WO2021097894A1 - 一种Ag 2S薄膜的制备方法 - Google Patents

一种Ag 2S薄膜的制备方法 Download PDF

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WO2021097894A1
WO2021097894A1 PCT/CN2019/121709 CN2019121709W WO2021097894A1 WO 2021097894 A1 WO2021097894 A1 WO 2021097894A1 CN 2019121709 W CN2019121709 W CN 2019121709W WO 2021097894 A1 WO2021097894 A1 WO 2021097894A1
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reaction chamber
silver
source
thin film
reaction
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French (fr)
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卢维尔
夏洋
李楠
赵丽莉
明帅强
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中国科学院微电子研究所
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    • 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
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • 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
    • C23C16/305—Sulfides, selenides, or tellurides
    • 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
    • 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
    • C23C16/52—Controlling or regulating the coating process

Definitions

  • This application relates to the field of semiconductor technology, in particular to a method for preparing an Ag 2 S thin film.
  • Inorganic semiconductor materials and ceramic insulating materials are usually brittle materials.
  • silver sulfide is an inorganic semiconductor material with excellent ductility similar to metals at room temperature. It has mechanical properties different from conventional inorganic semiconductor materials, especially good ductility and flexibility, and is expected to be widely used in the field of flexible electronics.
  • the excellent ductility of ⁇ -Ag 2 S material is mainly due to its intrinsic structure and chemical bonds.
  • silver sulfide bulk materials are mainly prepared by ingot casting method and spark plasma sintering method; while silver sulfide film materials are mainly obtained by spin coating of quantum dot colloidal solution, but these preparation methods are not suitable for semiconductor industrial production.
  • the embodiment of the present invention provides a method for preparing an Ag 2 S film to solve the technical problems in the prior art that the thickness of the silver sulfide film cannot be accurately controlled, and the silver sulfide film cannot be produced on a large scale at the same time.
  • the embodiment of the present invention provides a method for preparing an Ag 2 S thin film, the method includes: placing a substrate in a reaction chamber for atomic layer deposition, and evacuating the reaction chamber The substrate, the reaction chamber, the pipeline as the reaction source and the auxiliary gas channel in the reaction, and the reaction source are respectively heated to a specified temperature, wherein the reaction source includes a silver source and a sulfur source; the following cycles are performed in sequence Four stages: pass the silver source into the reaction chamber with the first pulse time, purge the reaction chamber with an inert gas at the first purge time, and pass the sulfur source with the second pulse time Into the reaction chamber, and purge the reaction chamber with the inert gas for the second purge time, so that the silver source and the sulfur source undergo atomic layer deposition in the reaction chamber to obtain Silver sulfide film sample; after the silver sulfide film sample is cooled to room temperature in a vacuum environment in the reaction chamber, the silver sulfide film sample is taken out of the
  • the specified temperature ranges for heating of the substrate, the reaction chamber, the pipeline, and the reaction source are all 25°C to 200°C.
  • the silver source is silver trimethylphosphine hexafluoroacetylacetonate, silver neodecanoate, silver 2,2,6,6-tetramethyl-3,5-heptanedione, triethoxy One of silver phosphine, silver triethylphosphine, silver trimethylphosphine, and silver acetylacetonate.
  • the first pulse time ranges from 1 ms to 5 s, preferably 0.01 to 5 s.
  • the first purge time is 1-300S, preferably 1-180S.
  • the sulfur source is one of hexamethyldisilsulfane, hydrogen sulfide, sulfur powder, and ammonium sulfide.
  • the range of the second pulse time is 0.01-5S.
  • the second purge time is 1-180S.
  • the embodiment of the present invention provides a method for preparing an Ag 2 S thin film.
  • the method includes: placing a substrate in an atomic layer deposition reaction chamber, evacuating the reaction chamber, and separately applying a vacuum to the substrate and the substrate.
  • the reaction chamber, the pipeline as the reaction source and the auxiliary gas channel in the reaction, and the reaction source are heated to a specified temperature, wherein the reaction source includes a silver source and a sulfur source; the following four stages are cycled in sequence: Pass the silver source into the reaction chamber with a pulse time, purge the reaction chamber with an inert gas for a first purge time, and pass the sulfur source into the reaction chamber with a second pulse time,
  • the reaction chamber is purged with the inert gas for the second purge time, so that the silver source and the sulfur source are deposited in the reaction chamber by atomic layer deposition to obtain a silver sulfide film sample.
  • the silver sulfide film sample is taken out of the reaction chamber.
  • the silver source is cyclically passed into the reaction chamber, the reaction chamber is purged with an inert gas, and the reaction chamber is passed into the reaction chamber.
  • Sulfur source and inert gas is used to purge the reaction chamber, so as to perform atomic layer deposition in the cavity to obtain silver sulfide film, which solves the problem of the inability to accurately control the thickness of silver sulfide film in the prior art, and at the same time, it is impossible to produce silver sulfide on a large scale.
  • the technical problems of the film have achieved the good three-dimensional conformal properties of the silver sulfide film.
  • the thickness of the film is precisely controllable in the order of a single atomic layer, and the operation is simple. It is compatible with existing semiconductor production lines and is suitable for large-scale production. effect.
  • Fig. 1 is a flow chart of the preparation method of the Ag 2 S film in the embodiment of the specification.
  • the embodiment of the present invention provides a method for preparing an Ag 2 S film to solve the technical problem that the thickness of the silver sulfide film cannot be accurately controlled in the prior art and the silver sulfide film cannot be produced on a large scale at the same time. It maintains good three-dimensional conformal properties, the film thickness is precisely controllable in the order of a single atomic layer, and the operation is simple, compatible with existing semiconductor production lines, and suitable for the technical effects of large-scale production.
  • the preparation method of the Ag 2 S thin film adopts placing a substrate in a reaction chamber of atomic layer deposition, evacuating the reaction chamber and reacting to the substrate and the reaction chamber respectively.
  • the chamber, the pipeline and the reaction source are heated to a specified temperature, where the reaction source includes a silver source and a sulfur source; the silver source is passed into the reaction chamber with a first pulse time, and an inert gas is used for the first Purge the reaction chamber with a purge time; pass the sulfur source into the reaction chamber at a second pulse time, and purge the reaction chamber with the inert gas at a second purge time;
  • the silver source and the sulfur source are subjected to atomic layer deposition in the reaction chamber to obtain a silver sulfide film sample, the silver sulfide film sample is cooled to room temperature in a vacuum environment in the reaction chamber, and the The silver sulfide film sample is taken out from the reaction chamber to achieve the good three-dimensional conformality of the silver
  • the embodiment of the present invention provides a method for preparing an Ag 2 S thin film. Please refer to FIG. 1.
  • the method includes step 110 to step 140:
  • the substrate is placed in an atomic layer deposition reaction chamber, the reaction chamber is evacuated, and the substrate, the reaction chamber, the pipeline, and the reaction source are respectively heated to a specified temperature ,
  • the reaction source includes a silver source and a sulfur source;
  • the substrate may include silicon wafer, sapphire or glass.
  • the specified temperature ranges for heating of the substrate, the reaction chamber, the pipeline, and the reaction source are all 25°C to 200°C.
  • the Ag 2 S thin film is prepared by placing a silicon substrate in an evacuated reaction chamber, heating the silicon substrate, the reaction chamber, etc., and sequentially circulating the silver source into the reaction chamber. , Inert gas, sulfur source and inert gas, atomic layer deposition is carried out in the cavity to obtain silver sulfide film.
  • the silver source is passed in for the first pulse time
  • the sulfur source is passed in for the second pulse time.
  • the ranges of the first pulse time and the second pulse time are respectively 1 ms to 5 s, preferably 0.01 to 5 s.
  • the inert gas is used to purge the reaction chamber, and the purge time may be 1-300S, preferably 1-180S.
  • the inert gas can be used as an auxiliary gas in the reaction to purge the reaction residue.
  • an inert gas can also be used as a carrier gas.
  • the method is of great significance for the application of silver sulfide in the fields of storage, logic devices, integrated storage and computing, and flexible devices.
  • the ⁇ -Ag 2 S crystal has a zigzag fold layered monoclinic structure at room temperature with a band gap of about 1.03 eV; its room temperature conductivity is 0.09-0.16 Sm-1 and its electrical properties can be freely adjusted in the semiconductor region.
  • the ductility of ⁇ -Ag 2 S material is several orders of magnitude higher than that of other semiconductors, and even better than some alloy materials. Its tensile tension can reach 4.2%, compression tension can reach more than 50%, and bending tension can exceed 20%.
  • Traditional semiconductor materials are generally difficult to withstand any plastic deformation.
  • Atomic layer deposition is a method in which substances can be deposited layer by layer on the surface of a substrate in the form of a monoatomic film.
  • ALD is a self-limiting surface growth method, so ALD can achieve precise controllability of film thickness on the order of a single atomic layer and 100% uniform and conformal film coverage on three-dimensional nanostructures.
  • Atomic layer deposition technology has been used in the field of microelectronics as a key technology for the preparation of high-quality dielectric layers for DRAMs trench capacitors and high-dielectric constant gate oxide layers for CMOS transistors.
  • the use of ALD technology to deposit silver sulfide films is compatible with existing semiconductor production lines and suitable for mass production.
  • Temperature, wherein the reaction source includes a silver source and a sulfur source, and the specified temperature range for heating of the substrate, the reaction chamber, the pipeline, and the reaction source are all 25° C. to 200° C. .
  • step 120 the silver source is passed into the reaction chamber for a first pulse time, and the reaction chamber is purged with an inert gas for the first purge time.
  • the silver source is silver trimethylphosphine hexafluoroacetylacetonate, silver neodecanoate, silver 2,2,6,6-tetramethyl-3,5-heptanedione, triethyl Silver phosphine oxide, silver triethylphosphine, silver trimethylphosphine or silver acetylacetonate.
  • the range of the first pulse time is 0.01-5S. In some embodiments, the first purge time is 1 to 180S.
  • the heating temperature of the substrate is 120°C.
  • the heating temperature of the reaction chamber is 120°C
  • the heating temperature of the pipeline is 120°C
  • the silver trimethylphosphine hexafluoroacetylacetonate is 100-110°C
  • the hexamethyldisilethane is room temperature.
  • the silver source is introduced into the reaction chamber with a first pulse time of 0.01-5S, and the reaction chamber is purged with an inert gas with a first purge time of 1 ⁇ 180S, wherein the silver source is trimethyl Phosphine silver hexafluoroacetylacetonate, silver neodecanoate, silver 2,2,6,6-tetramethyl-3,5-peptadionate (I), silver triethoxyphosphine (trifluoroacetylacetone) , Triethylphosphine (6,6,7,7,8,8,8 heptafluoro-2,2-dimethyl-3,5-octyl) silver, trimethylphosphine (hexafluoroacetylacetone) silver, Silver acetylacetonate and so on.
  • the silver source is trimethyl Phosphine silver hexafluoroacetylacetonate, silver neodecanoate, silver 2,2,6,6-t
  • the solid-state silver trimethylphosphine hexafluoroacetylacetonate is heated to 100-110°C in the solid-state source heating device of the atomic layer deposition equipment to obtain three Methylphosphine hexafluoroacetylacetonate silver vapor is then passed into the reaction chamber, the pulse time of the trimethylphosphine hexafluoroacetylacetonate silver source is 0.8-1.2S, and then the reaction chamber is purged with inert gas 20 ⁇ 60S.
  • step 130 the sulfur source is passed into the reaction chamber at a second pulse time, and the reaction chamber is purged with the inert gas at a second purge time.
  • the sulfur source is hexamethyldisilethane, hydrogen sulfide, sulfur powder, ammonium sulfide, and the like.
  • the range of the second pulse time is 0.01-5S.
  • the second purge time is 1 to 180S.
  • the sulfur source is passed into the reaction chamber with a second pulse time of 0.01 to 5S, and the reaction chamber is purged with the inert gas for a second purge time of 1 to 180S.
  • the sulfur source is hexamethyldisilsulfane, hydrogen sulfide, sulfur powder, ammonium sulfide and the like.
  • the pulse time of the hexamethyldisilsulfane is 0.2-0.8S, and then the reaction chamber is purged for 20-60S with inert gas. .
  • steps 120 and 130 can be performed alternately in a loop, so that step 140 is performed.
  • step 140 the silver source and the sulfur source are subjected to atomic layer deposition in the reaction chamber to obtain a silver sulfide film sample, and then the silver sulfide film sample is placed in a vacuum environment in the reaction chamber. After cooling to room temperature, the silver sulfide film sample was taken out of the reaction chamber.
  • the silver source and the sulfur source are subjected to atomic layer deposition in the reaction chamber to obtain a silver sulfide thin film sample, the silver sulfide thin film sample has good three-dimensional shape retention, and the silver sulfide The thickness of the film is precisely controllable on the order of a single atomic layer.
  • the silver sulfide film sample is cooled to room temperature in the vacuum environment in the reaction chamber, and the silver sulfide film sample is taken out of the reaction chamber for later use. This method is simple to operate and is beneficial to mass production and integration. Compatible with semiconductor production processes.
  • the embodiment of the present invention provides a method for preparing an Ag 2 S thin film.
  • the method includes: placing a substrate in an atomic layer deposition reaction chamber, evacuating the reaction chamber, and separately applying a vacuum to the substrate and the substrate.
  • the reaction chamber, the pipeline, and the reaction source are heated to a specified temperature, wherein the reaction source includes a silver source and a sulfur source; the silver source is passed into the reaction chamber with a first pulse time, and an inert gas is used to Purge the reaction chamber at a first purge time; pass the sulfur source into the reaction chamber at a second pulse time, and purge the reaction chamber with the inert gas at a second purge time;
  • the silver source and the sulfur source are subjected to atomic layer deposition in the reaction chamber to obtain a silver sulfide film sample, the silver sulfide film sample is cooled to room temperature in a vacuum environment in the reaction chamber, and The silver sulfide film sample is taken out of the reaction chamber.
  • the first pulse of silver source pulse and the second pulse of sulfur source pulse are passed into the reaction chamber, and the reaction is flushed with inert gas at the same time
  • atomic layer deposition is performed in the chamber to obtain a silver sulfide film. It solves the technical problems in the prior art that the thickness of the silver sulfide film cannot be accurately controlled, and the silver sulfide film cannot be produced on a large scale at the same time, and the silver sulfide film maintains good three-dimensional conformality, and the film thickness is on the order of a single atomic layer. It is precise and controllable, simple to operate, compatible with existing semiconductor production lines, and suitable for the technical effects of mass production.

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Abstract

一种Ag 2S薄膜的制备方法，将衬底放置于原子层沉积的反应腔室中，将反应腔室抽真空且分别对衬底、反应腔室、管路与反应源加热至指定温度（S110）；其中，反应源包括银源和硫源；依次循环地进行沉积；以第一脉冲时间将银源通入反应腔室，用惰性气体以第一吹扫时间吹扫反应腔室（S120）；以第二脉冲时间将硫源通入反应腔室，用惰性气体以第二吹扫时间吹扫反应腔室（S130）；银源与硫源在反应腔室中进行原子层沉积，获得硫化银薄膜样品，将硫化银薄膜样品在反应腔室中的真空环境中冷却至室温后，将硫化银薄膜样品从反应腔室取出（S140）。解决了现有技术中存在无法精确控制硫化银薄膜的厚度，同时无法大规模生产硫化银薄膜的技术问题，达到了硫化银薄膜维持良好的三维保形性，薄膜厚度在单原子层量级的精确可控，能够适合大规模生产的技术效果。

Description

一种Ag 2S薄膜的制备方法
相关申请的交叉引用
本申请要求2019年11月19日提交中国专利局的专利申请No.201911137328.7的优先权，其全部内容在此通过引用合并在本申请中。
技术领域
本申请涉及半导体技术领域，特别涉及一种Ag 2S薄膜的制备方法。
背景技术
在传统材料中，金属材料和合金具有室温延展性，金属键在外力作用下可以产生塑性形变。而无机半导体材料和陶瓷绝缘材料通常都属于脆性材料。而近期有研究表明硫化银是一种在室温条件下具有类似金属的优异延展性的无机半导体材料。其具有不同于常规无机半导体材料的力学性能，特别是拥有良好的可延展性及弯曲性，有望在柔性电子学领域获得广泛应用。α-Ag 2S材料的优异延展性主要是源于其本征的结构和化学键。满足延展性的条件主要有两点：(1)可以实现原子、缺陷或者界面沿特定晶面的滑移(具有较小的滑移能垒EB)；(2)滑移面内具有相对强的原子间作用力以保证材料的完整性(具有较大的分裂能级Ec)。综合来看，α-Ag 2S具有很小的滑移势垒和较大的分裂能级，使得它具有优异的延展性。
目前而言，硫化银体相材料主要通过铸锭浇注法和放电等离子烧结法制备获得；而硫化银薄膜材料主要通过量子点胶体溶液旋涂得到，但这些制备方法并不适合半导体工业生产。
现有技术中存在无法精确控制硫化银薄膜的厚度，同时无法大规模生产硫化银薄膜的技术问题。
发明内容
本发明实施例提供了一种Ag 2S薄膜的制备方法，用以解决现有技术中存在的无法精确控制硫化银薄膜的厚度，同时无法大规模生产硫化银薄膜的技术问题。
为了解决上述问题，本发明实施例提供了一种Ag 2S薄膜的制备方法，所述方法包括：将衬底放置于用于原子层沉积的反应腔室中，将所述反应腔室抽真空且分别对衬底、所述反应腔室、作为反应源和反应中的辅助气体通道的管路以及反应源加热至指定温度，其中，所述反应源包括银源和硫源；依次循环进行以下四个阶段：以第一脉冲时间将所述银源通入所述反应腔室，用惰性气体以第一吹扫时间吹扫所述反应腔室，以第二脉冲时间将所述硫源 通入所述反应腔室，用所述惰性气体以第二吹扫时间吹扫所述反应腔室，以使所述银源与所述硫源在所述反应腔室中进行原子层沉积，获得硫化银薄膜样品；将所述硫化银薄膜样品在所述反应腔室中的真空环境中冷却至室温后，将所述硫化银薄膜样品从所述反应腔室取出。根据一些实施例，所述衬底包括：硅片、蓝宝石、玻璃中的一种。
根据一些实施例，所述衬底、所述反应腔室、所述管路与所述反应源的加热的指定温度范围均为25℃～200℃。
根据一些实施例，所述银源为三甲基膦六氟乙酰丙酮银、新癸酸银、2，2，6，6-四甲基-3，5-庚二酮酸根银、三乙氧基膦银、三乙基膦银、三甲基膦银、乙酰丙酮银中的一种。
根据一些实施例，所述第一脉冲时间的范围为1ms～5s，优选为0.01～5S。
根据一些实施例，所述第一吹扫时间为1～300S，优选为1～180S。
根据一些实施例，所述硫源为六甲基二硅硫烷、硫化氢、硫粉、硫化铵中的一种。
根据一些实施例，所述第二脉冲时间的范围为0.01～5S。
根据一些实施例，所述第二吹扫时间为1～180S。
本发明实施例中的上述一个或多个技术方案，至少具有如下一种或多种技术效果：
本发明实施例提供了一种Ag 2S薄膜的制备方法，所述方法包括：将衬底放置于原子层沉积的反应腔室中，将所述反应腔室抽真空且分别对衬底、所述反应腔室、作为反应源和反应中的辅助气体通道的管路以及反应源加热至指定温度，其中，所述反应源包括银源和硫源；依次循环进行以下四个阶段：以第一脉冲时间将所述银源通入所述反应腔室，用惰性气体以第一吹扫时间吹扫所述反应腔室，以第二脉冲时间将所述硫源通入所述反应腔室，用所述惰性气体以第二吹扫时间吹扫所述反应腔室，以使所述银源与所述硫源在所述反应腔室中进行原子层沉积，获得硫化银薄膜样品，将所述硫化银薄膜样品在所述反应腔室中的真空环境中冷却至室温后，将所述硫化银薄膜样品从所述反应腔室取出。通过在抽真空的反应腔室内放置衬底，并对衬底、反应腔室等加热，依次循环地往反应腔室内通入银源、以惰性气体吹扫反应腔室、往反应腔室内通入硫源、以惰性气体吹扫反应腔室，从而在腔体中进行原子层沉积，获得硫化银薄膜,解决了现有技术中存在无法精确控制硫化银薄膜的厚度，同时无法大规模生产硫化银薄膜的技术问题，达到了硫化银薄膜维持良好的三维保形性，薄膜厚度在单原子层量级精确可控，操作简单，能够与现有的半导体生产线兼容，又能够适合大规模生产的技术效果。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技 术手段，而可依照说明书的内容予以实施，并且为了让本发明的上述和其它目的、特征和优点能够更明显易懂，以下特举本发明的具体实施方式。
附图说明
图1为本说明书实施例中Ag 2S薄膜的制备方法的流程图。
具体实施方式
本发明实施例提供了一种Ag 2S薄膜的制备方法，用以解决现有技术中存在无法精确控制硫化银薄膜的厚度，同时无法大规模生产硫化银薄膜的技术问题，达到了硫化银薄膜维持良好的三维保形性，薄膜厚度在单原子层量级的精确可控，操作简单，能够与现有的半导体生产线兼容，又能够适合大规模生产的技术效果。
本发明实施例中的技术方案，所述Ag 2S薄膜的制备方法采用将衬底放置于原子层沉积的反应腔室中，将所述反应腔室抽真空且分别对衬底、所述反应腔室、管路与反应源加热至指定温度，其中，所述反应源包括银源和硫源；以第一脉冲时间将所述银源通入所述反应腔室，用惰性气体以第一吹扫时间吹扫所述反应腔室；以第二脉冲时间将所述硫源通入所述反应腔室，用所述惰性气体以第二吹扫时间吹扫所述反应腔室；所述银源与所述硫源在所述反应腔室中进行原子层沉积，获得硫化银薄膜样品，将所述硫化银薄膜样品在所述反应腔室中的真空环境中冷却至室温，将所述硫化银薄膜样品从所述反应腔室取出，达到了硫化银薄膜维持良好的三维保形性，薄膜厚度在单原子层量级的精确可控，操作简单，能够与现有的半导体生产线兼容，又能够适合大规模生产的技术效果。
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明实施例提供了一种Ag 2S薄膜的制备方法，请参考图1，所述方法包括步骤110-步骤140：
在第一步骤110中，将衬底放置于原子层沉积的反应腔室中，将所述反应腔室抽真空且分别对衬底、所述反应腔室、管路与反应源加热至指定温度，其中，所述反应源包括银源和硫源；
在一些实施例中，所述衬底可以包括：硅片、蓝宝石或玻璃。在一些实 施例中，所述衬底、所述反应腔室、所述管路与所述反应源的加热的指定温度范围均为25℃～200℃。
在一个具体实施例中，Ag 2S薄膜的制备方法是通过在抽真空的反应腔室内放置硅衬底，并对硅衬底、反应腔室等加热，往反应腔室内依次循环通入银源、惰性气体、硫源和惰性气体，在腔体中进行原子层沉积，获得硫化银薄膜。在上述过程中，通入银源持续第一脉冲时间，通入硫源持续第二脉冲时间。所述第一脉冲时间和第二脉冲时间的范围分别为1ms～5s，优选为0.01～5S。所述惰性气体用于冲扫反应腔室，吹扫时间可以为1～300S，优选为1～180S。惰性气体可以作为反应中的辅助气体，用于吹扫反应残留物。另外，在通入硫源和银源时，也可以用惰性气体作为载气。
所述方法对于硫化银在存储、逻辑器件、存算一体以及柔性器件等领域应用具有重要意义。其中，α-Ag 2S晶体在室温下具有锯齿形的褶皱层状单斜结构，带隙约1.03eV；其室温电导率0.09-0.16Sm-1且电性能在半导体区间可实现自由调控。α-Ag 2S材料的延展性比其他半导体提高了几个数量级，甚至优于一些合金材料，其拉伸张力可达4.2％，压缩张力高达50％以上，弯曲张力超过20％。而传统的半导体材料通常难以承受任何塑性形变，具有优异延展性的α-Ag 2S材料的发现则打破了半导体材料脆性的定律，故本申请实施例采用原子层沉积生成硫化银薄膜。原子层沉积(atomic layer deposition，ALD)，是一种可以将物质以单原子膜形式一层一层的镀在基底表面的方法。ALD是一种自我限制的表面生长方式，所以ALD可以实现薄膜厚度在单原子层量级的精确可控和在三维纳米结构上100％均匀保形的薄膜覆盖。原子层沉积技术在微电子领域已经作为一种制备动态随机存取存储器(DRAMs)沟槽电容器的高质量电介质层和CMOS晶体管的高介电常数的栅极氧化物层制备的关键技术。采用ALD技术沉积硫化银薄膜，既能够与现有的半导体生产线兼容，又能够适合大规模生产。首先，在原子层沉积的反应腔室中放置硅片、蓝宝石、玻璃等衬底，将所述反应腔室抽真空且分别对衬底、所述反应腔室、管路与反应源加热至指定温度，其中，所述反应源包括银源和硫源，其中，所述衬底、所述反应腔室、所述管路与所述反应源的加热的指定温度范围均为25℃～200℃。
具体地，在步骤120中，以第一脉冲时间将所述银源通入所述反应腔室，用惰性气体以第一吹扫时间吹扫所述反应腔室。
在一些实施例中，所述银源为三甲基膦六氟乙酰丙酮银、新癸酸银、2，2，6，6-四甲基-3，5-庚二酮酸根银、三乙氧基膦银、三乙基膦银、三甲基膦银或乙酰丙酮银。在一些实施例中，所述第一脉冲时间的范围为0.01～5S。在一些实施例中，所述第一吹扫时间为1～180S。
具体而言，通过上述步骤110，待所述衬底、所述反应腔室、所述管路与所述反应源等加热并稳定在特定温度时，如所述衬底的加热温度为120℃、所述反应腔室的加热温度为120℃、所述管路的加热温度为120℃、三甲基膦六氟乙酰丙酮银100～110℃、六甲基二硅硫烷为室温。以第一脉冲时间0.01～5S将所述银源通入所述反应腔室，用惰性气体以第一吹扫时间1～180S吹扫所述反应腔室，其中，所述银源为三甲基膦六氟乙酰丙酮银、新癸酸银、2，2，6，6-四甲基-3，5-庚二酮酸根银(I)、三乙氧基膦(三氟乙酰丙酮)银、三乙基膦(6，6，7，7，8，8，8七氟-2，2-二甲基-3，5-辛)银、三甲基膦(六氟乙酰丙酮)银、乙酰丙酮银等。例如，当选用三甲基膦六氟乙酰丙酮银作为所述银源时，将固态三甲基膦六氟乙酰丙酮银在原子层沉积设备的固态源加热装置中加热至100～110℃得到三甲基膦六氟乙酰丙酮银蒸汽再通入所述反应腔室，所述三甲基膦六氟乙酰丙酮银源的脉冲时间0.8～1.2S，然后用惰性气体清洗吹扫所述反应腔室20～60S。
在步骤130中，以第二脉冲时间将所述硫源通入所述反应腔室，用所述惰性气体以第二吹扫时间吹扫所述反应腔室。
在一些实施例中，所述硫源为六甲基二硅硫烷、硫化氢、硫粉、硫化铵等。在一些实施例中，所述第二脉冲时间的范围为0.01～5S。在一些实施例中，所述第二吹扫时间为1～180S。
具体而言，以第二脉冲时间0.01～5S将所述硫源通入所述反应腔室，用所述惰性气体以第二吹扫时间1～180S吹扫所述反应腔室。其中，所述硫源为六甲基二硅硫烷、硫化氢、硫粉、硫化铵等。例如，当选用六甲基二硅硫烷为所述硫源时，所述六甲基二硅硫烷的脉冲时间0.2～0.8S，然后用惰性气体清洗吹扫所述反应腔室20～60S。
上述步骤120和130可以交替地循环进行，以便进行步骤140。
在步骤140中，所述银源与所述硫源在所述反应腔室中进行原子层沉积，获得硫化银薄膜样品，然后将所述硫化银薄膜样品在所述反应腔室中的真空环境中冷却至室温后，将所述硫化银薄膜样品从所述反应腔室取出。
具体而言，所述银源与所述硫源在所述反应腔室中进行原子层沉积，获得硫化银薄膜样品，所述硫化银薄膜样品具有很好的三维保形性，所述硫化银薄膜厚度在单原子层量级精确可控。将所述硫化银薄膜样品在所述反应腔室中的真空环境中冷却至室温，将所述硫化银薄膜样品从所述反应腔室取出备用，该方法操作简单，有利于量产和与现有半导体生产工艺兼容。
本申请实施例中提供的技术方案，至少具有如下技术效果或优点：
本发明实施例提供了一种Ag 2S薄膜的制备方法，所述方法包括：将衬底放置于原子层沉积的反应腔室中，将所述反应腔室抽真空且分别对衬底、所 述反应腔室、管路与反应源加热至指定温度，其中，所述反应源包括银源和硫源；以第一脉冲时间将所述银源通入所述反应腔室，用惰性气体以第一吹扫时间吹扫所述反应腔室；以第二脉冲时间将所述硫源通入所述反应腔室，用所述惰性气体以第二吹扫时间吹扫所述反应腔室；所述银源与所述硫源在所述反应腔室中进行原子层沉积，获得硫化银薄膜样品，将所述硫化银薄膜样品在所述反应腔室中的真空环境中冷却至室温，将所述硫化银薄膜样品从所述反应腔室取出。通过在抽真空的反应腔室内放置衬底，并对衬底、反应腔室等加热，往反应腔室内通入第一脉冲银源脉冲和第二脉冲硫源脉冲，同时以惰性气体冲扫反应腔室，在腔体中进行原子层沉积，获得硫化银薄膜。解决了现有技术中存在无法精确控制硫化银薄膜的厚度，同时无法大规模生产硫化银薄膜的技术问题，达到了硫化银薄膜维持良好的三维保形性，薄膜厚度在单原子层量级的精确可控，操作简单，能够与现有的半导体生产线兼容，又能够适合大规模生产的技术效果。
尽管已描述了本发明的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例做出另外的变更和修改。所以，所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。
显然，本领域的技术人员可以对本发明实施例进行各种改动和变型而不脱离本发明实施例的精神和范围。这样，倘若本发明实施例的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。

Claims (9)

  1. 一种Ag 2S薄膜的制备方法，包括：
    将衬底放置于原子层沉积的反应腔室中，将所述反应腔室抽真空且分别对衬底、所述反应腔室、作为反应源和反应中的辅助气体通道的管路、以及反应源加热至指定温度，其中，所述反应源包括银源和硫源；
    进行以下步骤：以第一脉冲时间将所述银源通入所述反应腔室，用惰性气体以第一吹扫时间吹扫所述反应腔室，以第二脉冲时间将所述硫源通入所述反应腔室，以及用所述惰性气体以第二吹扫时间吹扫所述反应腔室，以使所述银源与所述硫源在所述反应腔室中进行原子层沉积，获得硫化银薄膜样品；以及
    将所述硫化银薄膜样品在所述反应腔室中的真空环境中冷却至室温后，将所述硫化银薄膜样品从所述反应腔室取出。
  2. 如权利要求1所述的Ag 2S薄膜的制备方法，其中，所述衬底包括：硅片、蓝宝石、玻璃中的一种。
  3. 如权利要求1所述的Ag 2S薄膜的制备方法，其中，所述衬底、所述反应腔室、所述管路与所述反应源的加热的指定温度范围均为25℃～200℃。
  4. 如权利要求1所述的Ag 2S薄膜的制备方法，其中，所述银源为三甲基膦六氟乙酰丙酮银、新癸酸银、2，2，6，6-四甲基-3，5-庚二酮酸根银、三乙氧基膦银、三乙基膦银、三甲基膦银、乙酰丙酮银中的一种。
  5. 如权利要求1所述的Ag 2S薄膜的制备方法，其中，所述第一脉冲时间的范围为0.01～5S。
  6. 如权利要求1所述的Ag 2S薄膜的制备方法，其中，所述第一吹扫时间为1～180S。
  7. 如权利要求1所述的Ag 2S薄膜的制备方法，其中，所述硫源为六甲基二硅硫烷、硫化氢、硫粉、硫化铵中的一种。
  8. 如权利要求1所述的Ag 2S薄膜的制备方法，其中，所述第二脉冲时间的范围为0.01～5S。
  9. 如权利要求1所述的Ag 2S薄膜的制备方法，其中，所述第二吹扫时间为1～180S。
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