WO2018186535A1 - Procédé de préparation d'un matériau bidimensionnel à l'aide d'un traitement de surface par inhibiteur d'adsorption - Google Patents

Procédé de préparation d'un matériau bidimensionnel à l'aide d'un traitement de surface par inhibiteur d'adsorption Download PDF

Info

Publication number
WO2018186535A1
WO2018186535A1 PCT/KR2017/006884 KR2017006884W WO2018186535A1 WO 2018186535 A1 WO2018186535 A1 WO 2018186535A1 KR 2017006884 W KR2017006884 W KR 2017006884W WO 2018186535 A1 WO2018186535 A1 WO 2018186535A1
Authority
WO
WIPO (PCT)
Prior art keywords
adsorption
dimensional material
surface treatment
metal
inhibitor
Prior art date
Application number
PCT/KR2017/006884
Other languages
English (en)
Korean (ko)
Inventor
안지훈
전우진
정성준
Original Assignee
한국해양대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한국해양대학교 산학협력단 filed Critical 한국해양대학교 산학협력단
Publication of WO2018186535A1 publication Critical patent/WO2018186535A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/24—Deposition of silicon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber

Definitions

  • the present invention relates to a method for producing a two-dimensional material that improves the electrical properties by increasing the crystal size by the introduction of the adsorption inhibitor.
  • Two-dimensional materials represented by graphene, silicene, phosphorine, hexagonal boron nitride, and metal chalcogenides are planar interatomic bonds. Refers to a material made of strong covalent bonds, while weak van der Waals bonds to the other out of phase.
  • These two-dimensional materials can be formed very thin ( ⁇ 1 nm) in molecular layers because of the nature of their bonding.
  • it exhibits much higher charge mobility and photo-electronic conversion efficiency than conventional semiconductor materials, and has the advantage of making transparent and flexible materials. Therefore, it is expected to be widely used as the next-generation electronic device and photoelectric device. Basic and applied researches on this are being actively conducted.
  • CVD chemical vapor deposition
  • atomic layer deposition has been mentioned as the only alternative as a process for mass production of electronic devices and products using two-dimensional materials.
  • the crystal size of the two-dimensional material is very small due to the characteristics of the atomic layer deposition method, and the electrical properties thereof are very low compared to the known ones.
  • the present invention is to provide a method for producing a two-dimensional material having a uniform thin film form over a large area, and to provide a method for producing a two-dimensional material having excellent crystal structure and charge mobility while using an atomic layer deposition method. For that purpose.
  • the present invention comprises the steps of (1) adsorbing the adsorption inhibitor by introducing an adsorption inhibitor to the substrate having an adsorption site (adsorption site); (2) forming a two-dimensional material at an adsorption site where the adsorption inhibitor is not adsorbed by using atomic layer deposition; And (3) crystallizing the formed two-dimensional material. It provides a method for producing a two-dimensional material using an adsorption inhibiting surface treatment comprising a.
  • the method for producing a two-dimensional material using the adsorption-inhibiting surface treatment according to the present invention it is possible to obtain a two-dimensional material having a uniform thin film form over a large area, and to apply at a low process temperature to apply a plastic substrate that is weak to heat. As the crystal structure of the two-dimensional material is improved, the two-dimensional material having excellent charge mobility can be produced.
  • Figure 1 shows the comparison of the metal precursor adsorption behavior, three-dimensional reaction formula and the reaction energy in the manufacturing process of the two-dimensional material according to Examples 1-2 and Comparative Examples 1-2.
  • Figure 2 shows the results of measuring the adsorption density of the metal precursor in the manufacturing process of the two-dimensional material according to Example 1 and Comparative Example 2.
  • Figure 3 shows the Raman analysis of the two-dimensional material according to Example 1 and Comparative Example 2.
  • Figure 4 shows the results of measuring the adsorption density of the metal precursor in the manufacturing process of the two-dimensional material according to Example 1 and Example 2.
  • Figure 6 shows the results of the AFM analysis for the two-dimensional material according to Examples 1-2 and Comparative Examples 1-2.
  • Example 8 is a transmission microscope (TEM) photograph of a side portion of a two-dimensional material according to Example 2 and Comparative Examples 1 to 2;
  • FIG. 9 is a transmission microscope (TEM) photograph of a planar portion of a two-dimensional material prepared according to Example 2 and Comparative Example 1.
  • TEM transmission microscope
  • FIG. 10 illustrates a result of measuring bottom gate voltage (V g ) -drain current (I ds ) of a FET including a two-dimensional material manufactured according to Comparative Example 1.
  • V g bottom gate voltage
  • I ds drain current
  • FIG. 11 shows a result of measuring bottom gate voltage (V g ) -drain current (I ds ) of a FET including a two-dimensional material prepared according to Example 2.
  • V g bottom gate voltage
  • I ds drain current
  • the present invention relates to a method for preparing a two-dimensional material having improved crystal size by the introduction of an adsorption inhibitor to improve electrical properties, and to a method for producing a two-dimensional material showing high crystallinity and charge mobility while using atomic layer deposition. It is about.
  • the term 'adsorption site' refers to a functional group present on the surface of the substrate, and refers to a site where a precursor or the like may be adsorbed onto the substrate by reacting with a precursor of a two-dimensional material. .
  • the ALD reactor described herein is used in the manufacturing process of the two-dimensional material and is not specifically described in the embodiments of the present invention, but will be easily understood by those skilled in the art. It is made up of possible configurations.
  • step (1) of adsorbing the adsorption inhibitor will be described.
  • the substrate may be any substrate, and may be a rigid or flexible substrate.
  • it may be a glass substrate, a plastic substrate, or a substrate made of another material, and a substrate made of a transparent plastic material may be used if necessary.
  • the substrate may be a SiO 2 / Si substrate.
  • the substrate is characterized by having an 'adsorption site' on its surface. In addition to the adsorption site, precursors of two-dimensional materials can be adsorbed, as well as adsorption inhibitors and adsorption activators, which will be described later.
  • the adsorption inhibitor refers to a material that is treated on the surface of the substrate before the two-dimensional material is adsorbed on the substrate, and means a material that serves to prevent the precursor of the two-dimensional material from adsorbing to the adsorption site of the substrate.
  • the type of the adsorption inhibitor is not particularly limited as long as it prevents the precursor of the two-dimensional material from adsorbing to the adsorption site of the substrate.
  • alcohol compounds having 1 to 10 carbon atoms perylene-3,4,9,10-tetra -Tetracarboxylic acid tetra potassium salt (PTAS), copper (II) 1, 2, 3, 4, 8, 9, 10, 11, 15, 16, 17, 18,22,23,24,25-hexadecafluoro-29H, 31H-phthalocyanine ⁇ copper (II) 1,2,3,4,8,9,10,11,15,16,17, 18,22,23,24,25-hexadecafluoro-29H, 31H-phthalocyanine: F 16 CuPc ⁇ , perylene-3,4,9,10-tetracarboxylic dianhydride ⁇ perylene-3,4,9,10-tetracarboxylic acid dianhydride: PTCDA ⁇ , copper (II) phthalocyanine ⁇ copper (II) phthalocyanine: CuPc ⁇ , dibenzo ⁇ (f, f ′)-4,4 ′, 7,7′
  • the adsorption site is present at a specific density on the surface of the substrate, when using the ALD method is the most important factor in determining the growth behavior of the initial thin film.
  • the precursor of the two-dimensional material is adsorbed to the adsorption site according to a specific probability affected by chemisorption kinetics, and even when applying an adsorption inhibitor or an adsorption activator to the substrate, respectively Adsorbed on the site.
  • adsorption inhibitors or adsorption activators When adsorbed to the adsorption sites of the substrate, they exhibit different adsorption behavior for precursors of two-dimensional materials because they are chemically different from the adsorption sites that are not pretreated.
  • the adsorption activator forms new covalent bonds with the functional groups of the adsorption site, but is adsorbed on the substrate, but forms relatively unstable bonds, thereby increasing the reactivity of the adsorption site thereby increasing the adsorption probability of the two-dimensional material precursor.
  • the adsorption inhibitor since the adsorption inhibitor covalently bonds with the functional group of the adsorption site to form a relatively stable bond, it lowers the reactivity of the adsorption site, thereby reducing the adsorption probability of the two-dimensional material precursor.
  • Step (1) may be performed at a temperature of 200 to 500 ° C, preferably 250 to 450 ° C, more preferably 300 to 400 ° C. If the temperature of step (1) is less than 200 °C, there is a problem that the adsorption inhibitor is difficult to be sufficiently adsorbed on the adsorption site, when the temperature exceeds 500 °C there is a problem that the use of a substrate weak in heat.
  • step (1) may be performed for 10 to 300 seconds, preferably 10 to 250 seconds, more preferably 10 to 200 seconds. If the advancing time of step (1) is less than 10 seconds, there is a problem in that the adsorption inhibitor is not sufficiently adsorbed, and if it exceeds 300 seconds, the excess adsorption inhibitor is adsorbed so that the two-dimensional material is not sufficiently formed.
  • step (2) of forming the two-dimensional material will be described.
  • Step (2) is characterized by atomic layer deposition.
  • the atomic layer deposition method refers to a nano thin film deposition technique using a monoatomic layer phenomenon, it is possible to deposit an ultrafine thin film having an atomic layer thickness.
  • a two-dimensional material refers to a material composed of weak van der Waals bonds on the other side of the out-of-phase bonds, whereas the planar interatomic bonds are made of strong covalent bonds, specifically, graphene and silicene. ), Phosphorene, hexagonal boron nitride, and metal chalcogenides.
  • the metal chalcogenide compound may be used as a two-dimensional material.
  • Metal chalcogenide compounds consist of metals and chalcogen elements.
  • the metal chalcogenide compound is at least one metal selected from the group consisting of Mo, W, Nb, Ga, Ta, Zr, Ti, Hf, Sn, In and Ge, S, Se and Te It may be composed of one or more chalcogen elements selected from the group consisting of.
  • the metal chalcogenide compound may have a chemical formula of MX, MX 2 or M 2 X 3 .
  • M is a metal, preferably Mo, W, Nb, Ga, Ta, Zr, Ti, Hf, Sn, In and Ge may be any one selected from the group consisting of.
  • X is a chalcogen element, and preferably may be any one selected from the group consisting of S, Se, and Te.
  • step (2) is (a) introducing a metal precursor into the reactor to the metal adsorption site where the adsorption inhibitor is not adsorbed Adsorbing; (b) purging the metal precursor from inside the reactor; (c) introducing a chalcogen precursor into the reactor to synthesize a metal chalcogenide compound; And (d) purging the chalcogenide precursor from the inside of the reactor.
  • Step (2) may be carried out at a temperature of 100 to 400 °C, preferably at a temperature of 150 to 350 °C, more preferably 200 to 300 °C.
  • step (2) may be performed for 60 to 240 seconds, preferably 80 to 200 seconds, more preferably 100 to 160 seconds.
  • step (3) for crystallizing the two-dimensional material will be described.
  • Step (3) may be performed at a temperature of 350 to 500 ° C, preferably 400 to 500 ° C, more preferably at a temperature of 420 to 480 ° C. In addition, step (3) may be performed for 5 to 120 seconds, preferably 5 to 90 seconds, more preferably 5 to 60 seconds. When the temperature and the performance time of step (3) satisfy the above range, it is possible to effectively induce the crystallization of the two-dimensional material.
  • step (1) to (3) may be carried out at a temperature of 500 °C or less.
  • a temperature of 500 °C or less When forming a two-dimensional material by the conventional CVD method requires a high process temperature of 600 °C or more, there was a limitation in applying a substrate of a material susceptible to heat.
  • the present invention by the ALD method can form a thin film of a two-dimensional material at a relatively low temperature, has the advantage that can be applied to a substrate of various materials as needed.
  • Two-dimensional material the average particle size (hereinafter, d grain) 20 to be 120 nm, and preferably from 25 to 100 nm, more preferably of from 30 to 80 nm d grain Can have
  • d grain of the two-dimensional material satisfies the above range, a two-dimensional material having an excellent crystal structure can be obtained.
  • the proportion of particles having a particle size of 10 nm or more (hereinafter, c grain ) among the particles constituting the two-dimensional material may be 20 to 100%, preferably 25 to 98%, more preferably 30 to 95% Can be.
  • c grain of the two-dimensional material satisfies the above range, it is possible to obtain a two-dimensional material showing excellent charge mobility.
  • the excellent electrical properties of the two-dimensional material are due to the excellent crystal structure of the two-dimensional material, and securing an excellent crystal structure becomes an important factor for improving the electrical properties.
  • the crystal structure of the two-dimensional material depends on the concentration of precursor adsorbed at the initial stage of formation of the two-dimensional material.
  • the precursor concentration of the adsorbed two-dimensional material directly affects the nuclear density of the two-dimensional material on the surface of the substrate, and d grain and c grain of the crystal structure of the two-dimensional material according to the increase or decrease of the nuclear density of the two-dimensional material. This is greatly affected.
  • the nuclear density of the two-dimensional material increases because the precursor of the two-dimensional material is sufficiently adsorbed on the substrate. If the nuclear density is increased, the crystal structure of the two-dimensional material does not grow enough to form a thin film. However, when treating the adsorption inhibitor, the concentration at which the precursor of the two-dimensional material is adsorbed on the substrate is reduced, resulting in a decrease in nuclear density. If the nuclear density is reduced, the crystal structure of the two-dimensional material is fully grown, which can dramatically improve d grain and c grain .
  • the d grain and c grain of the crystal structure forming the two-dimensional material is improved as described above, a thin film of the two-dimensional material having a uniform and continuous layer structure can be obtained, and as described later, a uniform and continuous layer structure can be obtained. It is possible to greatly improve the electrical properties of the two-dimensional material.
  • the two-dimensional material according to the preferred embodiment of the present invention may be characterized by forming a continuous layered structure.
  • the layered structure has a structure of about 3 to 10 layers, and may preferably have a layered structure of 5 to 8 layers, more preferably 6 to 7 layers.
  • it can be characterized by forming a continuous layered structure without interruption over a length of about 150nm or more, and the number of laminated layers is homogeneous.
  • the crystal structure does not grow sufficiently or includes an amorphous portion, thereby forming a non-continuous layered structure.
  • the layered structure is not continuous, it may negatively affect the carrier movement process, which may cause deterioration of electrical characteristics.
  • the two-dimensional material according to the preferred embodiment of the present invention has a continuous layer structure and does not exhibit a decrease in carrier mobility, it is possible to obtain a two-dimensional material having excellent electrical properties.
  • Adsorption inhibitor pretreatment was performed on the substrate using an ALD reactor.
  • the pretreatment step was performed at 350 ° C. for 30 seconds, using a SiO 2 / Si substrate, and using DES (Sigma-Aldrich) as the adsorption inhibitor.
  • the bubbler type canister for DES was maintained at 35 ° C. during the pretreatment.
  • DES was introduced into the reactor with Ar carrier gas and the chamber pressure was maintained at 0.5 torr.
  • the substrate was moved to a loadlock chamber to prevent contamination due to air exposure.
  • the DES remaining in the reactor was then purged with Ar gas and the chamber susceptor was cooled to 250 ° C. for the next step.
  • a metal precursor and a sulfur precursor were introduced into a substrate pretreated with DES to form a metal chalcogenide compound.
  • Mo (CO) 6 UP Chemical
  • DEDS diethyl disulfide
  • Formation of the metal chalcogenide compound was composed of four steps of 'metal precursor supply, Ar purification, sulfur precursor supply and Ar purification', and was performed for 0.5 seconds, 60 seconds, 3 seconds and 60 seconds, respectively.
  • the pressure in the reactor was maintained at 0.5 torr and the reaction temperature was maintained at 250 ° C.
  • the metal precursor was introduced without using a carrier gas by heating the canister to 35 ° C.
  • the sulfur precursor was introduced into the reactor at a flow rate of 100 sccm (standard cubic centimeters per minute) using pure Ar carrier gas (99.999%), and a bubbler-type canister heated to 65 ° C was used.
  • a MoS 2 thin film was prepared in the same manner as in Example 1 except that the pretreatment step using DES was performed for 150 seconds.
  • a MoS 2 thin film was prepared in the same manner as in Example 1 except that the pretreatment step using DES was not performed.
  • the pretreatment was performed for 150 seconds using the adsorption activator DEDS instead of the adsorption inhibitor DES, and the same as in Example 1 except that the bubbler type canister for DEDS was maintained at 60 ° C. during the pretreatment.
  • MoS 2 thin film was prepared by the method.
  • reaction energy was calculated using the Vienna Ab initio Simulation Package (VASP).
  • VASP Vienna Ab initio Simulation Package
  • Generalized gradient approximation for exchange-correlation interactions was applied, and by default, plane waves with kinetic energy below 400 eV were included. Ion position has been updated until you exceed this 0.02eV / ⁇ residual force (residual forces), the electron density is the total energy change 10 - eased until the excess of 5 eV. All calculations were performed at the gamma point, and the tridymite structure was adapted to cover with isolated silanol groups where surface adsorption was most advantageous. In addition, the unit cell is set large enough to minimize spurious interactions between the cells.
  • Figure 1 shows the comparison of the metal precursor adsorption behavior, the three-dimensional reaction equation and the reaction energy in the manufacturing process of the two-dimensional material according to Examples 1 and 2 and Comparative Examples 1 and 2 according to.
  • the effect of the DES preprocessing will be described with reference to FIG. 1.
  • the surface of the SiO 2 / Si substrate is covered with —OH functional groups that serve as adsorption sites.
  • OH bonds are broken through reaction between the metal precursor Mo (CO) 6 and the adsorption site (—OH group), and Mo and O form covalent bonds. The metal precursor can thereby be adsorbed.
  • Examples 1 and 2 undergoing DES pretreatment as an adsorption inhibitor DES reacts with the adsorption site to release ethane thiol to form a covalent bond between oxygen (O) and carbon (C). Since the OC bond thus formed corresponds to a relatively stable bond, it was shown that the reaction in which the metal precursor Mo (CO) 6 was adsorbed to the DES pretreated adsorption site was thermodynamically undesirable.
  • the adsorption site pretreated with DES is expected that the tightly bound ethyl group can block the access of Mo (CO) 6 in three dimensions to further reduce the reactivity.
  • Figure 2 shows the results of measuring the adsorption density of the metal precursor in the manufacturing process of the two-dimensional material according to Example 1 and Comparative Example 2.
  • Mo adsorption density was found to be very low in Example 1 after DES pretreatment.
  • Comparative Example 2 subjected to DEDS pretreatment, as the cycle of the ALD process was increased, the Mo adsorption density was increased almost linearly to clearly confirm the difference in reactivity.
  • Figure 3 shows the Raman analysis of the two-dimensional material according to Example 1 and Comparative Example 2.
  • Example 1 which was subjected to DES pretreatment, a wide peak was observed around 1500 cm ⁇ 1 , unlike the case of Comparative Example 2. This indicates CC bonding, and in Example 1, the surface of the substrate is coated with a composite carbon compound.
  • Figure 4 shows the results of measuring the adsorption density of the metal precursor in the manufacturing process of the two-dimensional material according to Example 1 and Example 2. Referring to FIG. 4, it can be seen that the Mo adsorption density is lower as the pretreatment process time by DES is longer, and in particular, when the DES pretreatment time is 10 seconds or more, the Mo adsorption density is remarkably lowered.
  • X-ray photoelectron spectroscopy (XPS) analysis was performed to confirm and evaluate the chemical structure and stoichiometry of the two-dimensional material prepared according to Example 1, Comparative Examples 1 and 2.
  • Example 5 shows XPS analysis results for the two-dimensional material according to Example 1 and Comparative Examples 1 and 2; Referring to FIG. 5, in the case of Example 1 which was subjected to DES pretreatment, only peaks corresponding to MoS 2 were confirmed. In addition, since the Mo 3d peak moved below the binding energy (BE) value and the intensity of the O 1s peak decreased, it was confirmed that the formation of MoO x was greatly reduced.
  • BE binding energy
  • Figure 6 shows the results of the AFM analysis for the two-dimensional material according to Examples 1-2 and Comparative Examples 1-2.
  • the video image of the surface morphology of samples via the computer calculated the average diameter of the particles (grain d) and the particle size of the coverage of the particles less than 10nm (c grain).
  • the results are summarized in Table 1 below.
  • Figure 7 shows the measurement results for the ratio of the average diameter of the particles to the two-dimensional material according to Example 1 and Example 2 and the particles having a diameter of 10nm or more.
  • Examples 1 and 2 subjected to DES pretreatment showed d grains of 28.49 nm and 75.47 nm, respectively, and 32.2% and 93.16% c grains , respectively.
  • Comparative Example 1 which did not undergo pretreatment, showed only 19.53 nm of d grain and 15.0% of c grain
  • Comparative Example 2 which had undergone DEDS pretreatment, decreased d grain to 3.01 nm and c grain of 3.0. The results were reduced by%. Therefore, in Examples 1 and 2 subjected to the DES pretreatment it was confirmed that the d grain and c grain increased significantly.
  • Results can be successfully controlled with the crystal structure of MoS 2 thin film by modifying the surface of the substrate through the DES pre From the above, and to determine that they can form a MoS 2 thin film of excellent crystal structure having a relatively large particle size there was.
  • FIG. 8 is a transmission microscope (TEM) photograph of a side portion of a two-dimensional material according to Example 2 and Comparative Examples 1 to 2
  • FIG. 9 is a view of a two-dimensional material prepared according to Example 2 and Comparative Examples 1 to 2; Transmission microscopy (TEM) images of planar sections. 8 to 9, although all the samples have almost the same thickness corresponding to about 5 to 7 layers, it can be seen that the microstructure is different from sample to sample.
  • TEM transmission microscope
  • Example 2 after the DES pretreatment, the layered structure parallel to the substrate can be clearly observed. In addition, it can be seen that a continuous layer structure is formed throughout the region (about 150 nm) that can be seen from the TEM photograph, the number of laminated layers is homogeneous, and no amorphous phase is observed.
  • Comparative Example 1 which was not subjected to pretreatment, a partial layer structure was observed, but the number of laminated layers varied, and thus it was confirmed that they were not continuously connected. This means that the MoS 2 particles are not well connected on the entire thin film, which may negatively affect the carrier migration process and cause electrical properties to deteriorate.
  • Comparative Example 2 which was subjected to DEDS pretreatment, the layered structure could not be confirmed, and only randomly scattered small flake layers were identified.
  • XPS analysis of Comparative Example 2 a considerable amount of MoO x was mixed, it can be understood that the higher the MoO x ratio hinders the growth of the MoS 2 structure, and thus a continuous layered structure cannot be formed. have.
  • a bottom gate field effect transistor including an Au / Ti electrode and a 200 nm wide SiO 2 gate insulator was manufactured. .
  • Example 10 and 11 show the results of measuring the bottom gate voltage (V g ) -drain current (I ds ) of the FET including the two-dimensional material according to Comparative Example 1 and Example 2, respectively.
  • V g bottom gate voltage
  • I ds drain current
  • Comparative Example 1 which did not undergo pretreatment, exhibited a p-channel characteristic with a field effect hole mobility of about 0.004 cm 2 V ⁇ 1 s ⁇ 1 . Relatively low mobility appears to be due to small particle size and structural heterogeneity, and the p-type characteristic appears to be derived from MoO x . It was also confirmed that Comparative Example 2, which had been subjected to DEDS pretreatment, did not exhibit significant switching behavior.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un matériau bidimensionnel dont les propriétés électriques sont améliorées par l'augmentation d'une taille cristalline par adoption d'un inhibiteur d'adsorption. Plus précisément, l'invention concerne un procédé de préparation d'un matériau bidimensionnel à l'aide d'un traitement de surface par inhibiteur d'adsorption, le procédé comprenant les étapes consistant : (1) à adopter un inhibiteur d'adsorption dans un substrat ayant des sites d'adsorption destinés à adsorber l'inhibiteur d'adsorption sur lui ; (2) à former, à l'aide d'un dépôt de couche atomique, un matériau bidimensionnel sur les sites d'adsorption sur lesquels l'inhibiteur d'adsorption n'a pas été adsorbé ; et (3) à cristalliser le matériau bidimensionnel ainsi formé. Selon la présente invention, le procédé de préparation d'un matériau bidimensionnel à l'aide d'un traitement de surface par inhibiteur d'adsorption a pour effet : d'obtenir un matériau bidimensionnel sous la forme d'un film mince qui est uniforme par rapport à une zone large ; de permettre à un matériau plastique, qui est vulnérable à la chaleur, d'être librement appliqué à un substrat lorsque le procédé est mis en œuvre à une basse température de traitement ; et d'augmenter la cristallinité d'un matériau bidimensionnel. Par conséquent, il est apte à préparer un matériau bidimensionnel ayant une excellente mobilité de charge.
PCT/KR2017/006884 2017-04-06 2017-06-29 Procédé de préparation d'un matériau bidimensionnel à l'aide d'un traitement de surface par inhibiteur d'adsorption WO2018186535A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20170044579 2017-04-06
KR10-2017-0044579 2017-04-06

Publications (1)

Publication Number Publication Date
WO2018186535A1 true WO2018186535A1 (fr) 2018-10-11

Family

ID=63713201

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/006884 WO2018186535A1 (fr) 2017-04-06 2017-06-29 Procédé de préparation d'un matériau bidimensionnel à l'aide d'un traitement de surface par inhibiteur d'adsorption

Country Status (1)

Country Link
WO (1) WO2018186535A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115000205A (zh) * 2022-05-11 2022-09-02 浙江芯科半导体有限公司 一种高性能异质结及其制备方法
CN117088390A (zh) * 2023-10-19 2023-11-21 深圳新宙邦科技股份有限公司 一种六氟磷酸盐的制备方法、电解液及二次电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130103913A (ko) * 2012-03-12 2013-09-25 성균관대학교산학협력단 금속 칼코게나이드 박막의 제조 방법
KR20140115723A (ko) * 2013-03-22 2014-10-01 경희대학교 산학협력단 칼코겐 화합물의 2차원 대면적 성장 방법, cmos형 구조체의 제조 방법, 칼코겐 화합물의 막, 칼코겐 화합물의 막을 포함하는 전자 소자 및 cmos형 구조체
KR20150015183A (ko) * 2013-07-31 2015-02-10 건국대학교 산학협력단 MoS2 박막 및 이의 제조방법
JP2016097599A (ja) * 2014-11-21 2016-05-30 富士通株式会社 層状物質の積層構造及びその製造方法
KR101703814B1 (ko) * 2015-09-16 2017-02-08 한국과학기술연구원 결정성장유도체 및 용매를 이용한 2차원 소재 박막의 두께를 조절하는 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130103913A (ko) * 2012-03-12 2013-09-25 성균관대학교산학협력단 금속 칼코게나이드 박막의 제조 방법
KR20140115723A (ko) * 2013-03-22 2014-10-01 경희대학교 산학협력단 칼코겐 화합물의 2차원 대면적 성장 방법, cmos형 구조체의 제조 방법, 칼코겐 화합물의 막, 칼코겐 화합물의 막을 포함하는 전자 소자 및 cmos형 구조체
KR20150015183A (ko) * 2013-07-31 2015-02-10 건국대학교 산학협력단 MoS2 박막 및 이의 제조방법
JP2016097599A (ja) * 2014-11-21 2016-05-30 富士通株式会社 層状物質の積層構造及びその製造方法
KR101703814B1 (ko) * 2015-09-16 2017-02-08 한국과학기술연구원 결정성장유도체 및 용매를 이용한 2차원 소재 박막의 두께를 조절하는 방법

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115000205A (zh) * 2022-05-11 2022-09-02 浙江芯科半导体有限公司 一种高性能异质结及其制备方法
CN117088390A (zh) * 2023-10-19 2023-11-21 深圳新宙邦科技股份有限公司 一种六氟磷酸盐的制备方法、电解液及二次电池
CN117088390B (zh) * 2023-10-19 2024-02-09 深圳新宙邦科技股份有限公司 一种六氟磷酸盐的制备方法、电解液及二次电池

Similar Documents

Publication Publication Date Title
WO2017018834A1 (fr) Procédé de fabrication d'un film mince de dichalcogénure de métal de transition à deux dimensions
WO2015016412A1 (fr) Couche mince de mos2 et procédé de fabrication de celle-ci
WO2012064102A2 (fr) Tôle d'acier recouverte de graphène, et procédé de fabrication associé
CN109652785A (zh) 通过循环沉积在衬底上沉积金属硫族化物的方法
Kamiyama et al. Comparison between SiO2 films deposited by atomic layer deposition with SiH2 [N (CH3) 2] 2 and SiH [N (CH3) 2] 3 precursors
US5593497A (en) Method for forming a deposited film
Chen et al. Wide band gap silicon carbon nitride films deposited by electron cyclotron resonance plasma chemical vapor deposition
WO2016122081A1 (fr) Procédé de fabrication de couche mince de chalcogénure de métal
WO2018186535A1 (fr) Procédé de préparation d'un matériau bidimensionnel à l'aide d'un traitement de surface par inhibiteur d'adsorption
KR20180011899A (ko) 고균일 2차원 전이금속 디칼코지나이드 박막의 제조 방법
US10246795B2 (en) Transfer-free method for forming graphene layer
JP2020531682A (ja) プラズマ化学気相成長法によって調製した単層および多層シリセン
US4873125A (en) Method for forming deposited film
Barreau et al. Characteristics of photoconductive MoS2 films grown on NaCl substrates by a sequential process
EP0240305B1 (fr) Méthode de fabrication d'une couche déposée
WO2014178686A1 (fr) Procédé de fabrication de couche mince de sulfure de nickel
Anutgan et al. Comparison of Chromium-and Aluminum-Gated Nanocrystalline Silicon TFTs
WO2023075277A1 (fr) Procédé de fabrication d'une couche mince à l'aide d'une couche de graphène à surface fonctionnalisée et couche mince fabriquée par ce procédé
KR20200040169A (ko) 단결정 이종 2차원 물질의 애피택셜 성장 방법 및 적층 구조체
WO2024117712A1 (fr) Dispositif à semi-conducteurs et son procédé de fabrication
US11837635B2 (en) Method of forming graphene on a silicon substrate
WO2023200144A1 (fr) Composé d'indium, composition de dépôt de couche mince contenant de l'indium le comprenant, et procédé de fabrication de couche mince contenant de l'indium
WO2013118937A1 (fr) Procédé de fabrication d'un film fin d'oxyde de zinc et d'étain
JPH04180617A (ja) 大結晶粒径の多結晶シリコンを製造する方法およびそれを使用した薄膜半導体
KR100738659B1 (ko) 니켈 할로겐 화합물 분위기를 이용한 다결정 규소박막의제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17904399

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17904399

Country of ref document: EP

Kind code of ref document: A1