CN114203541B - A method for transferring metal electrodes onto two-dimensional materials - Google Patents
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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Abstract
本发明公开了一种将金属电极转移至二维材料上的方法，其包括：获取待转移结构，所述待转移结构包括衬底、形成于衬底上的过渡层以及形成于过渡层上的金属电极图案；对所述过渡层进行湿法刻蚀，去除未被金属电极图案覆盖的所述过渡层；通过有机柔性材料将待转移结构中的金属电极图案从所述过渡层上整体粘起并贴合至目标结构中的二维材料上；去除所述有机柔性材料，完成金属电极与二维材料的范德华接触。通过引入过渡层并结合湿法刻蚀和干法转移，使得容易实现待转移图案的整体剥离，大大提高了制备的成功率，且通过范德华力结合金属电极和二维材料，能够大大提高两者的接触性能。
The present invention discloses a method for transferring a metal electrode to a two-dimensional material, which comprises: obtaining a structure to be transferred, the structure to be transferred comprising a substrate, a transition layer formed on the substrate, and a metal electrode pattern formed on the transition layer; wet etching the transition layer to remove the transition layer not covered by the metal electrode pattern; using an organic flexible material to integrally bond the metal electrode pattern in the structure to be transferred from the transition layer and adhere it to the two-dimensional material in the target structure; removing the organic flexible material to complete the van der Waals contact between the metal electrode and the two-dimensional material. By introducing a transition layer and combining wet etching and dry transfer, it is easy to realize the overall peeling of the pattern to be transferred, greatly improving the success rate of preparation, and by combining the metal electrode and the two-dimensional material through van der Waals force, the contact performance of the two can be greatly improved.
Description
Technical Field
The invention belongs to the technical field of semiconductor structure preparation, and particularly relates to a method for transferring a metal electrode to a two-dimensional material.
Background
Today, the increasing information processing capacity, the ever increasing integration of circuits, has driven devices to be miniaturized. However, as the size is further reduced, conventional silicon-based devices face physical limitations such as short channel effects. As a novel material, the two-dimensional material shows excellent properties in the aspects of light, electricity, magnetism, heat and the like, and attracts wide research interest. When the size is reduced to below 10nm, the two-dimensional material can still maintain good grid control capability, and the short channel effect can be effectively relieved. Therefore, a two-dimensional material is expected to become a next-generation semiconductor material.
However, contact resistance is a non-negligible problem in low-dimensional devices. In the traditional device preparation process flow, due to the fact that metal is directly deposited on a two-dimensional material, the contact performance between the metal and the two-dimensional material is reduced due to complex interaction on an interface between the metal and the two-dimensional material, such as chemical bonds formed between the metal and the two-dimensional material, interfacial strain generated between the metal and the two-dimensional material, water and hydrocarbon adsorbed on the surface of the two-dimensional material, high-energy metal atom bombardment on the surface of the two-dimensional material in the device preparation process, photoresist residues in the preparation process and the like. Also, as device dimensions decrease, the contact resistance between the metal electrode and the two-dimensional material becomes more pronounced, even leading to the electrical performance of the device. Therefore, there is a need to propose an effective way to improve the contact problem of metals with two-dimensional materials.
Disclosure of Invention
In order to solve the above defects or improvement demands of the prior art, the invention provides a method for transferring a metal electrode to a two-dimensional material, and aims to solve the technical problem of poor contact performance between the metal electrode and the two-dimensional material.
To achieve the above object, according to one aspect of the present invention, there is provided a method of transferring a metal electrode onto a two-dimensional material, comprising:
Obtaining a structure to be transferred, wherein the structure to be transferred comprises a substrate, a transition layer formed on the substrate and a metal electrode pattern formed on the transition layer;
Wet etching is carried out on the transition layer, and the transition layer which is not covered by the metal electrode pattern is removed;
Sticking the metal electrode pattern in the structure to be transferred from the transition layer integrally by using an organic flexible material and attaching the metal electrode pattern to a two-dimensional material in a target structure;
and removing the organic flexible material to complete van der Waals contact between the metal electrode and the two-dimensional material.
Preferably, the acquiring the structure to be transferred includes:
providing a transfer substrate;
Growing a transition layer on the transfer substrate;
forming a patterned photoresist layer on the transition layer;
evaporating metal material and removing the photoresist layer to obtain the metal electrode pattern on the transition layer.
Preferably, the height range of the transition layer is 250 nm-350 nm.
Preferably, the metal electrode pattern includes Cr at the bottom and Au at the top, wherein the height range of Cr is 8nm to 12nm, and the height range of Au is 40nm to 120nm.
Preferably, the transition layer is etched to remove the transition layer not covered by the metal electrode pattern and the transition layer partially covered by the metal electrode pattern.
Preferably, the organic flexible material includes a flexible supporting layer and a flexible adhesive layer on the flexible supporting layer, and the organic flexible material sticks up the metal electrode pattern through the flexible adhesive layer.
Preferably, the flexible support layer comprises PDMS or PMMA and the flexible adhesive layer comprises PVA;
Removing the organic flexible material includes:
heating the target structure to tear the flexible support layer away from the target structure;
and placing the target structure with the flexible supporting layer removed in a solution to dissolve and remove the flexible adhesive layer.
Preferably, after the metal electrode pattern in the structure to be transferred is integrally stuck from the transition layer through the organic flexible material, the metal electrode pattern and the target structure are aligned and attached through an alignment assembly on the transfer table.
Preferably, the transition layer is an oxide layer.
Overall, the present application has the following advantages over the prior art:
(1) The transfer process comprises wet etching and dry transfer, and wet etching is performed before dry transfer, so that the adhesion between the metal electrode and the bottom structure can be effectively reduced in the wet etching process, and compared with the dry transfer in the traditional method, the overall stripping of the pattern to be transferred can be realized more easily in the transfer process, and the success rate of preparation is greatly improved;
(2) The traditional method for depositing the metal electrode involves bombardment of high-energy metal atoms on materials at target sites, and chemical action can be generated between the metal atoms and the two-dimensional materials to form chemical bonds under the high-energy action;
(3) According to the application, the metal electrode pattern is naturally pressed on the target site by the transfer method, and adsorbates on the surface of the two-dimensional material can be extruded in the natural bonding process, so that the performance of a contact interface between the two-dimensional material and metal is further improved;
(4) In the traditional process, before the two-dimensional material is formed, the alignment mark is required to be formed through a photoetching process, so that alignment is conveniently carried out when the patterned metal electrode is formed through an etching process.
Drawings
FIG. 1 is a flow chart of method steps for transferring a metal electrode to a two-dimensional material in accordance with one embodiment of the present application;
FIG. 2 is a flow chart of an experiment in one embodiment of the present application;
FIG. 3 is a block diagram of steps performed in accordance with one embodiment of the present application;
FIG. 4 is a schematic diagram of an etching process in accordance with an embodiment of the present application;
FIG. 5 (a) is a graph showing the effect of PVA adhering to an electrode during electrode transfer in example 1 of the present application;
FIG. 5 (b) is a physical diagram of the electrode transfer according to example 1 of the present application;
FIG. 6 (a) is a view of the electrode transfer according to example 2 of the present application, which is observed under a microscope;
FIG. 6 (b) is a graph comparing the performance of the device prepared in example 2 of the present application with that of a conventional photolithography process.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
FIG. 1 is a flowchart showing steps in a method for transferring a metal electrode to a two-dimensional material according to an embodiment of the present application, the method comprising:
Step S100, a structure to be transferred is obtained, wherein the structure to be transferred comprises a substrate, a transition layer formed on the substrate and a metal electrode pattern formed on the transition layer.
In one embodiment, the step of obtaining the structure to be transferred includes:
Step S110, providing a transfer substrate.
The transfer substrate may be a conventional silicon substrate, or may be another semiconductor substrate.
And step S120, growing a transition layer on the transfer substrate.
Specifically, the transition layer may be an oxide layer, and the transition layer grown on the silicon substrate is silicon oxide.
And 130, forming a patterned photoresist layer on the transition layer.
Specifically, a photoresist layer is spin-coated on a silicon wafer with a silicon transition layer surface, and a pattern on the photoresist layer is obtained by using a photoetching/Electron Beam Lithography (EBL) process.
And step 140, evaporating the metal material and removing the photoresist layer to obtain the metal electrode pattern on the transition layer.
Specifically, metal is evaporated on a silicon substrate by utilizing an Electron Beam Evaporation (EBE) process, and finally, a silicon wafer is placed in an acetone or Dimethylformamide (DMF) solution to remove photoresist, so that the preparation of a metal electrode pattern is completed.
In an embodiment, the material of the metal electrode pattern may include Cr on the bottom layer and Au on the top, as shown in fig. 2, and the preparation of the metal electrode is completed through step S100, which results in the structure of the (a) diagram as shown in fig. 3.
And step 200, carrying out wet etching on the transition layer to remove the transition layer which is not covered by the metal electrode pattern.
And soaking the transition layer in etching solution, removing the exposed transition layer, wherein the transition layer at the bottom of the metal electrode pattern is not completely etched due to the protection of the metal electrode pattern, but a porous loose structure is formed. The applicant has found that, compared with directly forming the metal electrode pattern on the substrate, by adding a transition layer and combining wet etching, the adhesion between the metal electrode pattern and the underlying structure can be reduced, which is beneficial to the subsequent stripping of the metal electrode pattern.
In one embodiment, the etching time can be properly increased, and the transition layer not covered by the metal electrode pattern and the transition layer partially covered by the metal electrode pattern are removed, so that the adhesion between the metal electrode pattern and the carrier is further reduced.
In an embodiment, in order to improve the success rate of the overall transfer, the height of the transition layer is limited, and the height range of the transition layer is 250 nm-350 nm. In an embodiment, the height of the metal electrode pattern is also defined, and the metal electrode pattern includes Cr at the bottom and Au at the top, wherein the height range of Cr is 8nm to 12nm, and the height range of Au is 40nm to 120nm. Within this range, the metal electrode pattern can be peeled off smoothly.
Specifically, referring to fig. 2, a silicon wafer with a transition layer as an example of silicon oxide is placed in NaOH or KOH solution, and the NaOH (KOH) reacts with the silicon oxide, so that the silicon oxide is etched, and after the etching is completed, the silicon wafer is taken out, washed with absolute ethyl alcohol and deionized water, and then dried on a heating table, thereby obtaining the structure of the graph (b) as shown in fig. 3.
And step 300, sticking the metal electrode pattern in the structure to be transferred from the transition layer to the two-dimensional material in the target structure through the organic flexible material.
The organic flexible material is selected as a transfer medium, so that damage to the metal electrode pattern during transfer can be avoided. It will be appreciated that the organic flexible material is capable of adhering to the metal electrode pattern. In one embodiment, the organic flexible material may include two portions, one portion being a thicker flexible support layer and the other portion being a thinner adhesion layer on the support layer for contacting and adhering the metal electrode pattern. In one embodiment, the flexible support layer may be PDMS (polydimethylsiloxane) or PMMA (polymethyl methacrylate), and the flexible adhesive layer may be PVA (polyvinyl alcohol). Specifically, the method can be specifically described with reference to fig. 2 and 3, and the metal electrode pattern is integrally bonded by dry transfer, and the process is shown in fig. 3 (c), and is bonded with a two-dimensional material, so as to obtain the structure of fig. 3 (d).
And step 400, removing the organic flexible material to complete van der Waals contact between the metal electrode and the two-dimensional material.
And finally, as shown in a graph (e) of fig. 3, slowly lifting the PDMS, putting the silicon wafer bonded with the PVA into deionized water to dissolve and remove the PVA, taking out and drying the silicon wafer, and then completing electrode transfer to obtain the graph structure (f) of fig. 3.
For ease of understanding, two specific examples are described below.
Example 1
(1) Spin-coating a photoresist layer on a silicon wafer with a silicon oxide layer surface, obtaining an electrode pattern on the photoresist by utilizing a photoetching/Electron Beam Lithography (EBL) process, evaporating a 10nm/50nm Cr/Au metal electrode on a silicon substrate by utilizing an Electron Beam Evaporation (EBE) process, and finally placing the silicon wafer in a Dimethylformamide (DMF) solution to remove the photoresist, thereby completing the preparation of the metal electrode pattern;
(2) Etching oxide layer on the surface of silicon wafer, namely placing the silicon wafer with the prepared metal electrode pattern in NaOH solution with the mass fraction of 40%, wherein NaOH can react with silicon oxide, so that the effect of etching silicon oxide can be achieved, as shown in figure 4;
(3) The metal electrode transfer is carried out, namely, the silicon oxide at the bottom of the metal electrode is not completely etched due to strong adhesion between the metal electrode and the silicon oxide, the metal electrode is adhered to a silicon wafer with small adhesion after the silicon oxide is partially etched, then, a small piece of PVA is adhered to one surface of PDMS, the whole set of electrode patterns is adhered to the PVA on a two-dimensional material transfer platform to obtain the result shown in the figure 5 (a), then, the two-dimensional material transfer platform is precisely aligned, the electrode patterns are adhered to a target two-dimensional material WSe2, the transfer platform is heated to 50 ℃ to enable the PVA to be tightly adhered to the silicon wafer, finally, the PDMS is slowly lifted, the silicon wafer adhered with the PVA is put into deionized water to be dissolved and removed, and the electrode transfer is completed after the silicon wafer is taken out and dried, so that the result shown in the figure 5 (b) is obtained.
Example two
(1) Spin-coating a photoresist layer on a silicon wafer with a silicon oxide layer surface, obtaining an electrode pattern on the photoresist by utilizing a photoetching/Electron Beam Lithography (EBL) process, evaporating a 10nm/50nm Cr/Au metal electrode on a silicon substrate by utilizing an Electron Beam Evaporation (EBE) process, and finally placing the silicon wafer in an acetone solution to remove the photoresist to finish the preparation of the metal electrode pattern;
(2) Etching the oxide layer on the surface of the silicon wafer, namely placing the silicon wafer with the prepared metal electrode pattern in KOH solution with the mass fraction of 30%, and taking out the silicon wafer after 72 hours, cleaning the silicon wafer with absolute ethyl alcohol and deionized water, and drying by using a laboratory ear-washing ball;
(3) The metal electrode transfer is carried out by that, because there is strong adhesive force between the metal electrode and silicon oxide, silicon oxide at the bottom of the metal electrode will not be completely etched, after silicon oxide is partially etched, the metal electrode will adhere to silicon wafer with small adhesive force, then a small piece of PVA is stuck on one surface of PDMS, the whole set of electrode pattern is stuck to PVA on a two-dimensional material transfer platform, then the two-dimensional material transfer platform is precisely aligned, the electrode pattern is adhered to a target two-dimensional material ReS2, then the transfer platform is heated to 50 ℃ to enable the PVA to be tightly adhered to the silicon wafer, finally PDMS is slowly lifted, the silicon wafer adhered with PVA is put into deionized water to dissolve and remove PVA, and the silicon wafer is taken out and dried to complete the electrode transfer, thus obtaining the result shown in figure 6 (a).
(4) Device electrical property measurement, namely, the electrical property of the device is measured by a Keithley 4200 semiconductor analyzer and is compared with the electrical property of the device obtained by a common photoetching process, and the comparison result is shown in fig. 6 (b), and experiments prove that the contact between the metal electrode and the two-dimensional material is realized by the scheme, so that the I/V performance of the obtained semiconductor device is better.
In summary, the transfer process in the application comprises wet etching and dry transfer, and wet etching is performed before dry transfer, so that the adhesion between the metal electrode and the bottom structure can be effectively reduced in the wet etching process. Meanwhile, the application can avoid the formation of chemical bonds or the occurrence of strain between the metal and the two-dimensional material by a transfer method, and reduce the contact resistance. In addition, the transfer method can naturally press the metal electrode pattern on the target site, and the adsorbate on the surface of the two-dimensional material can be extruded in the natural bonding process, so that the performance of the contact interface between the two-dimensional material and the metal is further improved. Furthermore, in the application, the step of preparing the alignment mark can be omitted, and the alignment and lamination can be directly carried out through the alignment assembly, so that the process steps are simplified.
It will be readily appreciated by those skilled in the art that the foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
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