CN117641944A - Method for realizing in-situ controllable single-molecule rectifier based on intramolecular hydrogen bond - Google Patents
Method for realizing in-situ controllable single-molecule rectifier based on intramolecular hydrogen bond Download PDFInfo
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- CN117641944A CN117641944A CN202310772013.XA CN202310772013A CN117641944A CN 117641944 A CN117641944 A CN 117641944A CN 202310772013 A CN202310772013 A CN 202310772013A CN 117641944 A CN117641944 A CN 117641944A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 19
- 239000001257 hydrogen Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 12
- 230000005540 biological transmission Effects 0.000 claims abstract 2
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 230000007613 environmental effect Effects 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000005641 tunneling Effects 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000005442 molecular electronic Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000003776 cleavage reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000007017 scission Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 150000002576 ketones Chemical class 0.000 description 5
- XMRYQPHPFFLECV-UHFFFAOYSA-N 1,3-dipyridin-4-ylpropane-1,3-dione Chemical compound C=1C=NC=CC=1C(=O)CC(=O)C1=CC=NC=C1 XMRYQPHPFFLECV-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 150000002085 enols Chemical group 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 230000008863 intramolecular interaction Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for realizing an in-situ controllable single-molecule rectifier based on intramolecular hydrogen bonds relates to the fields of molecular electronics, nanomaterials, chemistry and the like, and a scanning tunnel microscope cleavage technology is used for measuring a volt-ampere characteristic curve graph of a class of beta-diketone derivatives, and the generation of the rectification effect is found to be due to the obvious rectification effect of the intramolecular hydrogen bonds which exist stably in an enol-type configuration of the beta-diketone derivatives, and the intramolecular hydrogen bonds participate in charge transmission. The discovery proves that the beta-diketone derivative single-molecule junction has the potential of realizing the performance of a molecular rectifier in the extremely short molecular length of about 1 nanometer, compared with the prior molecular rectifier with an asymmetric complex structure, the molecular rectifying functional group in the method has the advantages of simple structure, easy synthesis and modification, lower cost and higher conductivity, and can realize the active in-situ regulation and control of the rectifying performance of molecules by changing the external environment. In addition, the energy consumption is low, the noise is small in the process of realizing the rectification function, and the method is favorable for the integrated application of the molecular devices in the future.
Description
Technical Field
The invention is applied to the preparation of a nanoscale in-situ controllable rectifier under the molecular scale, and relates to the fields of molecular electronics, nanomaterials, chemistry and the like.
Background
With the rapid development of the information age, the upper limit of the size of silicon-based semiconductor electronic devices is gradually approaching, and miniaturization and integration of electronic components such as rectifiers, switches, transistors, and memories are becoming urgent. In recent years, nano-scale oligomer single molecules are considered as alternatives for silicon-based semiconductors to break through Moore's law due to the characteristics of wide candidates for optical, electrical, ionic, magnetic, thermal, mechanical and chemical reaction properties, easy modification and the like, and development of single-molecule devices is considered as a potential solution to overcome the problem. As such, molecular electronics is being vigorously developed, with the next generation of molecular level rectifier components being of great interest. Heretofore, there have been various methods of implementing molecular rectifiers, such as by designing diblock molecules comprising two different conjugated modules with opposite electron requirements, which effect is similar to a semiconductor p-n junction, to implement the function of a molecular rectifier, in addition to a transition metal gate induced molecular rectifier design and an anchor group induced molecular rectifier design. However, the molecular structure required for the above-mentioned molecular rectifier is complicated, long, low in electric conduction, difficult to synthesize, and high in cost, that is, it is important to realize rectifying performance in a short molecule. In addition, in the current single-molecule rectifier research, after a molecule rectifier is introduced into a circuit, it is also a very difficult task to control the rectification characteristic in situ without damaging the circuit.
Hydrogen bonding is a common intermolecular force, which refers to the attractive force between hydrogen on a strong polar bond and an atom which has great electronegativity, contains lone pair electrons and has partial negative charges. Research has shown that the existence of intramolecular hydrogen bonds can possibly lead a molecular device to have rectifying performance, but the intramolecular hydrogen bonds often cannot exist stably due to unstable molecular conformation and the like. In β -diketone derivatives, the intramolecular hydrogen bond will help stabilize its enol-isomer, and conversely, it is because of its stable enol-configuration that is more stable than other hydrogen bonds.
The scanning tunneling microscope (STM-BJ) technology is mostly used for constructing and researching the electrical characteristics of single-molecule devices, and the device has the advantages of good stability, simple device, easy operation and high repeatability.
Here, we measured the voltammogram of a class of β -diketone derivatives (molecular length only about 1 nm and ease of synthesis) using STM-BJ, which were found to have a significant rectifying effect, demonstrating the performance of β -diketone derivative single-molecule junctions as molecular rectifiers. In addition, the rectification performance of the molecular rectifier can be controlled in situ by means of changing the external environment such as ultraviolet irradiation.
Disclosure of Invention
The invention provides a method for realizing a molecular rectifier function based on stable intramolecular hydrogen bonds, and the existence of the rectifying effect is derived from molecules, is irrelevant to electrodes, solvents, instruments and other environmental factors, can be realized in a single molecular junction and a self-assembled molecular layer, and has the potential of integration. In addition, the rectification performance of the molecular rectifier can be controlled in situ by means of changing external environment, such as ultraviolet irradiation, polarity change and the like. The structure and the condition for forming the rectifier are simple and clear, the preparation process is simple, and the integration is easy.
The experimental scheme adopted by the invention is as follows:
the structure used in the method is composed of a gold tip top electrode, a molecular solution or self-assembled monolayer, a silicon substrate, a 10 nm chromium coating and a bottom electrode composed of a 200 nm gold coating, and a gold-molecule-gold single-molecule structure is formed. And (3) electrically testing the single-molecule junction by using an STM-BJ technology, and scanning a volt-ampere characteristic curve within a scanning range of-1.5V to 1.5V.
The invention has the technical advantages that: the method utilizes the intramolecular interaction force to realize the performance of the molecular rectifier, the rectification effect comes from the supply-receiving action of the intramolecular interaction force in the molecule, the asymmetry of the molecular structure is not required, the external regulation and control are not depended, the nano-ampere level rectification performance is realized, and the rectification ratio of 2.1 times is achieved in the extremely short molecular length of about 1 nanometer. The molecular rectifying functional group has simple structure, easy synthesis and modification, lower cost and higher conductivity. It is worth mentioning that the rectification performance of the molecular rectifier can be controlled in situ by means of changing external environment such as ultraviolet irradiation, polarity change, etc. In the running process, the rectifier has diversity in use of base materials and electrode materials, groups bringing intramolecular interaction force are easy to modify, the bias voltages at the two ends of the electrodes are extremely small, and low energy consumption is realized.
Drawings
FIG. 1 is a schematic diagram of a single molecular junction of a β -diketone derivative.
FIG. 2 is a graph of voltammetric properties of an enol-type single-molecule junction of a β -diketone derivative.
FIG. 3 is a schematic representation of a single molecular junction of an enol-form to a keto-form following cleavage of intramolecular hydrogen bonds of a β -diketone derivative.
FIG. 4 is a graph of voltammetric properties of a ketone single molecular junction of a β -diketone derivative.
FIG. 5 is a graph comparing voltammetric properties of single molecular junctions of keto and enol forms of β -diketone derivatives.
In the figure: 1 is the top electrode, 2 is the bottom electrode, 3 is the molecule to be tested, 1, 3-di (pyridin-4-yl) propane-1, 3-dione (enol form), 4 is 1, 3-di (pyridin-4-yl) propane-1, 3-dione (ketone form).
Detailed Description
The following describes the embodiments of the present invention in detail with reference to the drawings.
Examples: the top electrode (1) is a gold electrode made of gold balls with the diameter of 0.25 mM calcined by a butane flame outer flame, the bottom electrode is a gold electrode made by sputtering a 10 nm chromium layer and a 200 nm gold layer on a 1×2 cm silicon substrate, the 1, 3-di (pyridin-4-yl) propane-1, 3-dione of the molecule to be tested is an enol configuration (3, containing intramolecular hydrogen bonds) in a nonpolar solvent of 1,2, 4-Trichlorobenzene (TCB), a 1, 3-di (pyridin-4-yl) propane-1, 3-dione solution in 0.1 mM TCB is prepared for later use, and 1.5 microliter of the target solution is dripped between the top electrode (1) and the bottom electrode (2) using a pipette gun to obtain a single-molecule junction as shown in fig. 1. The voltammetric characteristic curve measurement was performed using an STM-BJ instrument, and the voltammetric characteristic curve (not less than 1000 curve statistical fits) with a rectification ratio of 2.1 shown in fig. 2 was obtained.
In order to break the intramolecular hydrogen bond, the molecular configuration was converted to ketone to achieve in situ control of the molecular rectification performance, and ultraviolet light of 365 nm (ultraviolet torch, 20 cm away from the molecular junction) was irradiated to the single molecular junction, and after 2 hours, the molecule was completely converted to ketone, to obtain the single molecular junction shown in fig. 3. At this time, the voltammetric characteristic curve measurement was performed using an STM-BJ instrument, and the voltammetric characteristic curve without rectification performance shown in FIG. 4 (not less than 1000 curve statistical fits) was obtained.
Fig. 5 is a combination diagram of fig. 2 and fig. 4, and it can be clearly seen that after the molecule to be detected is converted from enol form to ketone form, the conductivity is reduced, and the rectification ratio is 1, so that the primary taste regulation and control of the rectification performance are realized.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various equivalent methods within the spirit and scope of the appended claims.
Claims (5)
1. A method for realizing an in-situ controllable single-molecule rectifier function based on intramolecular hydrogen bonds is characterized by comprising the following steps: the performance of the single-molecule rectifier is realized in the electrode-molecule-electrode single-molecule junction through an asymmetric structure brought by stable intramolecular hydrogen bonds and an additional electron transmission channel, and the rectification performance of molecules can be controlled in situ through a means of changing external environment.
2. The method for realizing the single-molecule rectifier according to claim 1, wherein: including but not limited to electrode-molecule-electrode single molecule junctions constructed by scanning tunneling microscope cleaving devices (STM-BJs) or mechanically controllable nanosplitting devices (MCBJs).
3. The method for realizing the single-molecule rectifier according to claim 1, wherein: intramolecular hydrogen bonds include, but are not limited to, O-H … O, O-H … N, N-H … O, N-H … O, O-H … F, N-H … F.
4. The method for realizing the single-molecule rectifier according to claim 1, wherein: the rectifying performance comes from the molecule itself, and the rectifying performance of the molecular junction can be realized by using two end electrode materials including but not limited to gold, silver, copper and the like.
5. The method for realizing the single-molecule rectifier according to claim 1, wherein: means for achieving primary taste control of such molecular rectifiers include, but are not limited to, ultraviolet light irradiation in various wavebands, changing solvents and environmental polarities, changing environmental PH, adding hydrogen bond breakers such as ethanol, urea, and the like.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310772013.XA CN117641944A (en) | 2023-06-28 | 2023-06-28 | Method for realizing in-situ controllable single-molecule rectifier based on intramolecular hydrogen bond |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310772013.XA CN117641944A (en) | 2023-06-28 | 2023-06-28 | Method for realizing in-situ controllable single-molecule rectifier based on intramolecular hydrogen bond |
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| CN117641944A true CN117641944A (en) | 2024-03-01 |
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| CN202310772013.XA Pending CN117641944A (en) | 2023-06-28 | 2023-06-28 | Method for realizing in-situ controllable single-molecule rectifier based on intramolecular hydrogen bond |
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- 2023-06-28 CN CN202310772013.XA patent/CN117641944A/en active Pending
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