WO2019184035A1

WO2019184035A1 - Method for preparing controllable patterned electrical device

Info

Publication number: WO2019184035A1
Application number: PCT/CN2018/084157
Authority: WO
Inventors: 吴雨辰; 刘芸; 江雷
Original assignee: 北京赛特超润界面科技有限公司
Priority date: 2018-03-27
Filing date: 2018-04-24
Publication date: 2019-10-03
Also published as: CN110310964B; CN110310964A

Abstract

Provided is a method for preparing controllable patterned electrical device, the preparing method comprises the following steps: 1) vacuum sputtering the patterned hydrophilic electrode by vapor phase method on a flat plate substrate; 2) soaking the flat plate substrate on which the patterned hydrophilic electrode is evaporated in the mercaptan for 10-50 hours, then taking out the flat plate substrate for washing and blowing dry; 3) preparing a substrate having a microcolumn structure by photolithography; 4) the organic molecular solution is directly dropped onto the substrate having the microcolumn structure and covered with the flat plate substrate on which the patterned hydrophilic electrode is evaporated, the side of the flat plate substrate on which the patterned hydrophilic electrode is evaporated having the hydrophilic electrode faces the solution, and the orientation of the hydrophilic electrode intersects with the orientation of the microcolumn, sandwich assembly system is constructed, and as the process of reducing infiltration is performed, by forming a regular array of organic molecular one-dimensional structure between the hydrophilic electrodes, the controllable patterned electrical device is obtained.

Description

Method for preparing controllable patterned electrical device

Technical field

The invention belongs to the field of microelectronic devices. Specifically, by adjusting the parameters of the position, number, and morphology of the hydrophilic electrode (gold electrode) and the opposite silicon column, the solution method is directly prepared and constructed on the hydrophilic electrode. The electrical device provides a simple and efficient method of preparing a controllable patterned electrical device.

Background technique

Electrical devices such as field effect transistors, pressure sensors, and organic memory elements based on polymer molecules have the advantages of low cost, flexibility, and large-area preparation, and thus have a wide range of applications. Compared with the thin film material, the one-dimensional micro-nano material has fewer defects and more ordered molecular alignment, and thus has more excellent performance. At present, the one-dimensional structure of the device mostly adopts the bottom gate top electrode structure. Firstly, a one-dimensional structure array of organic molecules with large-area ordered arrangement is prepared, and then the gold electrode is fabricated on the organic molecules by vacuum evaporation technology. However, due to the use of evaporation technology to prepare the top electrode on the one-dimensional micro-nano structure, the mask paste has high technical requirements, long-time operation, low efficiency, and the position of the device, the channel length, the number of organic nanowires and other parameters. Can not be accurately regulated, so we urgently need to develop a simple and effective method to achieve precise control of the channel length, channel width, number of organic nanowires, etc., which will facilitate the precision and largeness of micro-structure devices. Scale preparation.

technical problem

SUMMARY OF THE INVENTION The object of the present invention is to provide a simple and convenient method for using a patterned gold electrode substrate having asymmetric wettability and a lithographically processed silicon wafer having a microcolumn structure, which is formed by re-wetting in a solution to obtain a gold electrode. The position of the one-dimensional structure of the organic molecules is precisely regulated. The device can directly test the electrical properties, and can obtain different devices by adjusting the position, number, and shape of the gold electrode and the silicon column relative to it. The method is simple and universal, and has a wide range of applications.

Technical solution

A method of preparing a controllable patterned electrical device, the method comprising the steps of:

1) patterning the hydrophilic electrode by vapor phase vacuum sputtering on a flat substrate;

2) immersing the plate substrate on which the patterned hydrophilic electrode is evaporated in mercaptan for 10-50 hours, taking out washing and drying;

3) preparing a substrate having a microcolumn structure by photolithography;

4) The organic molecular solution is directly dropped on a substrate having a microcolumn structure and covered with a flat substrate on which a patterned hydrophilic electrode is evaporated, and the side of the flat substrate on which the patterned hydrophilic electrode is evaporated has a hydrophilic electrode Oriented to the solution, and the orientation of the hydrophilic electrode intersects with the orientation of the microcolumn, and is constructed into a sandwich assembly system. As the de-wetting process progresses, a one-dimensional array of organic molecules arranged in a regular arrangement is formed between the hydrophilic electrodes, that is, Control patterned electrical devices.

Preferably, in step 1), the thickness of the hydrophilic electrode is 50-200 nm, and it is necessary to sputter 5-15 nm of chromium before sputtering the hydrophilic electrode.

Preferably, the step substrate of the step 1) is an indium tin oxide film or a conductive silicon wafer, and those skilled in the art can also select other types of flat substrate as needed.

Preferably, the pattern of the patterned hydrophilic electrode is one or more of a triangle, a quadrangle, a pentagon, a hexagon, and a circle, and those skilled in the art may also select patterns of other shapes as needed.

Preferably, the hydrophilic electrode is a gold electrode, and those skilled in the art can also select electrodes made of other hydrophilic materials as needed.

Preferably, the mercaptan in step 2) is perfluorothiol, and the solution has a concentration of 5-15%.

Preferably, in step 3), the substrate in the substrate having the micropillar structure is a silicon wafer or a glass sheet. Those skilled in the art can also select other substrates for optoelectronic devices as needed.

Preferably, the depth of the micropillar structure in the substrate having the micropillar structure is from 1 micrometer to 20 micrometers.

Preferably, in step 4), the orientation of the hydrophilic electrode intersects perpendicularly with the orientation of the microcolumn.

Preferably, in step 4), the organic molecular one-dimensional structure array has a length of 2 micrometers to 50 micrometers, a width of 100 nanometers to 2 micrometers, and a height of 20 nanometers to 1 micrometer.

In accordance with a preferred embodiment of the present invention, a method of fabricating a controllable patterned electrical device, the method of preparation comprising the steps of:

1) Patterned gold electrode substrate preparation: A patterned gold electrode lithography mask was designed. First, 10 nm chromium was sputtered by vapor phase vacuum sputtering, and then 100 nm gold was sputtered.

2) Asymmetric infiltration treatment (interfacial micro-area infiltration treatment): using gold and mercaptan (thiol is perfluorothiol, concentration is 7.68 %) reaction, thiol treatment time is 24h, preparation of hydrophobic gold surface, non- The gold area is hydrophilic.

3) Patterned microcolumn structure Wafer preparation: Using a photolithography technique, a silicon wafer substrate having a microcolumn structure (silicon pillar depth of 20 μm) was obtained.

4) Preparation of electrical devices (field effect transistors, photodetectors, electroluminescent devices). A one-dimensional structure array of organic molecules arranged regularly between gold electrodes was prepared by a solution method.

The number of the lithographic silicon wafers of the present invention can be adjusted, and the range of organic molecular solutions used is wide.

The invention belongs to the field of microelectronic devices, and relates to a method for directly preparing a plurality of organic molecular one-dimensional structure arrays on a freely controllable patterned gold electrode and constructing an electrical device such as a field effect transistor. The invention comprises the following steps: 1) vapor phase sputtering of gold to prepare a patterned gold electrode; 2) thiol modification of the gold electrode to obtain a gold electrode substrate having asymmetric wettability; 3) photolithographic silicon wafer to have a silicon pillar structure corresponding to the patterned gold electrode; 4) directly dropping the organic solution between the silicon wafer having the microcolumn structure and the patterned gold electrode to construct a sandwich assembly system, and utilizing the difference in wettability to make the organic solution in two Under the action of the person, the immersion is gradually infiltrated, and finally a one-dimensional array of organic molecules arranged in a regular arrangement between the gold electrodes is obtained to obtain an electrical device.

Beneficial effect

The method for preparing an organic molecular one-dimensional structure array directly on a gold electrode according to the invention is simple and convenient, and can directly test electrical properties, and the channel length, width, number and position of the one-dimensional structure of the device can be precisely regulated.

DRAWINGS

1 is a schematic view showing a manufacturing process of a gold electrode substrate having asymmetric wettability in the present invention;

2 is an optical micrograph of a gold electrode substrate having asymmetric asymmetry after modification with a thiol in the present invention;

3 is a schematic view showing a contact angle of a gold electrode substrate after modification of a mercaptan in the present invention;

Figure 4 is an optical micrograph of a lithographic silicon wafer used in the present invention, the silicon pillars are arranged longitudinally, and the number of silicon pillars in the unit is 1;

Figure 5 is an optical micrograph of a lithographic silicon wafer used in the present invention, the silicon pillars are arranged longitudinally, and the number of silicon pillars in the unit is 2;

Figure 6 is an optical micrograph of a lithographic silicon wafer used in the present invention, the silicon pillars are arranged longitudinally, and the number of silicon pillars in the unit is 3;

Figure 7 is an optical micrograph of a lithographic silicon wafer used in the present invention, the silicon pillars are arranged longitudinally, and the number of silicon pillars in the unit is 4;

8 is an electron micrograph of a photolithographic silicon wafer having a number of micropillars of 4 in the present invention;

Figure 9 is an optical micrograph of an electrical device of a series of different numbers of organic molecular one-dimensional structures prepared by adjusting the number of silicon columns;

Figure 10 is an optical micrograph of an electrical device having a number 4 of micropillars prepared according to the present invention;

Figure 11 is an optical micrograph of a series of electrical devices having different channel lengths prepared by adjusting the spacing between gold electrodes;

Figure 12 is an optical micrograph of a series of electrical devices having different channel widths prepared by adjusting the concentration of the polymer solution.

Embodiments of the invention

The technical solution of the present invention will be further described below in conjunction with the embodiments.

实施例Example 11

In the present invention, a patterned gold electrode substrate is obtained by vapor phase sputtering of gold, and a gold-thiol reaction is used to obtain a patterned gold electrode substrate having asymmetric wettability. The silicon wafer with microcolumn structure was prepared by photolithography. The infiltration behavior of the organic solution was controlled by different infiltration properties to obtain a one-dimensional structure array of organic molecules built between the gold electrodes. Specific steps are as follows:

1) As shown in Figure 1, using a photolithographic mask to sputter 10 nm on a silicon wafer substrate Chromium, then 100 nm gold was sputtered, and finally a patterned (arbitrarily shaped) gold electrode was obtained with a 10 μm spacing between the gold electrodes.

2) The patterned gold electrode substrate was immersed in perfluorothiol (concentration: 7.68 %) for 24 hours, taken out, rinsed with ethanol, and blown dry with nitrogen. The optical micrograph of the gold electrode substrate after modification by thiol is shown in the figure. 2, the contact angle is shown in Figure 3. As can be seen from Figure 2, the gold electrodes are arranged laterally; from Figure 3, the contact angle of the non-gold region (such as silicon) on the substrate after modification with thiol, The contact angle of the gold region on the substrate after modification with thiol is 40.9 ± 1.6°, which is 109.8. ± 3.8°.

3) The polymer CDTBTZ was dissolved in o-dichlorobenzene solvent at a concentration of 5 mg/mL.

4) Using a photolithography method to prepare a silicon wafer having a microcolumn structure, the number of microcolumns is 1, 2, 3, and 4, respectively, as shown in Fig. 4-7, and the electron micrograph of the photolithographic silicon wafer having the number of microcolumns 4 As shown in Fig. 8, it can be seen from Fig. 8 that the depth of the silicon column is 20 μm.

5) 20 μL of the polymer solution was directly dropped on a silicon wafer having 1 to 4 microcolumns, and covered with a thiol-modified gold electrode substrate, with the gold electrode facing the solution.

6) Place the "sandwich assembly structure" in the above 5) in an oven at 80 ° C for 24 h. Finally, a series of electrical devices with adjustable number of nanowires (including electrodes, organic single crystal array) can be obtained, as shown in Fig. 9, wherein the optical micrograph of the electrical device with 4 microcolumns is shown in Fig. 10 ( Length 10 microns, width 1 micron, height 500 nanometers).

实施例Example 22

1) Using a photolithographic mask, first sputter 15 nm of chromium on an indium tin oxide film substrate, and then sputter 200 Nm gold, finally obtained a patterned gold electrode. The spacing between the gold electrodes is 5, 10, 50 μm, respectively.

2) The patterned gold electrode substrate was immersed in perfluorothiol (concentration: 5%) for 50 hours, taken out, rinsed with ethanol, and blown dry with nitrogen.

3) Dissolve the polymer CDTBTZ in o-dichlorobenzene solvent (organic solvent such as toluene, nitrogen-nitrocarbamoylamide, etc.) at a concentration of 5 Mg/mL.

4) A silicon wafer having a microcolumn structure was prepared by photolithography, and the number of microcolumns was four.

5) Take 20 μL of the polymer solution directly onto the glass piece with 4 microcolumns in 4), and cover the gold with 5, 10, 50 μm spacing of the thiol-modified gold electrode in 1) The electrode substrate has one side of the gold electrode facing the solution.

6) Place the "sandwich assembly structure" in the above 5) in an oven at 80 ° C for 24 h. Finally, a series of electrical devices with different channel lengths can be obtained, as shown in Figure 11 (lengths between 5 and 50 microns, widths between 500 nanometers and 1 micron, and heights between 200 nanometers and 500 nanometers).

实施例Example 33

1) Using a photolithography mask, 5 nm of chromium is first sputtered on the silicon wafer substrate, and then 50 nm of gold is sputtered, and finally a patterned gold electrode is obtained. The spacing between the gold electrodes is 10 μm.

2) The patterned gold electrode substrate was immersed in perfluorothiol (concentration: 15%) for 10 hours, taken out, rinsed with ethanol, and blown dry with nitrogen.

3) Configure a series of different concentrations of polymer CDTBTZ solution, the solvent is o-dichlorobenzene, the concentration is 10 Mg/mL, 8 mg/mL, 5 Mg/mL, 2 mg/mL.

4) A silicon wafer having a microcolumn structure was prepared by photolithography, and the number of microcolumns was 4, respectively.

5) Take 20 μL of each of the different concentrations of the polymer solution directly onto the silicon wafer with 4 microcolumns in 4), and cover with a thiol-modified gold electrode substrate with the gold electrode facing the solution. .

6) Place the "sandwich assembly structure" in the above 5) in an oven at 80 ° C for 24 h. Finally, a series of electrical devices with adjustable channel widths can be obtained, as shown in Figure 12 (length 10 microns, width 500 nm - 2 microns, height 500 nm - 1 micron).

Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and not limiting. While the present invention has been described in detail with reference to the embodiments of the present invention, it should be understood that Within the scope of the claims.

Claims

A method of preparing a controllable patterned electrical device, the method comprising the steps of:

1) patterning the hydrophilic electrode by vapor phase vacuum sputtering on a flat substrate;

2) immersing the plate substrate on which the patterned hydrophilic electrode is evaporated in mercaptan for 10-50 hours, taking out washing and drying;

3) preparing a substrate having a microcolumn structure by photolithography;

4) The organic molecular solution is directly dropped on a substrate having a microcolumn structure and covered with a flat substrate on which a patterned hydrophilic electrode is evaporated, and the side of the flat substrate on which the patterned hydrophilic electrode is evaporated has a hydrophilic electrode Oriented to the solution, and the orientation of the hydrophilic electrode intersects with the orientation of the microcolumn, and is constructed into a sandwich assembly system. As the de-wetting process progresses, a one-dimensional array of organic molecules arranged in a regular arrangement is formed between the hydrophilic electrodes, that is, Control patterned electrical devices.
The method for preparing a controllable patterned electrical device according to claim 1, wherein in the step 1), the thickness of the hydrophilic electrode is 50-200 nm, and sputtering 5-15 nm is required before sputtering the hydrophilic electrode. chromium.
The method for preparing a controllable patterned electrical device according to claim 1, wherein the step substrate 1) is an indium tin oxide film or a conductive silicon wafer.
The method of manufacturing a controllable patterned electrical device according to claim 1, wherein the pattern of the patterned hydrophilic electrode is one or more of a triangle, a quadrangle, a pentagon, a hexagon, and a circle. Kind.
The method of fabricating a controllable patterned electrical device according to claim 1, wherein the hydrophilic electrode is a gold electrode or a chromium electrode.
The method for preparing a controllable patterned electrical device according to claim 1, wherein the mercaptan is a perfluorothiol in step 2), and the solution has a concentration of 5-15%.
The method of fabricating a controllable patterned electrical device according to claim 1, wherein in the step 3), the substrate in the substrate having the micro-pillar structure is a silicon wafer or a glass sheet.
The method of fabricating a controllable patterned electrical device according to claim 1, wherein in the step 3), the depth of the micro-pillar structure in the substrate having the micro-pillar structure is from 1 micrometer to 20 micrometers.
The method of fabricating a controllable patterned electrical device according to claim 1, wherein in step 4), the orientation of the hydrophilic electrode intersects perpendicularly with the orientation of the microcolumn.
The method for preparing a controllable patterned electrical device according to claim 1, wherein in step 4), the one-dimensional structure array of organic molecules has a length of 2 micrometers to 50 micrometers, a width of 100 nanometers to 2 micrometers, and a height of 20 nanometers to 1 micron.