CN108611684B - Controllable thinning method of transition metal chalcogenide two-dimensional atomic crystal - Google Patents

Controllable thinning method of transition metal chalcogenide two-dimensional atomic crystal Download PDF

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CN108611684B
CN108611684B CN201810390559.8A CN201810390559A CN108611684B CN 108611684 B CN108611684 B CN 108611684B CN 201810390559 A CN201810390559 A CN 201810390559A CN 108611684 B CN108611684 B CN 108611684B
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CN108611684A (en
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刘碧录
任洁
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Shenzhen International Graduate School of Tsinghua University
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Tsinghua Berkeley Shenzhen College Preparatory Office
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Abstract

The invention provides a controllable thinning method of a transition metal chalcogenide two-dimensional atomic crystal, which comprises the following steps: the layered transition metal chalcogenide material is firstly soaked in chloroauric acid solution for a certain time, and then taken out and soaked in water for a certain time. And removing residual moisture on the surface of the sample to obtain the thinned transition metal chalcogenide material atomic crystal. The thinning method adopts chloroauric acid to process the layered material, can quickly thin the layered material, has the advantages of simple operation, high thinning speed, good controllability, no damage to sample quality and the like, and can prepare the thin-layer large-area transition metal chalcogenide two-dimensional atomic crystal.

Description

Controllable thinning method of transition metal chalcogenide two-dimensional atomic crystal
Technical Field
The invention belongs to the field of new materials, particularly relates to a thickness reduction method of a two-dimensional atomic crystal, and particularly relates to a controllable reduction method of a transition metal chalcogenide two-dimensional atomic crystal.
Background
Two-dimensional atomic crystals represented by graphene have gained wide attention in academia and industry due to their unique optical, electrical, thermal and mechanical properties. Two-dimensional atomic crystals are a class of materials having a layered structure with layers bonded with weak van der waals forces between the layers, and in-plane atoms bonded with strong chemical bonds. Wherein the transition metal chalcogenide (MX)2) The two-dimensional material has rich material types, proper forbidden band width (1.0-2.0 eV) adjustable along with the number of layers and high carrier mobility (200 + 500 cm)2V-1s-1) The transition metal chalcogenide (M ═ Mo, W, Nb and other transition metal elements, X ═ S, Se, Te and other elements) is expected to replace silicon-based and III-V group materials in the traditional semiconductor industry or be used complementary with the silicon-based and III-V group materials, and further becomes an important material for future nano-electronics and optoelectronics. At present, a great deal of scientific research work has proved that the transition metal chalcogenide has wide application prospects in various fields such as sensors, flexible electronic devices, field effect transistors, photodetectors, light emitting diodes and the like.
MX2The electrical and optical properties of the two-dimensional atom-like crystal are closely related to the thickness of the two-dimensional atom-like crystal, and theories and experiments prove that MX from two layers to a bulk phase2Mostly indirect bandgap semiconductor materials (e.g. MoS)2,WS2,MoSe2,WSe2Etc.) and its forbidden bandwidth decreases with increasing number of layers. In contrast, a single layerMX2Most of the materials are direct band gap semiconductor materials and have the maximum forbidden band width. Thus, how MX is controlled2The thickness and the number of layers of the two-dimensional atom-like crystal are the first problems to be solved in practical application and are also a current challenge. The mechanical stripping method is also called adhesive tape method, which is a traditional preparation method of two-dimensional thin layer material, and mainly comprises the steps of repeatedly sticking the bulk laminar material and transferring the thin layer of the two-dimensional material stuck on the adhesive tape to other substrates. Geim et al obtained monolayer graphite, graphene, for the first time using this method. This method has the advantage of being simple and easy to carry out, but has the disadvantage of extremely low yield, and the area of the obtained thin layer is very small, usually only 3 to 5 μm2The method is poor in controllability. Recently, Liu et al used a plasma physical etching method to thin a thick sample prepared by tape stripping to obtain a thin two-dimensional atomic crystal sample. Although the plasma thinning method can improve the yield of a thin-layer sample, the process parameters are complex, the energy consumption is high, and defects are introduced in the etching process, so that the quality of the two-dimensional atomic crystal is reduced. Therefore, developing a simple, easy and controllable two-dimensional atomic crystal thinning method is one of the problems to be solved urgently in the field.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a controllable thinning method of a transition metal chalcogenide two-dimensional atomic crystal, which can improve the yield of the two-dimensional atomic crystal and increase the area of a thin layer compared with the traditional mechanical stripping method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a controllable thinning method of a transition metal chalcogenide two-dimensional atomic crystal, which comprises the following steps:
and repeatedly sticking the layered material by using an adhesive tape, transferring a sample stuck on the adhesive tape onto a silicon wafer, soaking the silicon wafer with the sample in a chloroauric acid solution, soaking the silicon wafer in water, and removing residual moisture on the surface of the silicon wafer to obtain the two-dimensional atomic crystal.
AsAccording to the preferable technical scheme of the invention, the layered material is MX2M is any one of transition metals, and X is any one of VIA group elements.
Preferably, the M includes any one of Mo, W, or Nb.
Preferably, the X comprises any one of S, Se or Te.
In a preferred embodiment of the present invention, the number of times of repeatedly sticking the tape to the two-dimensional material single crystal is 1 to 100, such as 5, 20, 45, 65, 85, or 10. The invention can theoretically use the adhesive tape to stick the layered material for more times, but the excessive sticking times can not improve the yield of the two-dimensional atomic crystal.
As a preferable technical scheme of the invention, the surface of the silicon chip is plated with an oxide layer.
Wherein, the oxide layer is silicon oxide, and the thickness of the oxide layer can be any one of 90nm, 280nm or 300 nm. The oxide layer plated on the surface of the silicon wafer in the invention is silicon oxide, but the thickness of the oxide layer of the silicon wafer with different specifications is different, and the oxide layers with the 3 thicknesses are generally applied in the industry, and 300nm is preferred in the invention because the optical microscope contrast of the silicon wafer with the specification is good.
In a preferred embodiment of the present invention, the chloroauric acid solution has a viscosity of 0.2 to 5mmol/L, such as 0.2mmol/L, 0.5mmol/L, 1mmol/L, 1.5mmol/L, 2mmol/L, 2.5mmol/L, 3mmol/L, 3.5mmol/L, 4mmol/L, 4.5mmol/L, or 5mmol/L, but the viscosity is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable, preferably 1 mmol/L.
In a preferred embodiment of the present invention, the silicon wafer is immersed in the chloroauric acid solution at a temperature of 20 to 80 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃, but the temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the silicon wafer is soaked in the chloroauric acid solution for 20-60 min, such as 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
In a preferred embodiment of the present invention, the silicon wafer is immersed in water for 20 to 60min, such as 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but the immersion time is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In the present invention, the method for removing the residual moisture on the surface of the silicon wafer may be any one of drying, natural airing and nitrogen blow drying, and preferably nitrogen blow drying.
As a preferred technical scheme of the present invention, the thinning method comprises:
using adhesive tape to MX2The layered material is repeatedly pasted for 1-100 times, wherein M is any one of transition metals, X is any one of VIA group elements, a sample pasted on the adhesive tape is transferred to a silicon wafer with an oxide layer plated on the surface, the silicon wafer with the sample is soaked in a chloroauric acid solution of 0.2-5 mmol/L for 20-60 min at 20-80 ℃, then the silicon wafer is soaked in water for 20-60 min, and residual moisture on the surface of the silicon wafer is removed to obtain the binary atomic crystal.
Compared with the prior art, the invention at least has the following beneficial effects:
the invention provides a controllable thinning method of a transition metal chalcogenide two-dimensional atomic crystal, which adopts chloroauric acid to process a two-dimensional material, can quickly thin the two-dimensional material, is simple to operate and high in production efficiency, and can produce the two-dimensional atomic crystal with a large thin layer area.
Drawings
FIG. 1 is an optical micrograph of molybdenum sulfide on a silicon wafer before treatment in example 1;
FIG. 2 is an optical micrograph of molybdenum sulfide on a silicon wafer after treatment in example 1;
FIG. 3 is a Raman spectrum of molybdenum sulfide at the same position on the silicon wafer before and after the treatment in example 1;
FIG. 4 is a photoluminescence spectrum of molybdenum sulfide at the same position on the silicon wafer before and after the treatment in example 1;
FIG. 5 is an optical micrograph of molybdenum sulfide on a silicon wafer before treatment in example 2;
FIG. 6 is an optical micrograph of molybdenum sulfide on a silicon wafer after treatment in example 2;
FIG. 7 is a Raman spectrum of molybdenum sulfide at the same position on the silicon wafer before and after the treatment in example 2;
FIG. 8 is a photoluminescence spectrum of molybdenum disulfide at the same position on a silicon wafer before and after treatment in example 2;
FIG. 9 is an optical micrograph of tungsten sulfide on a silicon wafer before treatment in example 3;
FIG. 10 is an optical micrograph of tungsten sulfide on a silicon wafer after treatment in example 3;
FIG. 11 is a Raman spectrum of tungsten sulfide at the same position on the silicon wafer before and after the treatment in example 3;
FIG. 12 is a photoluminescence spectrum of tungsten sulfide at the same position on the silicon wafer before and after the treatment in example 3;
FIG. 13 is an optical micrograph of tungsten selenide on a silicon wafer before processing in example 4;
FIG. 14 is an optical micrograph of tungsten selenide on a silicon wafer after processing in example 4;
FIG. 15 is a Raman spectrum of tungsten selenide at the same position on a silicon wafer before and after processing in example 4;
FIG. 16 is a photoluminescence spectrum of tungsten selenide at the same position on a silicon wafer before and after processing in example 4;
FIG. 17 is an optical micrograph of molybdenum selenide on silicon wafer prior to processing in example 5;
FIG. 18 is an optical micrograph of molybdenum selenide on silicon wafer after processing in example 5;
FIG. 19 is an optical micrograph of molybdenum selenide on a silicon wafer prior to processing in example 6;
FIG. 20 is an optical micrograph of molybdenum selenide on a silicon wafer prior to processing in example 6;
FIG. 21 is a Raman picture of molybdenum selenide on a silicon wafer before and after processing in example 6;
FIG. 22 is a graph showing the change in thickness reduction with concentration of gold chlorate solution;
FIG. 23 is a graph of thinning versus process temperature;
FIG. 24 is a graph of thinning versus process time.
The present invention is described in further detail below. The following examples are only some examples of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a method for thinning a two-dimensional atomic crystal of a transition metal chalcogenide, which comprises the following steps:
repeatedly sticking the block body for 8 times by using an adhesive tape, transferring a sample stuck on the adhesive tape to a silicon wafer with an oxide layer plated on the surface, soaking the silicon wafer with the sample in a chloroauric acid solution of 1mmol/L for 30min at 25 ℃, soaking the silicon wafer in water for 30min, and removing residual moisture on the surface of the silicon wafer to obtain the MoS2A two-dimensional atomic crystal.
In general, optical microscope contrast is the most concise and effective method for determining the number of layers of a two-dimensional material, as shown in FIG. 1, the entire MoS before thinning2The layer is thicker and the transmittance is lower, compared with the sample before treatment, the sample after treatment as shown in figure 2 has the phenomenon of obvious thinning, and most of the sheet layer is semitransparent. And further combining the Raman spectrum and the photoluminescence spectrum to perform thinning verification. According to the literature report, the Raman spectrum of molybdenum sulfide has two characteristic peaks, namely, the peak is positioned at 384cm-1E of (A)1 2gAnd is located at 405cm-1A of (A)1gPeaks representing phonon vibration modes of sulfur atoms and molybdenum atoms in the plane of molybdenum sulfide and vibration modes between layers of molybdenum sulfide, respectively. The Raman peak position of the molybdenum sulfide has the characteristic of layer number dependence, namely, as the layer number of the sample increases, E1 2gThe peak will be red shifted, and A1gThe peak will blue shift, so that the displacement difference between the two peak positions becomes large. However, this rule applies only to samples of relatively thin thickness (. ltoreq.6 nm). For the judgment of thick layer samples, we need to introduce the Raman peak of the silicon wafer as a reference. Generally, the light transmittance of the thin layer sample is higher than that of the thick layer sample, so that a strong substrate silicon Raman peak and a weak sample characteristic peak exist, and at this time, the ratio of the substrate to the sample Raman peak can be used as the basis for judging the thickness. Likewise, photoluminescence spectroscopy can be used to detect the number of layers in a sample. Typically, the single layer of transition metal chalcogenide is a direct bandgap semiconductor. A single layer sample has a stronger photoluminescence intensity relative to a multilayer sample of indirect bandgap semiconductors. As in fig. 3, the MoS before processing2The Raman peak positions are respectively from 383.6cm-1And 406.5cm-1Moved to 384.3cm-1And 404.8cm-1Peak position difference 23cm-1Reduced to 20.5cm-1Furthermore, in the photoluminescence spectrum, the luminescence intensity of the sample after the treatment was significantly increased, and it was also confirmed that the thinning of the sample was achieved after the treatment.
Example 2
The embodiment provides a method for thinning a two-dimensional atomic crystal of a transition metal chalcogenide, which comprises the following steps:
MoS using adhesive tape2The two-dimensional material single crystal is repeatedly pasted for 5 times, a sample pasted on the adhesive tape is transferred to a silicon wafer with an oxide layer plated on the surface, the silicon wafer with the sample is soaked in 0.5mmol/L chloroauric acid solution for 40min at 50 ℃, then the silicon wafer is soaked in water for 40min, and residual moisture on the surface of the silicon wafer is removed to obtain the two-dimensional atomic crystal.
Similar to the evidence in example 1, the contrast of the optical microscope of the sample after treatment is improved as shown in fig. 6, the peak difference of the raman characteristic peak of the molybdenum sulfide sample is reduced as shown in fig. 7, and the photoluminescence spectrum intensity is improved as shown in fig. 8.
Example 3
The embodiment provides a method for thinning a two-dimensional atomic crystal of a transition metal chalcogenide, which comprises the following steps:
using adhesive tape to WS2The two-dimensional material single crystal is repeatedly pasted for 8 times, a sample pasted on the adhesive tape is transferred to a silicon wafer with an oxide layer plated on the surface, the silicon wafer with the sample is soaked in a chloroauric acid solution of 0.5mmol/L for 30min at 25 ℃, then the silicon wafer is soaked in water for 30min, and the residual moisture on the surface of the silicon wafer is removed to obtain the two-dimensional atomic crystal.
Similar to the evidence in example 1, the tungsten sulfide sample before treatment appeared yellowish white as in fig. 9, because the sample was too thick to reflect the incident light of the optical microscope greatly, and thus appeared brighter in the gray scale, while the sample after treatment showed blue-green with some light transmittance, and appeared darker in the gray scale, reflecting the thinning of the sample, as in fig. 10. Different from molybdenum sulfide, the judgment of the layer number of tungsten sulfide by using Raman spectrum is that the peak position is no longer a sensitive change index, the intensity of two characteristic peaks and the peak intensity relative to the substrate silicon wafer are more favorable judgment bases, as shown in FIG. 11, the peak intensity of the substrate silicon wafer is obviously improved after treatment, and simultaneously E1 2gAnd A1gThe peak intensity ratio of the tungsten sulfide is obviously improved, which shows that the tungsten sulfide after treatment has good thinning effect on the whole. In addition, as can be seen from fig. 12, the photoluminescence spectrum of tungsten sulfide after the treatment is improved by 3 orders of magnitude, which also proves the judgment of thinning.
Example 4
The embodiment provides a method for thinning a two-dimensional atomic crystal of a transition metal chalcogenide, which comprises the following steps:
using adhesive tape to WSe2The two-dimensional material single crystal is repeatedly pasted for 10 times, a sample pasted on the adhesive tape is transferred to a silicon wafer with an oxide layer plated on the surface, the silicon wafer with the sample is soaked in a chloroauric acid solution of 0.5mmol/L for 30min at 25 ℃, then the silicon wafer is soaked in water for 30min, and residual moisture on the surface of the silicon wafer is removed to obtain the binary atom crystal.
Similar to the evidence in example 3, the tungsten sulfide sample before treatment appeared yellowish white as in fig. 13, since the sample was too thick to be optically clearThe incident light of the microscope is greatly reflected and is brighter in the gray scale image, while the processed sample is blue-green-purple with certain light transmittance as shown in fig. 14, and is darker in the gray scale image, so that the thinning of the sample is reflected. Different from molybdenum sulfide and tungsten sulfide, the Raman spectrum is used for judging the number of layers of tungsten selenide, namely, the peak position is no longer a sensitive change index and is 308cm-1The existence of the left and right characteristic peaks and the peak intensity relative to the substrate silicon wafer are more favorable judgment criteria. Typically 308cm-1The presence of this peak was not detectable in the multilayer samples, but in the monolayer samples. With reference to FIG. 15, it can be seen that HAuCl has passed through4The fact that we successfully prepared a single layer sample of tungsten selenide is also supported in the intense photoluminescence spectrum peak of fig. 16.
Example 5
The embodiment provides a method for thinning a two-dimensional atomic crystal of a transition metal chalcogenide, which comprises the following steps:
use of adhesive tape to MoSe2The two-dimensional material single crystal is repeatedly pasted for 5 times, a sample pasted on the adhesive tape is transferred to a silicon wafer with an oxide layer plated on the surface, the silicon wafer with the sample is soaked in 0.2mmol/L chloroauric acid solution for 60min at the temperature of 20 ℃, then the silicon wafer is soaked in water for 60min, and residual moisture on the surface of the silicon wafer is removed to obtain the binary atom crystal. As shown in FIGS. 17 and 18, the contrast of the same sheet layer undergoes obvious thinning change before and after treatment
Example 6
The embodiment provides a method for thinning a two-dimensional atomic crystal of a transition metal chalcogenide, which comprises the following steps:
use of adhesive tape to MoSe2The two-dimensional material single crystal is repeatedly pasted for 10 times, a sample pasted on the adhesive tape is transferred to a silicon wafer with an oxide layer plated on the surface, the silicon wafer with the sample is soaked in 5mmol/L chloroauric acid solution for 20min at the temperature of 80 ℃, then the silicon wafer is soaked in water for 20min, and residual moisture on the surface of the silicon wafer is removed to obtain the two-dimensional atomic crystal. The contrast of the unified sheet before and after the treatment is obvious in FIGS. 19 and 20The thinning of (3) is varied. With simultaneous reference to FIG. 21, following MoSe according to the literature2The Raman peak at 240cm-1 part of the reduced layer number generates a certain red shift phenomenon, so that the treated MoSe can be known2The number of layers is reduced compared with the number of layers before treatment.
The silicon wafer used in the embodiments of the present invention is a silicon wafer plated with silicon oxide having a thickness of 300 nm.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (6)

1. A controllable thinning method of a transition metal chalcogenide two-dimensional atomic crystal is characterized by comprising the following steps:
repeatedly sticking the layered material by using an adhesive tape, transferring a sample stuck on the adhesive tape to a silicon wafer with an oxide layer plated on the surface, soaking the silicon wafer with the sample in a chloroauric acid solution with the temperature of 20-80 ℃ and the concentration of 0.01-50 mmol/L for 1-60 min, then soaking the silicon wafer in water for a certain time, and removing residual moisture on the surface of the silicon wafer to obtain the thinned binary atomic crystal;
the layered material is MX2M comprises any one of Mo, W, Ta or Nb or a mixture thereof, and X comprises any one of S, Se or Te or a mixture thereof.
2. The thinning method according to claim 1, wherein the number of times the tape is repeatedly stuck to the layered material is 1 to 100.
3. The thinning method according to claim 1, wherein the silicon wafer has a surface oxide layer thickness of 10-1000 nm.
4. The thinning method according to claim 1, wherein the concentration of the chloroauric acid solution is 1 to 5 mmol/L.
5. The thinning method according to claim 1, wherein the silicon wafer is immersed in water for 1-60 min.
6. The thinning method according to any one of claims 1 to 5, wherein the thinning method is:
using adhesive tape to make block layer MX2Repeatedly pasting the material for 1-100 times, wherein M is any one of transition metals, X is any one of chalcogen elements, transferring a sample pasted on the adhesive tape to a silicon wafer with an oxide layer plated on the surface, soaking the silicon wafer with the sample in 0.01-50 mmol/L chloroauric acid solution for 1-60 min at 20-80 ℃, and then soaking the silicon wafer in water for 1-60 min to remove residual moisture on the surface of the silicon wafer to obtain the thinned two-dimensional atomic crystal.
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CN106966371B (en) * 2017-04-28 2019-04-02 福州大学 A kind of method of liquid phase removing two chalcogenide nanometer sheet of transition metal
CN107190319A (en) * 2017-05-17 2017-09-22 暨南大学 A kind of preparation method and application of few layer molybdenum trioxide two-dimensional atomic crystal nanometer sheet
CN107324320A (en) * 2017-07-10 2017-11-07 安徽理工大学 A kind of method that mechanical shearing prepares two-dimension nano materials
CN107434261A (en) * 2017-07-19 2017-12-05 中国石油大学(北京) A kind of overcritical method for peeling off transient metal sulfide of macromolecule auxiliary
CN107555423B (en) * 2017-08-29 2019-12-27 雅迪科技集团有限公司 Stripping solution for preparing two-dimensional nano material and application thereof
CN107500281B (en) * 2017-09-15 2020-10-13 北京师范大学 Stripping method of two-dimensional material
CN107720825B (en) * 2017-11-30 2019-02-19 平顶山学院 A kind of method that simple intercalation stripping obtains molybdenum disulfide nano sheet
CN107827157B (en) * 2017-12-01 2020-04-21 济南大学 Liquid phase stripping method for monolayer molybdenum disulfide

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