KR101633631B1 - Exfoliationg method of semiconducting material for preparing 2d material using silk - Google Patents
Exfoliationg method of semiconducting material for preparing 2d material using silk Download PDFInfo
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- KR101633631B1 KR101633631B1 KR1020150112896A KR20150112896A KR101633631B1 KR 101633631 B1 KR101633631 B1 KR 101633631B1 KR 1020150112896 A KR1020150112896 A KR 1020150112896A KR 20150112896 A KR20150112896 A KR 20150112896A KR 101633631 B1 KR101633631 B1 KR 101633631B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/76—Making of isolation regions between components
- H01L21/762—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers
- H01L21/7624—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology
- H01L21/76251—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology using bonding techniques
- H01L21/76259—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology using bonding techniques with separation/delamination along a porous layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
- H01L27/1262—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate
- H01L27/1266—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate the substrate on which the devices are formed not being the final device substrate, e.g. using a temporary substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/30—Technical effects
- H01L2924/35—Mechanical effects
- H01L2924/351—Thermal stress
- H01L2924/3512—Cracking
- H01L2924/35121—Peeling or delaminating
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Abstract
More particularly, the present invention relates to a method of peeling a semiconductor material using silk, and more particularly, to a method of peeling a semiconductor material by using a silk, To a method of peeling a semiconductor material capable of obtaining a sufficient peeling effect.
Description
More particularly, the present invention relates to a method of peeling a semiconductor material using silk, and more particularly, to a method of peeling a semiconductor material by using a silk, To a method of peeling a semiconductor material capable of obtaining a sufficient peeling effect.
Semiconductor materials are materials with intermediate properties between metal and insulator. The metal has a very high electrical conductivity due to the absence of a bandgap, but the insulator has a very large band gap, so that even when a specific type of energy such as light is injected, the electrons can not move.
Electronic devices such as transistors, inverters, and phase shifters must be able to turn on / off the system, so they do not show conductivity in the ground state, but they must have a conductive material when certain energy is injected. The material that can be made is a semiconductor.
The semiconductor material has a bandgap of about 0 to 2 eV, so it has the same properties as the insulator at the bottom, but when the appropriate voltage is applied, the surface charge of the material moves and can be converted into a conductive material.
Such semiconductor materials are being studied in various devices such as transistors, batteries, and high capacity capacitors. Proper exfoliation of the material is important for semiconductor materials to be effectively applied to such devices. Removal refers to separating a bulk-type material, usually consisting of a multi-layer, into a thin-walled 2-dimensional material. If the semiconductor material is made of a semiconductor material having a thin thickness of about 1 to 3 layers through peeling, the electron mobility is increased and the band gap is increased due to relatively reduced electron scattering, The process of peeling is very important.
Conventionally, mechanical exfoliation, lithium ion intercalation, and liquid phase method are known as methods for peeling semiconductor materials.
The mechanical peeling method generally refers to a method of peeling a bulk semiconductor material into a thin material by separating the layer of material with the adhesive force of the tape while repeating the peeling off of the semiconductor material of an appropriate size on the adhesive tape. Such a mechanical peeling method has an advantage in that it can be easily peeled off through a tape, but it is not easy to move the peeled 2D material back to a soft substrate having a low strength and a soft nature, have.
Next, the lithium ion intercalation method is a method of peeling a semiconductor material using a solder containing an alkali-based metal. Specifically, when the semiconductor material is immersed in the alkali metal solution for a predetermined period of time, the alkali metal ions are inserted between the layers of the semiconductor material. After the alkali metal solution is removed, the semiconducting material is washed and immersed in the water, hydrogen gas is generated due to the reaction between the water and the alkali metal interposed between the layers, and the adjacent layers are pushed each other due to the pressure of the gas. . In this way, the exfoliated material is very thin and particularly monolayer material can be produced, but the residual ion gives electrons, causing the semiconductor material to undergo phase deformation and degrade the quality of the material This is a factor that causes a lethal adverse effect in an electronic device requiring high reliability and precision.
Finally, the liquid phase method is a method used to replace the intercalating lithium ion intercalation method, in which the interlayer intercalation material is not used but is exfoliated only by using the interaction between the solvent and the semiconductor material. Therefore, it is important to select an appropriate solvent. A surfactant may be used to effectively perform the dispersion, and a solvent capable of minimizing the surface energy between the two materials may be selected. This method has the disadvantage of relatively low peeling effect and low concentration of dispersion although the problem due to the phase deformation of the material can be avoided since the intercalant is not present as compared with the lithium ion intercalation method.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide a method of manufacturing a semiconductor device, in which, in addition to a separation process based on a liquid phase method, The present invention provides a method of peeling a semiconductor material for inducing additional peeling and increasing a dispersion concentration.
According to an aspect of the present invention, there is provided a method of obtaining a semiconductor 2D material by separating a raw material semiconductor material according to an embodiment of the present invention, the method comprising: immersing the raw material semiconductor material in a peeling solvent, a first peeling step of peeling the raw semiconductor material by a phase method; A second peeling step of applying silk to the peeling solution in which the raw semiconductor material is peeled off through the first peeling and dispersed in the peeling solvent; And a precipitate removing step of removing the precipitate that has not been dispersed in the peeling solution.
The raw material semiconductor material may be transition metal dichalcogenides (TMDs) in the first stripping step, and molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ) and diterium molybdenum (MoTe 2 ) , And the like.
A solvent having a value similar to the surface energy (J / m 2 ) of the raw material semiconductor material used in the first peeling step may be selected as the peeling solvent.
In the first peeling step, the starting semiconductor material may be molybdenum disulfide (MoS 2 ), and the peeling solvent may be N-methyl-2-pyrrolidone (NMP).
And a first decomposition treatment step of increasing the dispersion concentration of the peeling solution by performing sonication or ultrasonication of the peeling solution after the first peeling step.
The silk applied in the second peeling step is preferably an epoxy treated silk.
And a second decomposing step of increasing the dispersion concentration of the peeling solution by sonication or ultrasonication of the peeling solution after the second peeling step.
In the precipitate removing step, the precipitate can be removed through centrifugation.
In order to achieve the above-mentioned object, the semiconductor-to-silicate nanotube sheet according to another embodiment of the present invention is manufactured by the peeling method as described above, and the peeled semiconductor 2D material and the silk are bonded by non- And a semiconductor device using the same.
The method of separating a semiconductor material using the silk according to the present invention as described above is based on a liquid phase method and thus has no adverse effect due to the phase deformation of a semiconductor material unlike the case of performing separation by a lithium ion intercalation method. Thereby inducing additional exfoliation to obtain a high peeling efficiency and a dispersion concentration.
In addition, it is possible to maximize the yield of peeling through optimal conditions for the semiconductor material and the peeling solvent, the (sonic) decomposition treatment and the centrifugation, and finally, the relatively strong non-covalent bonding such as pi-pi bond and hydrophobic bond The present invention can broaden the range applicable to electronic devices by fabricating a hybrid material that takes advantage of the advantages of silk and semiconductor materials and has various characteristics.
In addition, it is possible to quickly calculate the dispersion concentration even in a small amount by performing only vacuum filtration once without performing mass synthesis or additional processing, which consumes a lot of time and cost in the process of confirming the dispersion concentration of the final solution .
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram illustrating the entire summary of the present invention.
FIG. 2 is a graph showing absorbance according to a wavelength of injection for a single molybdenum disulfide sample, a single silk sample, and a sample in which the amount of silk is changed according to a preferred embodiment of the present invention.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. Prior to the description, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical concept of the present invention.
Throughout this specification, when a member is " on " another member, this includes not only when the member is in contact with another member, but also when there is another member between the two members.
Throughout this specification, when an element is referred to as "including" an element, it is understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.
The terms "first "," second ", and the like are intended to distinguish one element from another, and the scope of the right should not be limited by these terms. For example, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.
In each step, the identification code is used for convenience of explanation, and the identification code does not describe the order of the steps, and each step may be performed differently from the stated order unless clearly specified in the context. have. That is, each of the steps may be performed in the same order as described, or may be performed substantially concurrently or in the reverse order.
The present invention relates to a method of obtaining a semiconductor 2D material by peeling a raw material semiconductor material, comprising: a first peeling step based on a liquid phase method; a second peeling step of inducing additional peeling by applying silk; And removing the undesired precipitate from the semiconductor material. A schematic diagram of the overall subject matter of the present invention is shown in FIG.
The present invention basically performs the first peeling based on the liquid phase method as mentioned above. Specifically, the raw material semiconductor material is firstly immersed in a peeling solvent to peel off the raw material semiconductor material through a liquid phase method.
Semiconductor materials are typically graphene, transition metal-dicalcogenides (TMDs), boron nitride, and the like. Graphene has been studied in various fields such as sensors and transparent electrodes because it has the advantage of having high electron mobility, strength, transparency and so on, which is a single layer of graphite separated from a thick graphite layer. However, graphene is often classified as a semiconducting material but has the disadvantage that it can not be used for devices such as transistors because there is no bandgap. Materials used in transistors require proper mobility and current on / off ratio, and transition metal-dicalcogenide materials are suitable for this purpose.
The transition metal-dicalogenconide material is composed of one transition metal atom located in groups 4 to 6 on the periodic table and a group 16 element of chalcogen, such as oxygen (O), sulfur (S), selenium (Se), and tellurium Two substances are combined. Materials suitable for use in the present invention as transition metal-dicalcogenide materials include molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ) and molybdenum disulfide (MoTe 2 ) Therefore, it is known that the bandgap increases. Therefore, it is suitable for the transistor application because the bandgap can be adjusted according to the thickness. Particularly, molybdenum disulfide (MoS 2 ) is most preferable.
The exfoliating solvent used in the first exfoliating step should be selected as the solvent to be compatible with the semiconductor material used. Specifically, it is preferable to employ a solvent capable of effectively removing the semiconductor material by interaction with the semiconductor material to increase the degree of dispersion of the material. The most important parameter to be considered here is the surface energy (surface tension), and as the surface energy of each of the semiconductor material and the solvent has a similar value, the semiconductor material can be well stripped and the dispersion can be increased. In one preferred embodiment, when molybdenum disulfide (MoS 2 ) is used as a semiconductor material, the surface energy of the molybdenum disulfide is 46.5 mJ / m 2, so that the surface energy of the molybdenum disulfide is 40.1 mJ / m 2 , It is most preferred to use N-methyl-2-pyrrolidone (NMP). It is preferable to disperse molybdenum disulfide in NMP to basically maximize the dispersion concentration even in the first peeling step.
As mentioned above, it is possible to employ a solvent that is optimal for use as a dispersion solvent in each semiconductor material, and the physical properties to be considered here are the surface energy values of the semiconductor material and the solvent, respectively. Considering the surface energy of most semiconductor materials including the semiconductor material used in the present invention, it is effective to use a solvent having a surface energy in the range of 30 to 40 mJ / m 2 for dispersion.
On the other hand, when the solubility parameter between the solute and the solvent is considered, the dispersion effect is maximized when the exfoliation energy is minimized, which can be explained by the concept of enthalpy of mixing. The basic equation is as follows.
(σ g , σ sol is the root value of the surface energy, Φ is the relative volume ratio of the substance (solute) to the whole mixture, and T flake is the thickness of the substance)
Since the enthalpy value H mix is a property that can not have a negative value, it has the theoretical minimum value when the surface energy value (σ g ) of the solute and the surface energy value (σ sol ) of the solvent are the same. In other words, preferably, the similarity of the surface energy of each of the semiconductor material and the dispersion solvent means that the material can be peeled with the lowest energy when most closely matching. Therefore, the meaning of 'similar value' in the present invention should be interpreted to mean that the smaller the difference in surface energy between the semiconductor material and the dispersing solvent is, the more preferable the boundary is not ambiguous.
In addition, in terms of the Hildebrand solubility parameter, which is an upgraded parameter from the concept of surface tension, the degree of various interactions between the two materials (semiconductor material and dispersion solvent) This is an element that can be considered in adopting.
After the first peeling step, sonication or ultrasonication can be performed on the peeling solution to obtain the maximum dispersion concentration (first decomposition step). In order to maximize the dispersion concentration, the processing time at which the dispersion concentration is saturated at the maximum should be calculated.
Sonic / ultrasonic processing is a treatment method that injects sound energy above 20 kHz into particles and separates the aggregated particles. There are two types of probe method and bath method, and the electron processing efficiency is high in the same time. This treatment method has been used to extract genetic material such as DNA and RNA inside a cell by injecting sound energy into a biological sample such as a cell and destroying the cell membrane. This treatment method can also be used for organic substances and inorganic substances. In particular, the solubility can be increased by injecting sonic / ultrasonic waves to eliminate intermolecular interactions of the material. It can also be used to inject energy to proceed a specific chemical reaction and is also useful for removing gaseous components dissolved in a solution. In particular, nanotechnology such as the present invention can be an effective means for dispersing nanoparticles in a solvent.
Next, after the first delamination is performed, a second delamination step is performed in which silk is applied to the delamination solution in which the semiconductor material is dispersed to induce additional delamination.
Silk is a material with very high flexibility and strength, usually obtained from butterflies or larvae. Initially, secretion protein is contained, which is strong hydrophilic, but in the process of heating and strong acid treatment to make silk solution, protein is removed and it changes to minor characteristic. The structure of this minor characteristic is called a β-sheet structure. By removing the solvent from the thus-prepared silk solution, it becomes possible to finally form a film or a composite structure.
Silk is apt to bind to other materials and to form complexes through bonding such as hydrophobic interaction and π-π stacking. The dominant hydrophobic domain also enhances the strength and elasticity of the silk. In addition, silk can be stretched to 20-25% of its original length without breaking, which has the advantage of retaining its shape even under various loads. At this time, when epoxy is applied to the silk, a cross-link between the silk molecules is formed, so that a higher strength silk can be formed.
Silicon and semiconducting materials, especially molybdenum disulfide, can achieve a significant level of non-covalent bonding, such as a pi-pi bond and a hydrophobic bond. The bond between two layers of adjacent semiconductor material is in the form of a relatively weak van der Waals bond, so that when the added silk is combined with the semiconductor material located in the upper layer region, it naturally induces additional interlayer separation. This makes it possible to maximize the peeling efficiency and the dispersion concentration by drawing additional secondary peeling as compared with the conventional peeling method in which the liquid phase method is performed singly.
In the present invention, a silk fibroin solution may be directly synthesized and used according to a preferred embodiment. Specifically, silk fibroin is synthesized from Bombyx mori cocoon. As described above, secretory proteins having hydrophilic properties are removed through heating in this process, so that a beta-sheet structure having hydrophobic characteristics is obtained. Later, solid-form silk was obtained through freeze-drying from the silk fibroin solution and used.
When the silk solution is directly synthesized and used, first, the transition metal-dicalcogenide material having hydrophobic properties such as molybdenum disulfide is highly hydrophobic and thus can maximize the interaction with them, and the second synthetic silk fibroin solution It is possible to obtain a silk to prevent the structural deformation problem of the silk due to the heat applied to the removal of the solvent component, thereby obtaining a stable solid state silk and ultimately improve the interaction with the semiconductor material.
Meanwhile, FIG. 2 shows a comparison group of a single molybdenum disulfide sample and a single silk sample according to an embodiment of the present invention, and a sample in which 5 mg, 10 mg, and 50 mg of silk were added to a solution in which molybdenum disulfide was first dispersed, Fig. Here, the method of measuring the degree of dispersion is a measurement method using a UV spectrophotometer described later. Referring to FIG. 2, the degree of dispersion of the samples inducing additional peeling by applying silk was higher than that of the single molybdenum disulfide sample. Particularly, as the supply amount of silk increased, the degree of dispersion increased proportionally.
After the silk is added to the peeling solution in the second peeling step, the above-mentioned sonic / ultrasonic treatment can be additionally performed. This can further promote the interaction of the silk with the semiconductor material.
Next, the undissolved precipitate in the final stripping solution is removed. It is preferable to remove the precipitate through centrifugation to maintain a stable solution state. Centrifugation is a method of separating solid particles or liquid fine particles in a liquid by centrifugal force. When two or more substances having different densities are mixed, centrifugal separation is performed. As the rotational speed increases, the centrifugal acceleration becomes much larger than the gravitational acceleration, and the material can be easily separated.
As the centrifugation speed and time increase, the stability increases but the dispersion concentration decreases. On the contrary, as the centrifugation speed and time decrease, the dispersion concentration increases but the stability decreases. Therefore, it is desirable to carry out the experiment while continuously changing the centrifugation speed and time, so that it is desirable to calculate the conditions for obtaining the optimum value in the two conflicting aspects of the two variables.
On the other hand, the Lamber-Beer law can be used to determine the dispersion concentration for the final product. The Lamber-Beer law is a law that can confirm the degree of dispersion of nanomaterials. It is composed of A / l = αC. Where A is the background subtracted absorbance, l is the cell length of the cuvette vessel, α is the extinction coefficient, and C is the dispersion concentration. The background-removed absorbance means a value obtained by subtracting the background scattering from the measured absorbance, and the background scattering means a straight line extracted from the high wavelength region as a value irrelevant to the sample. By subtracting this fraction from the measured absorbance, the inherent absorbance associated with the substance can be calculated. l means the physical length of the cuvette containing the solution and is usually about 10 to 20 mm. α is an intrinsic index showing how strongly a substance absorbs light as a coefficient of absorption. After determining the concentration of the substance in a specific solution and the length of the cuvette through vacuum filtration, the absorbance is measured by a UV spectrophotometer . Therefore, it is possible to calculate the dispersion concentration (C) when three variables A, l, and α are identified.
Conventionally, in order to confirm the dispersion concentration, a method is employed in which the solution is filtered through a vacuum filter paper, the solvent component is evaporated through heating, and the mass of the final solid component is confirmed to confirm the concentration. However, this method has drawbacks such as that it takes much time to remove the solvent and it requires mass synthesis for vacuum filtration. Therefore, in the present invention, vacuum filtration can be performed only once, and this disadvantage can be solved. This is because even if silk is added to the exfoliation solution, the silk does not show the optical properties for a wide range of wavelengths of the order of 200 to 1000 nm and thus does not affect the measured absorbance value. Accordingly, even if silks are added, the trend of the data is not changed and the overall graph shape is constant. As a result, only one vacuum filtration can be performed to obtain the extinction coefficient, and this coefficient can be applied to all samples, so that there is an advantage that mass synthesis or multiple vacuum filtration is unnecessary.
The present invention provides a semiconductor-silk nanosheet composite in which a semiconductor 2D material and silk are bonded together by non-covalent bonding, and a semiconductor device using the same, which is manufactured through the above-described separation method according to another preferred embodiment.
By separating the semiconductor material by the above method, not only the peeling efficiency can be increased but also the composite of the semiconductor material and the silk material bonded by the non-covalent bond can be obtained. Nanosheet composites are widely applicable to devices in various fields.
The present invention is not limited to the above-described specific embodiment and description, and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention as claimed in the claims. And such modifications are within the scope of protection of the present invention.
Claims (11)
A first peeling step of immersing the raw material semiconductor material in a peeling solvent and peeling the raw semiconductor material by a liquid phase method;
A second peeling step of applying silk to the peeling solution in which the raw semiconductor material is peeled off through the first peeling and dispersed in the peeling solvent; And
A precipitate removing step of removing the undissolved precipitate in the peeling solution;
Wherein the method comprises the steps of:
Wherein the source semiconductor material is a transition metal-dichalcogenide (TMDs) in the first stripping step.
Wherein the raw material semiconductor material in the first peeling step is at least one selected from the group consisting of molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ) and molybdenum disulfide (MoTe 2 ) Method of exfoliation of material.
Wherein a solvent having a value similar to the surface energy (J / m 2 ) of the raw material semiconductor material used in the first peeling step is selected as the peeling solvent and used.
Wherein the raw material semiconductor material is molybdenum disulfide (MoS 2 ) and the peeling solvent is N-methyl-2-pyrrolidone (NMP) in the first peeling step. A method for peeling a semiconductor material.
A first decomposition treatment step of increasing the dispersion concentration of the peeling solution by performing sonication or ultrasonication of the peeling solution after the first peeling step;
And removing the semiconductor material from the semiconductor material.
Wherein the silk applied in the second peeling step is an epoxy-treated silk.
A second decomposition treatment step of increasing the dispersion concentration of the peeling solution by performing sonication or ultrasonication of the peeling solution after the second peeling step;
And removing the semiconductor material from the semiconductor material.
Wherein the precipitate is removed through centrifugation in the step of removing the precipitate.
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