WO2023193637A1 - Method for growing large-area high-performance hole conductive tungsten diselenide single crystal on silicon-based insulating layer - Google Patents

Method for growing large-area high-performance hole conductive tungsten diselenide single crystal on silicon-based insulating layer Download PDF

Info

Publication number
WO2023193637A1
WO2023193637A1 PCT/CN2023/084420 CN2023084420W WO2023193637A1 WO 2023193637 A1 WO2023193637 A1 WO 2023193637A1 CN 2023084420 W CN2023084420 W CN 2023084420W WO 2023193637 A1 WO2023193637 A1 WO 2023193637A1
Authority
WO
WIPO (PCT)
Prior art keywords
boat
tungsten
halide
carrier
silicon
Prior art date
Application number
PCT/CN2023/084420
Other languages
French (fr)
Chinese (zh)
Inventor
吴燕庆
王欣
史新航
Original Assignee
北京大学
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 北京大学 filed Critical 北京大学
Publication of WO2023193637A1 publication Critical patent/WO2023193637A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/16—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds

Definitions

  • the invention belongs to the field of semiconductor material growth technology, and specifically relates to a silicon-based compatible method for directly growing a large-area high-performance hole-conducting tungsten diselenide single crystal by chemical vapor deposition on silicon oxide and a high dielectric constant insulating layer.
  • Transition metal chalcogenides have received widespread attention as a two-dimensional material that is not easy to react with water and oxygen, has good stability, is easy to grow using a variety of methods, has a wide band gap span, and has adjustable conductivity type.
  • tungsten diselenide as a bipolar transition metal chalcogenide, has broad application prospects in the field of integrated circuit nanosheet CMOS.
  • high-performance tungsten diselenide materials are mainly obtained by mechanical peeling.
  • mechanical peeling has the disadvantages of uncontrollable number of layers and limited size, making it unable to be applied on a large scale.
  • the chemical vapor deposition method can theoretically achieve large-area and high-quality thin film growth.
  • the current traditional chemical vapor deposition method still has problems such as poor quality, small size, low hole mobility, and difficulty in achieving multi-layer controllable growth, which limits the Development of CMOS circuits based on two-dimensional materials. Achieving high-performance hole-conducting tungsten diselenide growth is one of the key problems to be solved in the growth and development of two-dimensional materials at this stage.
  • the object of the present invention is to provide a method for directly growing large-area, high-performance hole-conducting tungsten diselenide single crystal on a silicon-based compatible silicon substrate insulating layer, in which the key reaction participants and lining of the preparation method are used.
  • the bottom placement method is improved, and a halide is mixed with a tungsten source material to participate in the reaction.
  • the reactant has a lower melting point and a higher vapor pressure than the tungsten source, and can grow a single or multiple layers of diselenide on the silicon-based insulating layer.
  • Tungsten diselenide by changing the placement of the substrate and tungsten source, can grow large-area single-layer tungsten diselenide films and multi-layer tungsten diselenide single crystals, and the hole mobility of tungsten diselenide is relatively high. Reaching more than 140 square centimeters per volt second.
  • a method for growing a large-area tungsten diselenide single crystal on a silicon-based insulating layer is used to grow tungsten diselenide on a silicon-based insulating layer substrate. It is characterized by placing a tungsten source and a halide. In the first carrier boat, insert the substrate into the first carrier boat obliquely with the growth surface facing downward, so that the tungsten source and halide are located in the triangular space surrounded by the substrate and the bottom surface and side walls of the first carrier boat.
  • the tungsten source and halide are close to the side wall of the first carrier boat and not in contact with the substrate;
  • the selenium source is placed in the second carrier boat, and the carrier gas flows from the second carrier boat to the first carrier It flows in the direction of the boat; heated to the set growth temperature, the halide melts and reacts with the tungsten source to generate an intermediate product, which then reacts with the selenium source brought by the carrier gas to chemical vapor deposition on the substrate surface to grow a tungsten diselenide single crystal.
  • the method for growing large-area tungsten diselenide single crystal provided by the invention is a molten salt-assisted chemical vapor deposition method. Different from the traditional method where the growth surface of the substrate to be deposited is placed horizontally above the tungsten source downwards, the substrate of the present invention is inserted obliquely into the first carrier boat, and the tungsten source is placed on the substrate and enclosed with the first carrier boat to form a In a triangular space, the tungsten source is required to be close to the wall of the first carrier boat and not in contact with the substrate.
  • the second carrier boat upstream of the tungsten source contains selenium source material, and the carrier gas flows from the second carrier boat to the first carrier boat; at the same time, in addition to the tungsten source material, there are also selenium sources in the first carrier boat.
  • the halide is a halide of an alkali metal (such as sodium or potassium), most preferably potassium chloride.
  • the mass ratio of the halide to the tungsten source is 1:120 ⁇ 1:8.
  • the substrate may be a silicon oxide layer or a high dielectric constant silicon nitride layer or other high dielectric constant insulating layer on a low resistance silicon substrate.
  • the silicon oxide layer on the silicon substrate, Silicon nitride can be obtained by thermal oxidation/nitridation, atomic layer deposition or plasma enhanced chemical vapor deposition.
  • the first cargo boat and the second cargo boat are placed into the pipe of the tubular heating furnace, and the heating method is to heat to the set temperature at a downstream position of the pipe away from the cargo boat, and then move the heating When the furnace reaches the position of the carrier boat, the chemical vapor deposition reaction starts after a shorter heating time than the heating time.
  • the purpose is to avoid premature melting of the halide during the relatively long heating time.
  • the preset growth temperature condition is 800-900°C
  • the heating center of the tubular heating furnace is located at the position of the first carrier boat; the second carrier boat is located at the edge of the tubular heating furnace , the temperature is lower, 300 ⁇ 500°C.
  • the grown tungsten diselenide single crystal can be a single layer or multiple layers of tungsten diselenide, and the number of layers of the tungsten diselenide single crystal is controlled by adjusting the amount of halide and the growth time.
  • the side length of the prepared tungsten diselenide single crystal is not less than 40 microns, preferably, the side length is not less than 200 microns.
  • the method of the present invention realizes large-area single-layer material films and large-sized multi-layer tungsten diselenide single crystals through the oblique insertion method, with a maximum side length of 221 microns.
  • Silicon-based compatible direct growth The two-dimensional material deposited on the insulating layer/silicon substrate of the present invention does not need to be transferred, and hole-conducting devices can be directly prepared, avoiding material damage and process residues caused by transfer, and ensuring The high quality of the materials.
  • the double-layer tungsten diselenide thin film single crystal prepared by the present invention is an equilateral triangle with a clean surface, sharp edges and no jagged edges. It has high quality and the hole mobility can reach 140 square centimeters per volt. Second.
  • Figure 1 is a schematic structural diagram of a device for preparing large-area tungsten diselenide single crystal by chemical vapor deposition in the present invention.
  • Figure 2 is an optical microscope image of a double-layer tungsten diselenide single crystal prepared in an embodiment of the present invention.
  • Figure 3 is the photoluminescence spectrum of the double-layer tungsten diselenide single crystal prepared in the embodiment of the present invention.
  • Figure 4 is a Raman spectrum of a double-layer tungsten diselenide single crystal prepared in an embodiment of the present invention.
  • the present invention achieves multi-layer growth of tungsten diselenide single crystal on a silicon-based insulating layer by using halide molten salt-assisted growth, and achieves the expansion and expansion of the multi-layer growth area by changing the positions of the substrate and the tungsten source. Increase in multi-layer size.
  • This embodiment provides a silicon-based compatible chemical vapor deposition method for growing double-layer tungsten diselenide.
  • Chemical vapor deposition is achieved in a tubular heating furnace.
  • the schematic diagram of the equipment is shown in Figure 1.
  • the halide (potassium chloride) is mixed and placed in the first carrier boat.
  • the substrate is inserted obliquely into the first carrier boat with the front side facing down so that the tungsten source and halide are located between the substrate and the bottom surface and side walls of the carrier boat.
  • the tungsten source and halide are required to be close to the side wall of the carrier boat without contacting the substrate; the selenium source (selenium powder) is contained in the second carrier boat, and the carrier gas flows from the second carrier boat to the third carrier boat.
  • the direction of flow of a cargo boat; the specific operation steps are as follows:
  • Clean the substrate Clean the low-resistance silicon substrate with the silicon oxide layer using the standard RCA method, and blow dry with high-purity nitrogen for use.
  • the tube heating furnace uses different sizes of pipes and requires different sample masses.
  • This example uses a quartz tube with an outer diameter of one inch.
  • the selenium powder, tungsten dioxide powder and potassium chloride used in the reaction are 200 respectively. mg, 40 mg and 3 mg.
  • the selenium powder is placed in the ceramic boat (the second carrier boat), the tungsten dioxide and potassium chloride powder are mixed evenly and placed in the corundum boat (the first carrier boat), and the cleaned substrate is placed upside down and tilted. Above the powder in the corundum boat, one edge of the substrate is in contact with the bottom of the corundum boat, and the other side rests on the edge of the side wall of the corundum boat, forming a triangular space with the corundum boat.
  • Figure 2 shows a double-layered tungsten diselenide single crystal under an optical microscope.
  • the single crystal is triangular and the side length can be up to 200 microns.
  • Figures 3 and 4 show the photoluminescence spectrum and Raman spectrum of double-layer tungsten diselenide respectively. The positions of the characteristic peaks are consistent with the double-layer tungsten diselenide reported in the literature. Testing of the double-layer tungsten diselenide single crystal material showed that the material is hole conductive and has a mobility of 140 square centimeters per volt second.

Abstract

A method for growing a large-area high-performance hole conductive tungsten diselenide single crystal on a silicon-based insulating layer. A molten salt reacts with a tungsten source to generate an intermediate product having lower melting point and higher vapor pressure, such that a tungsten diselenide single crystal is more easily grown on a silicon oxide or high-dielectric-constant insulating layer on a silicon substrate on the basis of the principle of chemical vapor deposition, and meanwhile, large-area growth of tungsten diselenide is achieved by changing a substrate placing mode. The method may effectively achieve layer number controlled growth of large-area multi-layer tungsten diselenide single crystals, thus a silicon-based compatible high-mobility hole conductive two-dimensional material can be obtained, the operation is easy, transfer is not needed, and the material quality is higher.

Description

在硅基绝缘层上生长大面积高性能空穴导电二硒化钨单晶的方法Method for growing large-area high-performance hole-conducting tungsten diselenide single crystal on silicon-based insulating layer 技术领域Technical field
本发明属于半导体材料生长技术领域，具体涉及一种硅基兼容的在氧化硅和高介电常数绝缘层上直接化学气相沉积生长大面积高性能空穴导电二硒化钨单晶的方法。The invention belongs to the field of semiconductor material growth technology, and specifically relates to a silicon-based compatible method for directly growing a large-area high-performance hole-conducting tungsten diselenide single crystal by chemical vapor deposition on silicon oxide and a high dielectric constant insulating layer.
背景技术Background technique
过渡金属硫族化物作为一种不易于水氧反应，稳定性好，易于使用多种方法生长，禁带宽度跨度广，导电类型可调的二维材料受到广泛的关注。其中，二硒化钨作为一种具有双极性的过渡金属硫族化物，在集成电路纳米片CMOS领域中拥有广泛的运用前景。Transition metal chalcogenides have received widespread attention as a two-dimensional material that is not easy to react with water and oxygen, has good stability, is easy to grow using a variety of methods, has a wide band gap span, and has adjustable conductivity type. Among them, tungsten diselenide, as a bipolar transition metal chalcogenide, has broad application prospects in the field of integrated circuit nanosheet CMOS.
目前高性能的二硒化钨材料主要由机械剥离方法得到，但是机械剥离存在层数不可控以及尺寸受限制的缺点，无法大规模应用。化学气相沉积法理论上可以实现大面积高质量的薄膜生长，但是目前的传统化学气相沉积方法仍存在质量差、尺寸小、空穴迁移率低、难以实现多层可控生长等问题，限制了以二维材料为基础的CMOS电路的发展。实现高性能的空穴导电二硒化钨生长是现阶段二维材料生长发展过程中重点解决的难题之一。At present, high-performance tungsten diselenide materials are mainly obtained by mechanical peeling. However, mechanical peeling has the disadvantages of uncontrollable number of layers and limited size, making it unable to be applied on a large scale. The chemical vapor deposition method can theoretically achieve large-area and high-quality thin film growth. However, the current traditional chemical vapor deposition method still has problems such as poor quality, small size, low hole mobility, and difficulty in achieving multi-layer controllable growth, which limits the Development of CMOS circuits based on two-dimensional materials. Achieving high-performance hole-conducting tungsten diselenide growth is one of the key problems to be solved in the growth and development of two-dimensional materials at this stage.
发明内容Contents of the invention
本发明的目的在于提供一种硅基兼容的硅衬底绝缘层上直接生长大面积高性能的空穴导电的二硒化钨单晶的方法，其中通过对制备方法关键的反应参与物和衬底放置方式进行改进，使用卤化物与钨源材料混合参与反应，反应物具有比钨源更低的熔点和更高的蒸气压，能够在硅基绝缘层上生长出单层或多层二硒化钨，通过改变衬底和钨源的放置方式，可以生长出大面积的单层二硒化钨薄膜和多层二硒化钨单晶，并且二硒化钨的空穴迁移率比较高，达到140平方厘米每伏秒以上。The object of the present invention is to provide a method for directly growing large-area, high-performance hole-conducting tungsten diselenide single crystal on a silicon-based compatible silicon substrate insulating layer, in which the key reaction participants and lining of the preparation method are used. The bottom placement method is improved, and a halide is mixed with a tungsten source material to participate in the reaction. The reactant has a lower melting point and a higher vapor pressure than the tungsten source, and can grow a single or multiple layers of diselenide on the silicon-based insulating layer. Tungsten diselenide, by changing the placement of the substrate and tungsten source, can grow large-area single-layer tungsten diselenide films and multi-layer tungsten diselenide single crystals, and the hole mobility of tungsten diselenide is relatively high. Reaching more than 140 square centimeters per volt second.
为实现上述目的，本发明采用如下技术方案：In order to achieve the above objects, the present invention adopts the following technical solutions:
一种在硅基绝缘层上生长大面积二硒化钨单晶的方法，采用化学气相沉积法在硅基绝缘层衬底上生长二硒化钨，其特征在于，将钨源和卤化物放置在第一载物舟内，将所述衬底生长面朝下斜***第一载物舟，使钨源和卤化物位于衬底与第一载物舟的底面和侧壁围成的三角形空间内，且钨源和卤化物靠近第一载物舟的侧壁，而与衬底不接触；将硒源放置在第二载物舟内，载气从第二载物舟到第一载物舟的方向流动；加热到设定的生长温度，卤化物熔融与钨源反应生成中间产物，中间产物再与载气带来的硒源在衬底表面上化学气相沉积生长二硒化钨单晶。A method for growing a large-area tungsten diselenide single crystal on a silicon-based insulating layer. The chemical vapor deposition method is used to grow tungsten diselenide on a silicon-based insulating layer substrate. It is characterized by placing a tungsten source and a halide. In the first carrier boat, insert the substrate into the first carrier boat obliquely with the growth surface facing downward, so that the tungsten source and halide are located in the triangular space surrounded by the substrate and the bottom surface and side walls of the first carrier boat. inside, and the tungsten source and halide are close to the side wall of the first carrier boat and not in contact with the substrate; the selenium source is placed in the second carrier boat, and the carrier gas flows from the second carrier boat to the first carrier It flows in the direction of the boat; heated to the set growth temperature, the halide melts and reacts with the tungsten source to generate an intermediate product, which then reacts with the selenium source brought by the carrier gas to chemical vapor deposition on the substrate surface to grow a tungsten diselenide single crystal. .
本发明提供的生长大面积二硒化钨单晶的方法是一种熔融盐辅助的化学气相沉积法。与传统的待沉积的衬底生长面朝下水平放置于钨源上方不同，本发明的衬底倒扣斜***第一载物舟，钨源放在衬底与第一载物舟围合形成的三角形空间内，同时要求钨源紧靠第一载物舟壁，与衬底不接触。在钨源上游的第二载物舟内盛放有硒源材料，载气从第二载物舟到第一载物舟的方向流动；同时，除钨源材料外第一载物舟内还盛放还有卤化物，卤化物位于钨源上方或与钨源混合均匀，在加热炉达到预先设定的生长温度时，硒源材料还未熔化时，卤化物能够熔融与钨源材料反应生成中间产物，中间产物再与载气带来的硒源在衬底表面上化学气相沉积生长二硒化钨单晶。The method for growing large-area tungsten diselenide single crystal provided by the invention is a molten salt-assisted chemical vapor deposition method. Different from the traditional method where the growth surface of the substrate to be deposited is placed horizontally above the tungsten source downwards, the substrate of the present invention is inserted obliquely into the first carrier boat, and the tungsten source is placed on the substrate and enclosed with the first carrier boat to form a In a triangular space, the tungsten source is required to be close to the wall of the first carrier boat and not in contact with the substrate. The second carrier boat upstream of the tungsten source contains selenium source material, and the carrier gas flows from the second carrier boat to the first carrier boat; at the same time, in addition to the tungsten source material, there are also selenium sources in the first carrier boat. There are also halides contained therein. The halides are located above the tungsten source or evenly mixed with the tungsten source. When the heating furnace reaches the preset growth temperature and the selenium source material has not yet melted, the halide can melt and react with the tungsten source material to form The intermediate product is then chemically vapor deposited with the selenium source brought by the carrier gas to grow a tungsten diselenide single crystal on the surface of the substrate.
优选的，所述卤化物为碱金属（例如钠或者钾）的卤化物，最优选为氯化钾。所述卤化物与钨源的质量比为1:120~1:8。Preferably, the halide is a halide of an alkali metal (such as sodium or potassium), most preferably potassium chloride. The mass ratio of the halide to the tungsten source is 1:120~1:8.
作为本发明的进一步优选，所述衬底可以是低阻硅衬底上具有氧化硅层或高介电常数的氮化硅层或者其他高介电常数绝缘层，硅衬底上的氧化硅、氮化硅可以通过热氧化/氮化、原子层沉积或者等离子增强化学气相沉积得到。As a further preference of the present invention, the substrate may be a silicon oxide layer or a high dielectric constant silicon nitride layer or other high dielectric constant insulating layer on a low resistance silicon substrate. The silicon oxide layer on the silicon substrate, Silicon nitride can be obtained by thermal oxidation/nitridation, atomic layer deposition or plasma enhanced chemical vapor deposition.
作为本发明的进一步优选，将第一载物舟和第二载物舟放入管式加热炉的管道中，加热方式采用在远离载物舟的管道下游位置加热到设定温度，再移动加热炉到载物舟位置，经过一段相对于加热时间更短的升温时间后化学气相沉积反应开始，目的是避免相对较长的加热时间提前熔化卤化物。As a further preference of the present invention, the first cargo boat and the second cargo boat are placed into the pipe of the tubular heating furnace, and the heating method is to heat to the set temperature at a downstream position of the pipe away from the cargo boat, and then move the heating When the furnace reaches the position of the carrier boat, the chemical vapor deposition reaction starts after a shorter heating time than the heating time. The purpose is to avoid premature melting of the halide during the relatively long heating time.
作为本发明的进一步优选，所述预先设定的生长温度条件为800～900℃，管式加热炉的加热中心位于第一载物舟的位置；第二载物舟位于管式加热炉的边缘，温度较低，为300~500℃。As a further preference of the present invention, the preset growth temperature condition is 800-900°C, the heating center of the tubular heating furnace is located at the position of the first carrier boat; the second carrier boat is located at the edge of the tubular heating furnace , the temperature is lower, 300~500℃.
作为本发明的进一步优选，生长得到的所述二硒化钨单晶可以是单层或多层二硒化钨，通过调节卤化物的用量和生长时间调控二硒化钨单晶的层数，例如单层、双层和三层二硒化钨，所制备的二硒化钨单晶的边长尺寸不小于40微米，优选的，边长尺寸不小于200微米。As a further preference of the present invention, the grown tungsten diselenide single crystal can be a single layer or multiple layers of tungsten diselenide, and the number of layers of the tungsten diselenide single crystal is controlled by adjusting the amount of halide and the growth time. For example, single-layer, double-layer and triple-layer tungsten diselenide, the side length of the prepared tungsten diselenide single crystal is not less than 40 microns, preferably, the side length is not less than 200 microns.
本发明的有益效果：Beneficial effects of the present invention:
（1）操作简单、结果可控：传统的机械剥离方法复杂且层数尺寸不可控，化学气相沉积法的设备简单，能实现高质量、大范围且可控的二维材料的单晶生长。(1) Simple operation and controllable results: The traditional mechanical peeling method is complex and the number of layers is uncontrollable. The chemical vapor deposition method has simple equipment and can achieve high-quality, large-scale and controllable single crystal growth of two-dimensional materials.
（2）材料尺寸大：本发明方法通过斜插法实现了大面积的单层材料薄膜和大尺寸的多层二硒化钨单晶，最大达到221微米边长。(2) Large material size: The method of the present invention realizes large-area single-layer material films and large-sized multi-layer tungsten diselenide single crystals through the oblique insertion method, with a maximum side length of 221 microns.
（3）硅基兼容直接生长：本发明在绝缘层/硅衬底上沉积得到的二维材料无需转移，可以直接制备空穴导电的器件，避免了转移带来的材料损伤和工艺残余，保证了材料的高质量。(3) Silicon-based compatible direct growth: The two-dimensional material deposited on the insulating layer/silicon substrate of the present invention does not need to be transferred, and hole-conducting devices can be directly prepared, avoiding material damage and process residues caused by transfer, and ensuring The high quality of the materials.
（4）材料高质量：本发明制备出的双层二硒化钨薄膜单晶为表面洁净边缘锐利无锯齿的等边三角形，具有很高的质量，空穴迁移率可以达到140平方厘米每伏秒。(4) High quality materials: The double-layer tungsten diselenide thin film single crystal prepared by the present invention is an equilateral triangle with a clean surface, sharp edges and no jagged edges. It has high quality and the hole mobility can reach 140 square centimeters per volt. Second.
附图说明Description of the drawings
图1为本发明中化学气相沉积法制备大面积二硒化钨单晶的装置结构示意图。Figure 1 is a schematic structural diagram of a device for preparing large-area tungsten diselenide single crystal by chemical vapor deposition in the present invention.
图2为本发明实施例制备的双层二硒化钨单晶的光学显微镜图像。Figure 2 is an optical microscope image of a double-layer tungsten diselenide single crystal prepared in an embodiment of the present invention.
图3为本发明实施例制备的双层二硒化钨单晶的光致发光光谱。 Figure 3 is the photoluminescence spectrum of the double-layer tungsten diselenide single crystal prepared in the embodiment of the present invention.​
图4为本发明实施例制备的双层二硒化钨单晶的拉曼光谱。Figure 4 is a Raman spectrum of a double-layer tungsten diselenide single crystal prepared in an embodiment of the present invention.
具体实施方式Detailed ways
为了使本发明所述的内容更加便于理解，下面结合具体实施例对本发明所述的技术方案做进一步的说明，但下述的实例仅仅是本发明其中的例子而已，并不代表本发明所限定的权利保护范围，本发明的权利保护范围以权利要求书为准。In order to make the content of the present invention easier to understand, the technical solutions of the present invention will be further described below in conjunction with specific embodiments. However, the following examples are only examples of the present invention and do not mean that the present invention is limited. The scope of rights protection of the present invention shall be determined by the claims.
总的来说，本发明通过使用卤化物熔融盐辅助生长实现硅基绝缘层上二硒化钨单晶的多层生长，通过改变衬底和钨源放置的位置实现多层生长区域的扩大和多层尺寸的增大。In general, the present invention achieves multi-layer growth of tungsten diselenide single crystal on a silicon-based insulating layer by using halide molten salt-assisted growth, and achieves the expansion and expansion of the multi-layer growth area by changing the positions of the substrate and the tungsten source. Increase in multi-layer size.
以下为具体实施例：The following are specific examples:
本实施例给出一种硅基兼容的化学气相沉积生长双层二硒化钨的方法，在管式加热炉内实现化学气相沉积，设备示意图如图1所示，钨源（氧化钨）和卤化物（氯化钾）混合后放置在第一载物舟内，衬底正面朝下斜***第一载物舟，使钨源和卤化物位于衬底与载物舟底面和侧壁围成的三角形空间内，要求钨源和卤化物靠近载物舟侧壁，而与衬底不接触；第二载物舟内盛放硒源（硒粉末），载气从第二载物舟到第一载物舟的方向流动；具体操作步骤如下：This embodiment provides a silicon-based compatible chemical vapor deposition method for growing double-layer tungsten diselenide. Chemical vapor deposition is achieved in a tubular heating furnace. The schematic diagram of the equipment is shown in Figure 1. The tungsten source (tungsten oxide) and The halide (potassium chloride) is mixed and placed in the first carrier boat. The substrate is inserted obliquely into the first carrier boat with the front side facing down so that the tungsten source and halide are located between the substrate and the bottom surface and side walls of the carrier boat. In a triangular space, the tungsten source and halide are required to be close to the side wall of the carrier boat without contacting the substrate; the selenium source (selenium powder) is contained in the second carrier boat, and the carrier gas flows from the second carrier boat to the third carrier boat. The direction of flow of a cargo boat; the specific operation steps are as follows:
1. 清洗衬底：将具有氧化硅层的低阻硅衬底采用标准RCA方法清洗，并用高纯氮气吹干待用。1. Clean the substrate: Clean the low-resistance silicon substrate with the silicon oxide layer using the standard RCA method, and blow dry with high-purity nitrogen for use.
2. 称量样品：管式加热炉使用不同尺寸的管道所需样品质量不同，本实施例使用一英寸外径的石英管，反应所用的硒粉末、二氧化钨粉末和氯化钾分别为200毫克、40毫克和3毫克。硒粉末放在陶瓷舟（第二载物舟）内，二氧化钨和氯化钾粉末混合均匀后放在刚玉舟（第一载物舟）内，清洗好的衬底倒扣斜插放在刚玉舟内粉末的上方，衬底一侧边缘与刚玉舟内底部接触，另一侧搭在刚玉舟侧壁边缘，与刚玉舟围成一个三角形空间。2. Weigh the sample: The tube heating furnace uses different sizes of pipes and requires different sample masses. This example uses a quartz tube with an outer diameter of one inch. The selenium powder, tungsten dioxide powder and potassium chloride used in the reaction are 200 respectively. mg, 40 mg and 3 mg. The selenium powder is placed in the ceramic boat (the second carrier boat), the tungsten dioxide and potassium chloride powder are mixed evenly and placed in the corundum boat (the first carrier boat), and the cleaned substrate is placed upside down and tilted. Above the powder in the corundum boat, one edge of the substrate is in contact with the bottom of the corundum boat, and the other side rests on the edge of the side wall of the corundum boat, forming a triangular space with the corundum boat.
3. 放样及升温：使用氩气将低压状态的石英管恢复常压以便打开挡板放样。使用金属杆将刚玉舟和陶瓷舟先后推至指定位置，在加热炉达到指定温度并推至反应位置时，刚玉舟位于加热炉中心，陶瓷舟位于加热炉边缘，两舟距离为19 cm。送样后盖上挡板并开启真空泵打开角阀进行抽气直到管内压强小于5帕。设置生长温度为850摄氏度，升温速率30摄氏度每分钟，升温过程氩气流量为50标准毫升每分钟。3. Setting out and heating up: Use argon gas to return the low-pressure quartz tube to normal pressure so that the baffle can be opened for setting out. Use a metal rod to push the corundum boat and ceramic boat to the designated position one after another. When the heating furnace reaches the designated temperature and is pushed to the reaction position, the corundum boat is located in the center of the heating furnace and the ceramic boat is located at the edge of the heating furnace. The distance between the two boats is 19 cm. After sending the sample, cover the baffle and turn on the vacuum pump, open the angle valve and evacuate until the pressure in the tube is less than 5 Pa. Set the growth temperature to 850 degrees Celsius, the heating rate to 30 degrees Celsius per minute, and the argon flow rate during the heating process to 50 standard milliliters per minute.
4. 反应：升温完成后，将加热炉滑到石英管上游设定位置，经过5分钟的升温过程达到850摄氏度，此时中心位置即刚玉舟位置温度850摄氏度，边缘位置即陶瓷舟位置300摄氏度；反应开始，反应时间15分钟，氩气和氢气的流量分别为105和7标准毫升每分钟，反应期间需要适时调整角阀保持压强在1000到2000帕。反应结束后滑动加热炉到下游自然降温，氩气流量为50标准毫升每分钟。4. Reaction: After the temperature rise is completed, slide the heating furnace to the set position upstream of the quartz tube. After 5 minutes of heating process, it reaches 850 degrees Celsius. At this time, the temperature of the center position, that is, the position of the corundum boat, is 850 degrees Celsius, and the edge position, that is, the position of the ceramic boat, is 300 degrees Celsius. ; The reaction starts, the reaction time is 15 minutes, the flow rates of argon and hydrogen are 105 and 7 standard milliliters per minute respectively. During the reaction, the angle valve needs to be adjusted appropriately to maintain the pressure at 1000 to 2000 Pa. After the reaction, slide the heating furnace to the downstream to naturally cool down, and the argon flow rate is 50 standard milliliters per minute.
5. 取样观察：待衬底温度降到常温后关闭角阀使用大流量氩气破真空取出样品并在显微镜下观察样品的尺寸形貌和层数。5. Sampling and observation: After the substrate temperature drops to normal temperature, close the angle valve, use a large flow of argon gas to break the vacuum, take out the sample, and observe the size, morphology, and number of layers of the sample under a microscope.
图2为光学显微镜下双层二硒化钨单晶，单晶为三角形，边长尺寸可达200微米。图3和图4分别为双层二硒化钨的光致发光谱以及拉曼光谱，特征峰的位置与文献报道的双层二硒化钨相符合。对双层二硒化钨单晶材料进行测试，可得材料为空穴导电且迁移率达到了140平方厘米每伏秒。Figure 2 shows a double-layered tungsten diselenide single crystal under an optical microscope. The single crystal is triangular and the side length can be up to 200 microns. Figures 3 and 4 show the photoluminescence spectrum and Raman spectrum of double-layer tungsten diselenide respectively. The positions of the characteristic peaks are consistent with the double-layer tungsten diselenide reported in the literature. Testing of the double-layer tungsten diselenide single crystal material showed that the material is hole conductive and has a mobility of 140 square centimeters per volt second.

Claims (10)

  1. 一种在硅基绝缘层上生长大面积二硒化钨单晶的方法，采用化学气相沉积法在硅基绝缘层衬底上生长二硒化钨，其特征在于，将钨源和卤化物放置在第一载物舟内，将所述衬底生长面朝下斜***第一载物舟，使钨源和卤化物位于衬底与第一载物舟的底面和侧壁围成的三角形空间内，且钨源和卤化物靠近第一载物舟的侧壁，而与衬底不接触；将硒源放置在第二载物舟内，载气从第二载物舟到第一载物舟的方向流动；加热到设定的生长温度，卤化物熔融与钨源反应生成中间产物，中间产物再与载气带来的硒源在衬底表面上化学气相沉积生长二硒化钨单晶。A method for growing a large-area tungsten diselenide single crystal on a silicon-based insulating layer. The chemical vapor deposition method is used to grow tungsten diselenide on a silicon-based insulating layer substrate. It is characterized by placing a tungsten source and a halide. In the first carrier boat, insert the substrate into the first carrier boat obliquely with the growth surface facing downward, so that the tungsten source and halide are located in the triangular space surrounded by the substrate and the bottom surface and side walls of the first carrier boat. inside, and the tungsten source and halide are close to the side wall of the first carrier boat and not in contact with the substrate; the selenium source is placed in the second carrier boat, and the carrier gas flows from the second carrier boat to the first carrier It flows in the direction of the boat; heated to the set growth temperature, the halide melts and reacts with the tungsten source to generate an intermediate product, which then reacts with the selenium source brought by the carrier gas to chemical vapor deposition on the substrate surface to grow a tungsten diselenide single crystal. .
  2. 如权利要求1所述的方法，其特征在于，所述卤化物位于钨源上方或者与钨源混合均匀。The method of claim 1, wherein the halide is located above the tungsten source or evenly mixed with the tungsten source.
  3. 如权利要求1所述的方法，其特征在于，所述卤化物为碱金属卤化物。The method of claim 1, wherein the halide is an alkali metal halide.
  4. 如权利要求3所述的方法，其特征在于，所述卤化物为氯化钾。The method of claim 3, wherein the halide is potassium chloride.
  5. 如权利要求1所述的方法，其特征在于，所述卤化物与钨源的质量比为1:120~1:8。The method of claim 1, wherein the mass ratio of the halide to the tungsten source is 1:120~1:8.
  6. 如权利要求1所述的方法，其特征在于，所述硅基绝缘层衬底是在低阻硅衬底上具有氧化硅层或高介电常数绝缘层。The method of claim 1, wherein the silicon-based insulating layer substrate has a silicon oxide layer or a high dielectric constant insulating layer on a low-resistance silicon substrate.
  7. 如权利要求1所述的方法，其特征在于，将第一载物舟和第二载物舟放入管式加热炉的管道中进行化学气相沉积，先在远离载物舟的管道下游位置将加热炉加热到设定温度，再移动加热炉到载物舟位置，快速启动化学气相沉积反应。The method according to claim 1, characterized in that the first cargo boat and the second cargo boat are put into the pipe of the tubular heating furnace for chemical vapor deposition, and the first cargo boat and the second cargo boat are first placed downstream of the pipe away from the cargo boat. The heating furnace is heated to the set temperature, and then the heating furnace is moved to the position of the carrier boat to quickly start the chemical vapor deposition reaction.
  8. 如权利要求6所述的方法，其特征在于，第一载物舟位置的温度为800～900℃，第二载物舟位置的温度为300~500℃。The method of claim 6, wherein the temperature of the first carrier boat is 800-900°C, and the temperature of the second carrier boat is 300-500°C.
  9. 如权利要求1所述的方法，其特征在于，其特征在于，所述第一载物舟采用刚玉舟，第二载物舟采用陶瓷舟。The method of claim 1, wherein the first cargo boat is a corundum boat, and the second cargo boat is a ceramic boat.
  10. 如权利要求1所述的方法，其特征在于，通过调节卤化物的用量和生长时间调控二硒化钨单晶的层数。The method according to claim 1, characterized in that the number of layers of the tungsten diselenide single crystal is controlled by adjusting the amount of halide and the growth time.
PCT/CN2023/084420 2022-04-07 2023-03-28 Method for growing large-area high-performance hole conductive tungsten diselenide single crystal on silicon-based insulating layer WO2023193637A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210358854.1 2022-04-07
CN202210358854.1A CN116926677A (en) 2022-04-07 2022-04-07 Method for growing large-area high-performance hole conductive tungsten diselenide monocrystal on silicon-based insulating layer

Publications (1)

Publication Number Publication Date
WO2023193637A1 true WO2023193637A1 (en) 2023-10-12

Family

ID=88244003

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/084420 WO2023193637A1 (en) 2022-04-07 2023-03-28 Method for growing large-area high-performance hole conductive tungsten diselenide single crystal on silicon-based insulating layer

Country Status (2)

Country Link
CN (1) CN116926677A (en)
WO (1) WO2023193637A1 (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140251204A1 (en) * 2013-03-11 2014-09-11 William Marsh Rice University Novel growth methods for controlled large-area fabrication of high-quality graphene analogs
CN106811731A (en) * 2016-11-17 2017-06-09 北京交通大学 A kind of controllable method for preparing of tungsten disulfide
CN108118395A (en) * 2017-12-15 2018-06-05 北京科技大学 A kind of method that chemical vapor deposition prepares two tungsten selenide monocrystal thin films
CN108193277A (en) * 2018-01-26 2018-06-22 西安电子科技大学 The method for preparing two tungsten selenide monocrystalline of large area individual layer
CN109183156A (en) * 2018-11-08 2019-01-11 西北工业大学 A kind of disulphide monocrystalline and its preparation method and application
US20190330735A1 (en) * 2017-04-17 2019-10-31 Massachusetts Institute Of Technology Chemical Vapor Transport Growth of Two-Dimensional Transition-Metal Dichalcogenides
CN111304738A (en) * 2020-03-16 2020-06-19 华中科技大学 Method for growing multilayer tungsten diselenide single crystal by molten salt assisted chemical vapor deposition
CN113755820A (en) * 2021-09-01 2021-12-07 西安电子科技大学 Large-area single-layer semiconductor two-dimensional WS2Thin film material and preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140251204A1 (en) * 2013-03-11 2014-09-11 William Marsh Rice University Novel growth methods for controlled large-area fabrication of high-quality graphene analogs
CN106811731A (en) * 2016-11-17 2017-06-09 北京交通大学 A kind of controllable method for preparing of tungsten disulfide
US20190330735A1 (en) * 2017-04-17 2019-10-31 Massachusetts Institute Of Technology Chemical Vapor Transport Growth of Two-Dimensional Transition-Metal Dichalcogenides
CN108118395A (en) * 2017-12-15 2018-06-05 北京科技大学 A kind of method that chemical vapor deposition prepares two tungsten selenide monocrystal thin films
CN108193277A (en) * 2018-01-26 2018-06-22 西安电子科技大学 The method for preparing two tungsten selenide monocrystalline of large area individual layer
CN109183156A (en) * 2018-11-08 2019-01-11 西北工业大学 A kind of disulphide monocrystalline and its preparation method and application
CN111304738A (en) * 2020-03-16 2020-06-19 华中科技大学 Method for growing multilayer tungsten diselenide single crystal by molten salt assisted chemical vapor deposition
CN113755820A (en) * 2021-09-01 2021-12-07 西安电子科技大学 Large-area single-layer semiconductor two-dimensional WS2Thin film material and preparation method and application thereof

Also Published As

Publication number Publication date
CN116926677A (en) 2023-10-24

Similar Documents

Publication Publication Date Title
TW544775B (en) Chemical vapor deposition apparatus and chemical vapor deposition method
CN108118395A (en) A kind of method that chemical vapor deposition prepares two tungsten selenide monocrystal thin films
CN105624782B (en) A kind of preparation method of gallium oxide film
CN113930743B (en) Method for growing two tungsten disulfide thin layers under normal pressure
CN109336069B (en) Preparation of molybdenum ditelluride nanowire material and molybdenum ditelluride nanowire material
CN112695381A (en) Method for rapidly growing ultrathin large-size single crystal transition metal sulfur/selenide
CN103400760A (en) Method and device for growing bismuth selenide single crystal film on silicon substrate
WO2023193637A1 (en) Method for growing large-area high-performance hole conductive tungsten diselenide single crystal on silicon-based insulating layer
CN113550006A (en) Method for preparing two-dimensional tellurium single crystal on mica substrate
CN105399061B (en) A kind of preparation method of one-dimensional tin selenide monocrystal nanowire
CN106830081A (en) A kind of MoO2The preparation method of nanometer rods
CN105603519A (en) Artificial growth method and device of IIb type diamond monocrystal with semiconductor properties
CN112159970A (en) Preparation method of wafer-level high-quality boron nitride/graphene heterojunction film
CN113322522B (en) Preparation method of large-single-domain large-area single-layer tungsten disulfide film by epitaxy
CN110512194A (en) Star-like microwave plasma CVD device and the method for preparing large-area two-dimensional material
US3078150A (en) Production of semi-conductor materials
CN113174583B (en) Open quartz boat and preparation method of large-area continuous two-dimensional transition metal sulfur compound film
CN113755820A (en) Large-area single-layer semiconductor two-dimensional WS2Thin film material and preparation method and application thereof
CN117842941B (en) Hafnium diselenide and preparation method thereof
CN112210829B (en) Single-layer single crystal MoS2And method for preparing the same
CN111074234A (en) Device and method for growing two-dimensional material based on push-pull trolley mode
CN113201726B (en) Preparation method of two-dimensional material
CN115354392B (en) Preparation method of large-size monocrystalline molybdenum disulfide
CN105525349B (en) A kind of preparation method of cuprous oxide monocrystal thin films
JP2667664B2 (en) Manufacturing method of silicon single crystal thin film

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: 23784201

Country of ref document: EP

Kind code of ref document: A1