration and traceability of scanning tunneling microscopes, atomic force microscopes, etc.

[0059] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A nano-geometric standard sample, characterized in that: The invention comprises a substrate and a nano-periodic structure two-dimensional supramolecular film attached to the substrate. The nano-periodic structure two-dimensional supramolecular film is obtained by self-assembly of 5,5'-(9H-fluorene-2,7-diyl) diphthalic acid and 1,2-bis(4-pyridyl)ethane.

2. The nano-geometric standard sample according to claim 1, characterized in that: The substrate is made of highly oriented pyrolysis graphite, gold or copper.

3. The method for preparing the nano-geometric standard sample according to claim 1 or 2, characterized in that: The following steps are involved: providing a substrate; 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane are self-assembled on the substrate to obtain the nano-geometric quantity standard sample.

4. The preparation method according to claim 3, characterized in that: The self-assembly of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane on the substrate comprises the following steps: sequentially dropping a 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution and a 1,2-bis(4-pyridyl)ethane solution on the substrate for self-assembly.

5. The preparation method according to claim 3, characterized in that: The self-assembly of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane on the substrate comprises the following steps: sequentially dropping 1,2-bis(4-pyridyl)ethane solution and 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution on the substrate for self-assembly.

6. The preparation method according to claim 3, characterized in that: The self-assembly of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid and 1,2-bis(4-pyridyl)ethane on the substrate comprises the following steps: dripping a mixed solution of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid / 1,2-bis(4-pyridyl)ethane on the substrate for self-assembly.

7. The preparation method according to claim 4 or 5, characterized in that: In the mixed system formed by the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid solution and the 1,2-bis(4-pyridyl)ethane solution, the molar ratio of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid to 1,2-bis(4-pyridyl)ethane is 1-1.5:1, the concentration of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid is 0.0005-0.002 mol / mL, and the pH value is 6-7.

5.

8. The preparation method according to claim 6, characterized in that: In the 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid / 1,2-bis(4-pyridyl)ethane mixed solution, the molar ratio of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid to 1,2-bis(4-pyridyl)ethane is 1-1.5:1, the concentration of 5,5'-(9H-fluorene-2,7-diyl)diphthalic acid is 0.0005-0.002 mol / mL, and the pH value is 6-7.

5.

9. The preparation method according to claim 3, characterized in that: The substrate is mechanically peeled off before use.

10. Use of the nano-geometric quantity standard sample according to any one of claims 1 to 2 or the nano-geometric quantity standard sample prepared by the preparation method according to any one of claims 3 to 9 in nano-measurement.

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