Chalcogenide-based thin film modifier, semiconductor substrate manufactured using same, and semiconductor device

Abstract

The present invention relates to a chalcogenide-based thin film modifier, a semiconductor substrate manufactured using the same, and a semiconductor device. The method for producing a metalloid-containing thin film according to the present invention uses a precursor compound containing a halogen and a specific chalcogenide-based thin film modifier capable of filling the position of the halogen removed from the precursor compound, thereby easily producing a high-purity thin film by a simple process while improving the reliability of the thin film.

Description

Technical Field

[0001] The present invention relates to a chalcogenide thin film modifier, a semiconductor substrate and a semiconductor device manufactured using the same, and specifically to a chalcogenide thin film modifier, a semiconductor substrate and a semiconductor device manufactured using the same, wherein the thin film modifier can be used for a chalcogenide thin film used to form a GST (Ge-Sb-Te) triple film, etc., to greatly increase the deposition rate of the thin film and greatly reduce impurities, thereby improving the reliability of the phase change device. Background Art

[0002] Chalcogenide refers to a compound containing a Group 16 chalcogen element, and has a property of rapidly undergoing a phase change between a crystalline state and an amorphous state when heated. This property can be utilized to realize a phase change memory device.

[0003] When forming data storage materials for phase change memory devices, in addition to process conditions such as precursor materials and deposition temperature, the content of by-product carbon compounds in chalcogenide-based films also has an important impact on the quality and performance of data storage materials.

[0004] Generally, a tetravalent germanium precursor can be used to form materials such as GeTe2, but not only can the reliability of the phase change device not be ensured due to the poor phase transfer characteristics, but there is also the problem of Te precipitation during the phase transfer operation.

[0005] In addition, deposition is usually performed at a low temperature of less than 200° C., and therefore, it is necessary to provide a technology for completely removing the ligand of the precursor.

[0006] Therefore, it is necessary to develop a sulfide-based thin film modifier that can ensure the reliability of phase change devices, improve the problem of Te precipitation during phase transfer operation, and have excellent reactivity sufficient to completely remove the ligands in the precursor, as well as a semiconductor substrate and semiconductor device manufactured thereby.

[0007] Furthermore, it is necessary to develop chalcogenide-based thin film modifiers that can be applied to memory devices such as NAND or DRAM, logic devices, etc. in addition to the above-mentioned phase change devices, as well as semiconductor substrates and semiconductor devices manufactured thereby.

[0008] Prior art literature

[0009] Korean Patent No. 10-1279925 Summary of the invention

[0010] Problem that the invention aims to solve

[0011] In order to solve the problems in the prior art as described above, the purpose of the present invention is to provide a compound of a predetermined structure as a chalcogenide-based thin film modifier to activate a substrate-adsorbed precursor to provide an activated substrate-adsorbed precursor, and having excellent reactivity sufficient to completely remove the ligand to provide a high-quality thin film under low-temperature deposition conditions, and further, to provide a semiconductor substrate and a semiconductor device including the thin film.

[0012] The above-mentioned object and other multiple objects of the present invention can be fully achieved by the present invention described below.

[0013] Means used to solve problems

[0014] In order to achieve the above-mentioned objectives, the present invention provides a chalcogenide-based thin film modifier, which activates a substrate adsorption precursor to provide an activated substrate adsorption precursor, wherein the central metal of the substrate adsorption precursor is Ge, Sb, Te, Se or Sn, and the second ligand of the chalcogenide-based thin film modifier is used to replace the first ligand of the substrate adsorption precursor.

[0015] The chalcogenide thin film may be made of Ge, GeTe, GST (GeSbTe), GSS (GeSbSe), SnTe, SST (SnSbTe) or GSST (GeSnSbTe).

[0016] The above-mentioned reaction gas can be substituted because the activation energy of the activated substrate-adsorbed precursor is smaller than the activation energy of the above-mentioned substrate-adsorbed precursor.

[0017] The first ligand may include both silicon and carbon, or may include both nitrogen and carbon, or may include both oxygen and carbon.

[0018] The second ligand has an activation energy (E) lower than that of the first ligand adsorbed on the substrate precursor. A ), (E A第一配体 >E A第二配体 ), the activation energy is determined when reacting with the subsequently injected precursor compound.

[0019] The substrate adsorption precursor does not contain halogen, and the chalcogenide-based film modifier may contain one or more halogens selected from iodine and bromine.

[0020] The chalcogenide-based film modifier may be hydrogen iodide (HI), hydrogen bromide (HBr), or a mixed gas of hydrogen iodide or hydrogen bromide mixed with an inert gas at a molar fraction of 1 to 99.

[0021] The chalcogenide-based thin film may be a germanium-tellurium thin film or a germanium supporting film constituting the germanium-tellurium thin film.

[0022] The germanium-tellurium thin film may include an antimony-tellurium thin film on an upper portion.

[0023] The above-mentioned thin film may be a deposited film.

[0024] Among them, deposition can be carried out by atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), metal organic chemical vapor deposition (MOCVD) or low pressure chemical vapor deposition (LPCVD).

[0025] The above-mentioned chalcogenide-based film modifier can replace the reaction gas.

[0026] The above-mentioned chalcogenide film modifier can utilize the second ligand (for example, halogen) of the chalcogenide film modifier to replace the first ligand of the precursor adsorbed on the substrate to activate the precursor adsorbed on the substrate, thereby facilitating reaction with the reaction precursor injected subsequently. Therefore, a reaction compound that is safe to handle due to its slightly lower reactivity can be used.

[0027] As an example, although a mechanism is followed in which highly reactive TeH2 is injected into a precursor adsorbed on a substrate (e.g., substrate-Ge-guan) to form, for example, substrate-Ge-Te-H and desorb in the form of Guan-H, there is a problem that the Guan ligand cannot be completely removed even with a highly reactive reaction compound (e.g., TeH2).

[0028] The present invention follows the mechanism of injecting a chalcogenide film modifier (e.g., HI) into a precursor adsorbed on a substrate (e.g., substrate-Ge-guan) to form, for example, substrate-Ge-I and desorb in the form of Guan-H, and completely removing the ligand of the substrate adsorbed precursor, i.e., hydrocarbon impurities, through a thorough reaction. Afterwards, a variety of tellurium precursors can be injected to form a chalcogenide film (e.g., substrate-Ge-Te-H).

[0029] That is, the second ligand of the chalcogenide film modifier has an activation energy (E) lower than that of the first ligand of the substrate adsorption precursor. A ), (E A第一配体 >E A第二配体 ), the activation energy can be determined when reacting with the subsequently injected precursor compound.

[0030] The above-mentioned reaction gas can be substituted because the activation energy of the activated substrate-adsorbed precursor is smaller than the activation energy of the above-mentioned substrate-adsorbed precursor.

[0031] In addition, the present invention provides a semiconductor substrate, comprising: a substrate, and a thin film; the thin film is a film deposited using the above-mentioned chalcogenide-based thin film modifier.

[0032] In addition, the present invention provides a semiconductor substrate, which includes: a substrate, and a thin film; the above-mentioned thin film includes a film formed by stacking an antimony-tellurium upper film and a germanium-tellurium lower film, and the above-mentioned germanium-tellurium lower film or the germanium supporting film constituting the above-mentioned germanium-tellurium lower film is a film deposited by replacing the ligand using the above-mentioned chalcogenide thin film modifier.

[0033] The above-mentioned film may be a multi-layer structure of two or more layers.

[0034] The by-produced carbon-containing compounds of the thin film measured by SIMS may be 3,000 counts / second or less.

[0035] The deposition rate of the above film can be above.

[0036] The iodine atom count of the thin film measured by SIMS may be 50 counts / second or more.

[0037] In addition, the present invention provides a semiconductor device including the above-mentioned semiconductor substrate.

[0038] The semiconductor device may be a memory including a phase change memory device, NAND and DRAM, a logic device, etc.

[0039] Effects of the Invention

[0040] According to the present invention, a chalcogenide-based thin film modifier can be provided that effectively desorbs the ligand of the precursor compound adsorbed on the substrate to improve the deposition rate and reduce impurities in the thin film, thereby improving the thin film productivity and being able to replace the reaction gas.

[0041] In addition, the characteristics of the phase change device can be improved, and further, there is an effect of providing a thin film manufacturing method using the same, and a semiconductor substrate and a semiconductor device manufactured thereby.

[0042] In addition, the above-mentioned chalcogenide film modifier can utilize the second ligand (for example, halogen) of the chalcogenide film modifier to replace the first ligand of the precursor adsorbed on the substrate to activate the precursor adsorbed on the substrate, thereby facilitating reaction with the reaction precursor injected subsequently. Therefore, a reaction compound that is safe to handle due to its slightly lower reactivity can be used.

[0043] In addition, although the mechanism of the prior art is to inject highly reactive TeH2 into the precursor adsorbed on the substrate (e.g., substrate-Ge-guan) to form, for example, substrate-Ge-Te-H and desorb in the form of Guan-H, the problem that even with the use of a highly reactive reaction compound (e.g., TeH2) the Guan ligand cannot be completely removed, it is possible to inject a chalcogenide film modifier (e.g., HI) into the precursor adsorbed on the substrate (e.g., substrate-Ge-guan) to form, for example, substrate-Ge-I and desorb in the form of Guan-H, and completely remove the ligand of the substrate-adsorbed precursor, that is, hydrocarbon impurities, through a thorough reaction, and then inject a variety of tellurium precursors to form a chalcogenide film (e.g., substrate-Ge-Te-H). BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 1 is a diagram showing the thin film deposition of Example 1 obtained under the condition of using a chalcogenide-based thin film modifier before and after the introduction of a precursor compound and without the introduction of ammonia gas according to one example of the present invention.

[0045] Figure 2 1 is a diagram showing the deposition of a thin film of Example 2 obtained under the condition that a chalcogenide-based thin film modifier is used before and after the introduction of a precursor compound and no ammonia gas is introduced according to another example of the present invention.

[0046] Figure 3 This is a diagram showing thin film deposition in Comparative Example 1 according to the prior art, in which ammonia gas is introduced as a reaction gas without using a chalcogenide-based thin film modifier. DETAILED DESCRIPTION

[0047] Hereinafter, the chalcogenide-based thin film modifier of the present invention, and the semiconductor substrate and semiconductor device produced using the same will be described in detail.

[0048] The inventors of the present invention have confirmed that providing a predetermined compound that effectively decouples a ligand from a precursor compound having a metalloid as a central metal for forming a chalcogenide thin film as a chalcogenide thin film modifier can significantly increase the deposition rate of the thin film and significantly reduce Cl, O, Si, H, NH, metals, metal oxides, and especially carbon remaining as process byproducts. Based on this, the inventors have studied chalcogenide low-temperature deposited thin films and completed the present invention.

[0049] Hereinafter, a chalcogenide-based thin film modifier, a semiconductor substrate including a thin film produced using the same, and a semiconductor device will be described in detail.

[0050] Chalcogenide film modifiers

[0051] The chalcogenide-based film modifier may be a substance that activates the substrate-adsorbed precursor in the present invention to provide an activated substrate-adsorbed precursor.

[0052] As an example, the central metal of the substrate adsorption precursor is Ge, Sb, Te, Se or Sn, and the ligands contain both silicon and carbon, or both nitrogen and carbon, or both oxygen and carbon to be adsorbed on the substrate.

[0053] Such a substrate adsorption precursor may be a substance that is not only activated but also provides reactivity sufficient to replace the reaction gas when it is activated with a predetermined structure under low temperature process conditions to be modified into an activated substrate adsorption precursor so that the ligand is sufficiently detached.

[0054] Unless otherwise specifically defined in the present invention, the term "predetermined structure" used in the present invention means that a ligand included in a substrate adsorption precursor is replaced with a halogen.

[0055] As an example, the ligand of the substrate adsorption precursor may include both silicon and carbon, or both nitrogen and carbon.

[0056] Preferably, the substrate adsorption precursor does not contain halogen, and the chalcogenide-based film modifier contains one or more halogens selected from iodine and bromine.

[0057] As a specific example, the chalcogenide film modifier may be hydrogen iodide (HI), hydrogen bromide (HBr), or a mixed gas obtained by mixing the HI and HBr in an inert gas at a molar ratio of 1 to 99. Based on the considerations of transporting gaseous substances and reaching the reaction surface, the substance represented by the above structure or a mixed gas thereof with an inert gas is preferred. At this time, the side reaction is suppressed and the film growth rate is adjusted to significantly reduce the by-product carbon-containing compounds in the film, thereby reducing corrosion and degradation, and having the effect of achieving a stoichiometric oxidation state when forming a chalcogenide film.

[0058] As a specific example, the above-mentioned chalcogenide film modifier is a pure 3N~15N hydrogen iodide, a gas mixture of 1~99 mol% of 3N~15N hydrogen iodide and an inert gas with the remainder making the total amount reach 100 mol%, or an aqueous solution mixture of 0.5~70 mol% of 3N~15N hydrogen iodide and water with the remainder making the total amount reach 100 mol%, wherein when the inert gas is nitrogen, helium or argon with a purity of 4N~9N, the effect of reducing process by-products is significant, the step coverage effect is excellent, and the film density improvement effect and the electrical properties of the film are more outstanding.

[0059] Preferably, the chalcogenide film modifier may be a pure 5N-6N hydrogen iodide, a gas mixture of 1-99 mol% of 5N-6N hydrogen iodide and an inert gas with the remainder making the total amount reach 100 mol%, or an aqueous solution mixture of 0.5-70 mol% of 5N-6N hydrogen iodide and water with the remainder making the total amount reach 100 mol%, wherein the inert gas may be nitrogen, helium or argon with a purity of 4N-9N. In this case, side reactions can be suppressed when forming a thin film, and the film growth rate can be adjusted to reduce process by-products in the thin film, thereby reducing corrosion and degradation, and improving the crystallinity of the thin film. Even if a thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film can be greatly improved.

[0060] Preferably, the above-mentioned chalcogenide film modifier can be a compound with a purity of 99.9% or more, a compound with a purity of 99.95% or more, or a compound with a purity of 99.99% or more. For reference, when a compound with a purity of less than 99% is used, impurities may remain in the film or cause side reactions with precursors or reactants. Therefore, materials with a purity of 99% or more should be used as much as possible.

[0061] Preferably, the vapor pressure of the chalcogenide film modifier at 180-240K can be one atmosphere. Within this range, the substance can be smoothly transported into the chamber, thereby having the effect of improving the reactivity of the chalcogenide film and the continuity and film quality of the film.

[0062] The above-mentioned chalcogenide-based film modifier can replace the reaction gas.

[0063] The above-mentioned reaction gas can be substituted because the activation energy of the activated substrate-adsorbed precursor is smaller than the activation energy of the above-mentioned substrate-adsorbed precursor.

[0064] The present invention may include the step of performing plasma post-treatment after vaporizing and injecting a chalcogenide-based film modifier or a precursor compound described later. In this case, the film growth rate can be improved and process byproducts can be reduced.

[0065] The above-mentioned thin film may be a deposited film.

[0066] The above deposition can be carried out by atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), metal organic chemical vapor deposition (MOCVD) or low pressure chemical vapor deposition (LPCVD).

[0067] The substrate may be a silicon wafer, an insulating film or a dielectric film containing -H or -OH terminal groups.

[0068] As an example, the central metal of the substrate adsorption precursor may be a transition metal, preferably, Ge or Te.

[0069] The substance having a structure in which the central metal and the above-mentioned ligand are bonded can be used as a substrate adsorption precursor, and can be activated by the above-mentioned chalcogenide film modifier to obtain an activated substrate adsorption precursor. In this case, when forming a chalcogenide film, the process by-product reduction effect is significant, and there is an advantage of excellent phase change characteristics.

[0070] When the above-mentioned substrate adsorption precursor is (N,N'-diisopropyl-dimethylguanidine) (dimethylamino) germanium (II), the structure of the substrate adsorption precursor activated by the above-mentioned chalcogenide film modifier can be: substrate-Ge-I, and when the oxidation number of the central metal is divalent, it is preferred in terms of reducing the reaction energy.

[0071] The substrate adsorption precursor may be a germanium compound represented by the following Chemical Formula 1.

[0072] [Chemical formula 1]

[0073]

[0074] In the above chemical formula 1, Y 1 and Y 2 are independently selected from R 3 NR 4 R 5 OR 6 , the above R 1 ~R 6 Each is independently a C1-C7 alkyl group.

[0075] In the above chemical formula 1, Y 1 and Y 2 They may independently be -N(CH3)2, -N(CH3)(CH2CH3), -CH3, -CH(CH3)2 or -C(CH3)3.

[0076] In the above chemical formula 1, the above R 1 ~R 2 The germanium compound may be independently methyl, ethyl, propyl or tert-butyl.

[0077] The above-mentioned substrate adsorption precursor is a germanium (II) halide, which can be a germanium compound of Ge (II) Br2, Ge (II) Cl2 (dioxane) or Ge (II) F2.

[0078] As an example, when the above-mentioned substrate adsorption precursor is bis(trimethylsilyl)telluride, the structure of the substrate adsorption precursor activated by the above-mentioned chalcogenide film modifier can be: -substrate-Ge-Te-I, and when the oxidation number of the central metal is divalent, it is preferred in terms of reducing the reaction energy.

[0079] In the present invention, the precursor compound used to form a thin film is a molecule having one or more ligands composed of C, N, Si, H, X (halogen) on the central metal atom (M). When it is a precursor with a vapor pressure of 1mTorr to 100Torr at 25°C, it can maximize the effect of filling the ligand leaving site using the chalcogenide-based thin film modifier described later.

[0080] The central metal may be Ge, Sb, Te, Se or Sn.

[0081] As an example, the precursor compound may be a compound represented by the following Chemical Formula 1.

[0082] [Chemical formula 1]

[0083]

[0084] (In the above chemical formula 1, Y 1 and Y 2 are independently selected from R 3 NR 4 R 5 OR 6 , the above R 1 ~R 6 are independently C1 to C7 alkyl groups.

[0085] In the above chemical formula 1, Y 1 and Y 2 They may independently be -N(CH3)2, -N(CH3)(CH2CH3), -CH3, -CH(CH3)2 or -C(CH3)3.

[0086] In the above chemical formula 1, the above R 1 ~R 2 The germanium compound may be independently methyl, ethyl, propyl or tert-butyl.

[0087] As a specific example, the substrate adsorption precursor can be a germanium compound of Ge(II)Br2(dioxane), Ge(II)Br2, Ge(II)Cl2, Ge(II)Cl2(dioxane), Ge(II)F2(dioxane), or Ge(II)F2.

[0088] As another example, the precursor compound may be a compound represented by the following Chemical Formula 2.

[0089] [Chemical formula 2]

[0090]

[0091] (In the above chemical formula 2, M2 is a metalloid and is different from germanium, tellurium or selenium which is the metal used in chemical formula 1, and R5 to R 10 are independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0092] The above-mentioned M2 may be tellurium (Te) or selenium (Se).

[0093] The above R5~R 10 Can be CH3 or C2H5 independently of each other.

[0094] As an example, the compound represented by the above Chemical Formula 2 may be one or more selected from the structures represented by Chemical Formulas 2-1 to 2-7.

[0095] [Chemical Formula 2-1] to [Chemical Formula 2-7]

[0096]

[0097] The above-mentioned various precursor compounds are molecules having metalloids as their respective central metal atoms (M1, M2) and different ligands. When they are precursors having a vapor pressure of 1 mTorr to 100 Torr at 25°C, they can maximize the reaction with the chalcogenide-based film modifier described later.

[0098] Examples of the tellurium precursor compound and the selenium precursor compound include bis(trimethylsilyl)telluride, tellurium tetrachloride, tellurium bromide, diphenyl ditelluride, tellurium dioxide, bis(trimethylsilyl)selenide, selenium dichloride, selenium tetrachloride, selenium dibromide, selenium tetrabromide, diphenyl selenide, and selenium dioxide. In this case, the reaction with the halide described below can be maximized.

[0099] As a specific example, the tellurium precursor compound may be a compound represented by the following Chemical Formula 3-1.

[0100] [Chemical formula 3-1]

[0101]

[0102] As an example, the above-mentioned precursor compound may be mixed with a polar solvent and then introduced into the chamber. In this case, there is an advantage that the viscosity and vapor pressure of the precursor compound can be easily adjusted.

[0103] Preferably, the polar solvent may be an amine solvent, and as a specific example, may be dimethylamine, diethylamine, trimethylamine or triethylamine. In this case, the polar solvent has the advantages of including an organic solvent with low reactivity and solubility and easy water management, and can improve step coverage even when the deposition temperature is increased during film formation.

[0104] As an example, the solubility of the polar solvent in water (25° C.) is less than 200 mg / L, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, the polar solvent has the advantages of low reactivity to precursor compounds and easy water management.

[0105] In the present invention, the solubility is not particularly limited as long as it is based on the measurement method and standard conventionally used in the art. As an example, a saturated solution can be measured by HPLC.

[0106] Preferably, based on the total weight of the precursor compound and the polar solvent, the content of the polar solvent may be 5 to 95 mol%, more preferably 10 to 90 mol%, even more preferably 40 to 90 mol%, and most preferably 70 to 90 mol%.

[0107] When the content of the above-mentioned polar solvent is greater than the above-mentioned upper limit value, impurities will be induced, thereby causing an increase in the impurity values ​​in the resistor and the film. When the content of the above-mentioned organic solvent is less than the above-mentioned lower limit value, there is a disadvantage that the effect of improving step coverage and reducing impurities such as chloride (Cl) ions by adding solvent is not significant.

[0108] film

[0109] This includes films obtained using the above-mentioned chalcogenide-based film modifiers.

[0110] The above-mentioned film may be a multilayer structure of two or more layers or a multilayer structure of two or three layers.

[0111] The above-mentioned thin film can form a germanium-tellurium thin film or a germanium supporting film constituting the above-mentioned germanium-tellurium thin film.

[0112] As an example, the above-mentioned thin film can be obtained by reacting an activated substrate adsorption precursor represented by the structure of the above-mentioned chemical formula 1 with a chalcogenide-based thin film modifier. At this time, the activated substrate adsorption precursor can be used, and the reaction energy with the reaction gas does not need to be considered. Therefore, a high-quality thin film can be manufactured.

[0113] As an example, the activated substrate-adsorbed precursor has excellent reactivity to replace the reactive gas because the activation energy of the activated substrate-adsorbed precursor is smaller than the activation energy of the substrate-adsorbed precursor.

[0114] As an example, the germanium-tellurium thin film may include an antimony-tellurium thin film on its upper portion.

[0115] The above-mentioned thin film may be a deposited film.

[0116] The above deposition can be carried out by atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), metal organic chemical vapor deposition (MOCVD) or low pressure chemical vapor deposition (LPCVD).

[0117] The by-produced carbon-containing compounds of the thin film measured by SIMS may be 3,000 counts / second or less, 1,000 counts / second or less, or 50 to 600 counts / second.

[0118] The deposition rate of the above film measured by ellipsometer can be above, Above or Within the above range, the film continuity and roughness in the plane direction and the density of the thin film can be improved.

[0119] The iodine atom count of the thin film measured by SIMS may be 50 counts / second or more.

[0120] Among them, one cycle can be a step of adsorbing the above-mentioned chalcogenide film modifier on the substrate, a step of purging the unadsorbed chalcogenide film modifier, a step of supplying the precursor compound represented by the above-mentioned Chemical Formula 2 or Chemical Formula 3 to the substrate, a step of purging the residual precursor compound, a step of modifying the precursor compound using a different chalcogenide film modifier, and a step of purging the residual chalcogenide film modifier as a unit cycle, and the above-mentioned unit cycles are repeated to form a film of a desired thickness.

[0121] The above-mentioned thin film can be provided on SiO2 on the substrate, but is not limited to this, and also includes -SiH, -SiH2, -SiH3, -SiOH, -Si(OH)2, -Si(OH)3, -Si-O-Si-.

[0122] The above-mentioned thin film can be used in a semiconductor device, and as an example, can be used in a phase change memory device.

[0123] In addition, the present invention can provide a stacked film, which is a film formed by stacking an antimony-tellurium upper film and a germanium-tellurium lower film, wherein the germanium-tellurium lower film is formed by activating a precursor compound using a chalcogenide-based thin film modifier to obtain an activated precursor compound represented by the above-mentioned Chemical Formula 1 or Chemical Formula 2, and then adding a chalcogenide-based thin film modifier to modify the ligand of the above-mentioned activated precursor compound.

[0124] Method for manufacturing thin film

[0125] The above-mentioned thin film can be manufactured by various methods as long as it includes the step of forming a metalloid thin film including a germanium-tellurium based material.

[0126] As an example, the step of forming the metalloid thin film including the germanium-tellurium material can be manufactured by the following method.

[0127] As a first step, a chalcogenide-based thin film modifier and a source gas containing a germanium precursor compound are sequentially injected onto a substrate loaded in a chamber.

[0128] As an example, the chalcogenide-based thin film modifier may contain one or more halogens selected from iodine and bromine, and iodine is preferably used.

[0129] In the present invention, the method of delivering the chalcogenide film modifier and the source gas containing the germanium precursor compound to the deposition chamber can adopt a flow control method (Mass Flow Controller; MFC) including a method of delivering volatile gas through a vapor flow control (Mass Flow Controller; MFC) method, a liquid flow control method (Liquid Mass Flow Controller; LMFC), and a liquid delivery method (Liquid Delivery System; LDS).

[0130] At this time, as a carrier gas or dilution gas for transporting the chalcogenide film modifier and the source gas containing the germanium precursor compound to the substrate, one or a mixed gas selected from argon (Ar), nitrogen (N2), and helium (He) can be used, but it is not limited to this.

[0131] In the present invention, as an example, an inert gas may be used as the purge gas, and preferably the above-mentioned carrier gas or diluent gas is used.

[0132] The above-mentioned chamber can be an atomic layer deposition (ALD) chamber, a plasma enhanced atomic layer deposition (PEALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma enhanced chemical vapor deposition (PECVD) chamber, an organic metal chemical vapor deposition (MOCVD) chamber or a low pressure chemical vapor deposition (LPCVD) chamber.

[0133] The substrate loaded in the chamber may include a semiconductor substrate such as a silicon substrate or silicon oxide.

[0134] The substrate may further have a conductive layer or an insulating layer formed on an upper portion thereof.

[0135] The substrate may be maintained at 50 to 500°C, 80 to 500°C, 80 to 350°C, or 80 to 200°C.

[0136] As an example, the substrate may be heated to 50 to 300° C., and as a specific example, heated to 50 to 250° C., 50 to 200° C., or 70 to 200° C., and the chalcogenide-based thin film modifier and the precursor compound may be sequentially injected.

[0137] The chalcogenide film modifier and the germanium precursor compound can be injected onto the substrate in an unheated or heated state. Depending on the deposition efficiency, it is also possible to heat the unheated state during the deposition process. For example, the substrate can be injected at 50 to 300° C. for 1 to 20 seconds.

[0138] As an example, the amount (mg / cycle) of the chalcogenide film modifier and the germanium precursor compound charged into the chamber may be the ratio of the amount (mg / cycle) of the chalcogenide film modifier to the precursor compound used in the third step described later.

[0139] As an example, the ratio of the chalcogenide film modifier to the above-mentioned germanium precursor compound is 1:1 to 1:20, preferably 1:1 to 1:15, and more preferably 1:1 to 1:10. Within this range, the effect of reducing by-product carbon-containing compounds and meeting the low-temperature process requirements are significant.

[0140] As the second step, the step of purging with an inert gas may be included one or more times. The inert gas may be the carrier gas or the diluent gas mentioned above.

[0141] In the step of purging the non-adsorbed materials, the amount of the purge gas introduced into the chamber is not particularly limited. As an example, it can be 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times the volume of the chalcogenide film modifier or germanium precursor compound introduced into the chamber. Within this range, the chalcogenide film modifier and the non-adsorbed germanium precursor compound can be sufficiently removed to form a uniform film and prevent the degradation of the film quality. The amounts of the purge gas and the germanium precursor compound introduced are based on one cycle, respectively, and the volumes of the chalcogenide film modifier and the germanium precursor compound represent the volumes of the vaporized precursor compound vapors.

[0142] In the present invention, the purge is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the film growth rate per cycle is properly controlled, and deposition is performed in an atomic mono-layer or in a manner close thereto, thereby having an advantage in terms of film quality.

[0143] As a third step, a chalcogenide film modifier is injected into the substrate to desorb the ligand of the germanium precursor compound adsorbed on the substrate and fill the desorbed position with halogen. At this time, the precursor adsorbed on the substrate is effectively desorbed to improve the reaction speed, and the film growth rate is appropriately reduced, and the by-product carbon-containing compounds are greatly reduced.

[0144] As an example, the halide may include one or more halogens selected from iodine and bromine, and iodine is preferably used.

[0145] In each cycle, the feeding time (Feeding Time, sec) of the chalcogenide film modifier to the surface of the above-mentioned substrate is preferably 0.01 to 10 seconds, more preferably 0.02 to 3 seconds, more preferably 0.04 to 2 seconds, and further preferably 0.05 to 1 second. Within this range, it has the advantages of low film growth rate, improved film density and excellent economy.

[0146] In the present invention, the supply amount of the chalcogenide film modifier is based on a flow rate of 1 to 300 sccm / cycle at a chamber volume of 15 to 20 L, and more specifically, based on a flow rate of 10 to 100 sccm / cycle at a chamber volume of 18 L.

[0147] In the present invention, the chalcogenide film modifier may be delivered to the deposition chamber by, for example, delivering gas through a Mass Flow Controller (MFC) method.

[0148] Preferably, the above-mentioned third step may further include the following steps: before the above-mentioned chalcogenide film modifier is introduced into the chamber, the temperature in the chamber is increased to the deposition temperature; and / or before the above-mentioned chalcogenide film modifier is introduced into the chamber, an inactive gas is injected into the chamber for purging.

[0149] As the fourth step, one or more steps of purging with an inert gas may be included. In the present invention, the purge gas may be, for example, the above-mentioned carrier gas or diluent gas.

[0150] In the present invention, the purge is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the film growth rate per cycle is properly controlled, and deposition is performed in an atomic mono-layer or in a manner close thereto, thereby having an advantage in terms of film quality.

[0151] In the step of purging the unabsorbed chalcogenide film modifier, the amount of the purge gas introduced into the chamber can be sufficient to remove the unabsorbed chalcogenide film modifier. For example, the amount can be 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the unabsorbed chalcogenide film modifier can be sufficiently removed to form a uniform film and prevent the degradation of the film quality. The amounts of the purge gas and the chalcogenide film modifier introduced are based on one cycle, respectively, and the volume of the chalcogenide film modifier represents the volume of the vaporized chalcogenide film modifier vapor.

[0152] As a specific example, when the above-mentioned chalcogenide film modifier is injected at a flow rate of 100 sccm and an injection time of 0.5 sec (per cycle), and in the step of purging the unadsorbed chalcogenide film modifier, the purge gas is injected at a flow rate of 3000 sccm and an injection time of 5 sec (per cycle), the injection amount of the purge gas is 300 times the injection amount of the chalcogenide film modifier.

[0153] Next, as a fifth step, a tellurium precursor compound may be implanted into the substrate to desorb the halogen bonded to the germanium central metal and form a thin film bonded with tellurium.

[0154] As an example, the tellurium precursor compound may be a compound represented by Chemical Formula 3.

[0155] As an example, the above-mentioned thin film forming method can be implemented at a deposition temperature in the range of 50°C to 300°C, preferably in the range of 50°C to 250°C, more preferably in the range of 50°C to 200°C, and even more preferably in the range of 120°C to 200°C low-temperature deposition temperature. Within this range, it has the effect of realizing process characteristics and growing a thin film with excellent film quality.

[0156] As an example, the above-mentioned thin film forming method can be implemented at a deposition pressure in the range of 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and most preferably at a deposition pressure in the range of 0.3 to 7 Torr. Within this range, the effect of obtaining a thin film with uniform thickness can be achieved.

[0157] In the present invention, the deposition temperature and the deposition pressure may be measured by the temperature and pressure formed in the deposition chamber or by the temperature and pressure applied to the substrate in the deposition chamber.

[0158] The sixth step may include a step of purging with an inert gas.

[0159] In the purge step performed immediately after the tellurium precursor compound supply step, the amount of the purge gas introduced into the chamber may be 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times the volume of the tellurium precursor compound introduced into the chamber. Within this range, the desired effect can be fully obtained. The amounts of the purge gas and the tellurium precursor compound introduced are based on one cycle, respectively.

[0160] In the present invention, the purge is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the film growth rate per cycle is properly controlled, and deposition is performed in an atomic mono-layer or in a manner close thereto, thereby having an advantage in terms of film quality.

[0161] As an example, in the above-mentioned thin film forming method, as needed, the number of repetitions of the implemented unit cycle can be 1 to 99,999 times, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the desired film thickness can be obtained and the effect to be achieved by the present invention can be fully achieved.

[0162] As a specific example of the above-mentioned thin film manufacturing method, the above-mentioned chalcogenide-based thin film modifier and two or more precursor compounds or a mixture thereof with a polar solvent are prepared respectively to deposit a thin film on the substrate placed in the above-mentioned chamber.

[0163] Afterwards, after the prepared multiple precursor compounds or their mixture with polar solvents are injected into the vaporizer, they are changed into vapor phase, transported to the deposition chamber and adsorbed on the substrate, the ligands of the tellurium precursor compounds are replaced by chalcogenide-based thin film modifiers, and the unadsorbed precursor compounds are purged.

[0164] Next, after the prepared tellurium precursor compound is injected into the vaporizer, it is changed into a vapor phase so as to be transported to the deposition chamber and adsorbed on the substrate, and then purging is performed to remove the unadsorbed tellurium precursor compound.

[0165] In the present invention, as an example, a chalcogenide film modifier and two or more precursor compounds may be delivered to a deposition chamber by using a vapor flow control (Mass Flow Controller; MFC) method to deliver a volatile gas (Vapor Flow Control; VFC) or a liquid flow control (Liquid Mass Flow Controller; LMFC) method to deliver a liquid (Liquid Delivery System; LDS).

[0166] At this time, as a carrier gas or dilution gas for transporting chalcogenide film modifiers and two or more precursor compounds to the substrate, one or a mixed gas selected from argon (Ar), nitrogen (N2), and helium (He) can be used, but it is not limited to this.

[0167] In the present invention, an inert gas is used as a purge gas to purge the unreacted residual objects, thereby removing not only the excess reaction gas but also the generated by-products.

[0168] As described above, as an example, the above-mentioned thin film forming method can include the steps of supplying a chalcogenide thin film modifier to a substrate, purging unabsorbed chalcogenide thin film modifier, adsorbing a germanium precursor compound to a substrate, purging unabsorbed germanium precursor compound, supplying a chalcogenide thin film modifier to a substrate, purging unabsorbed chalcogenide thin film modifier, supplying a tellurium precursor compound, and purging residual tellurium precursor compound as a unit cycle, and repeating the above-mentioned unit cycles to form a thin film of desired thickness.

[0169] As an example, the number of repetitions of the unit period may be 1 to 99,999 times, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the desired film properties can be well expressed.

[0170] When the injection time and purge time of the germanium precursor compound in the first and second steps are set to a and b respectively, the injection time and purge time of the halide in the third and fourth steps are set to c and d respectively, and the injection time and purge time of the tellurium precursor compound in the fifth and sixth steps are set to e and f respectively, 0.1≤a≤10, 2a≤b≤4a, 0.1 <c≤10、2c≤d≤8c、2<e≤10、2e≤b≤8e。

[0171] When the injection and purge of the germanium precursor compound and the halide, and the injection and purge of the tellurium precursor compound are taken as one cycle, the deposition rate of the germanium film can meet The above conditions.

[0172] When the injection and purge of the germanium precursor compound and the halide, and the injection and purge of the tellurium precursor compound are taken as a cycle, the following two conditions can be satisfied at the same time: 1) the deposition rate of the above-mentioned film is 2) The density of the film is 9.8~10.5g / cm 3 .

[0173] As an example, a thin film manufacturing apparatus capable of implementing the above-mentioned thin film manufacturing method includes an ALD chamber, a first vaporizer for vaporizing a chalcogenide thin film modifier, a first delivery unit for delivering the vaporized chalcogenide thin film modifier into the ALD chamber, a second vaporizer for vaporizing a germanium thin film precursor and a second delivery unit for delivering the vaporized thin film precursor into the ALD chamber, a third vaporizer for vaporizing a tellurium thin film precursor and a third delivery unit for delivering the vaporized thin film precursor into the ALD chamber. The vaporizer and the delivery unit may be any vaporizer and the delivery unit conventionally used in the art.

[0174] Semiconductor substrate

[0175] The present invention also provides a semiconductor substrate manufactured by the thin film forming method of the present invention or including the thin film, especially a laminated film, in which case the uniformity of the thickness of the thin film is very excellent and the density and reliability of the thin film are excellent.

[0176] Preferably, the film is deposited at a rate of Above and density is 9.8g / cm 3 In the above range, the performance as the diffusion prevention film is excellent, and in particular, the phase change reliability is improved, but the invention is not limited thereto.

[0177] As an example, the halogen remaining in the film may be Br2, Br, Br - , Cl2, Cl or Cl - The lower the residual halogen content in the film, the better the film quality, so it is preferred.

[0178] In addition, the lower the residual carbon content in the thin film is, the better the phase change reliability in the low-temperature deposition step is, which is preferred.

[0179] Preferably, the above-mentioned thin film includes a film formed by stacking an antimony-tellurium upper film and a germanium-tellurium lower film, and the above-mentioned germanium-tellurium lower film or the germanium supporting film constituting the above-mentioned germanium-tellurium lower film is a film deposited by replacing the ligand using the above-mentioned chalcogenide thin film modifier.

[0180] As an example, the film may be a multilayer structure of more than two layers, a multilayer structure of more than three layers, or a multilayer structure of two or three layers, as required. As a specific example, the multilayer film of the two-layer structure may be a lower film-middle film structure, and as a specific example, the multilayer film of the three-layer structure may be a lower film-middle film-upper film structure.

[0181] As an example, the above-mentioned lower layer film may include one or more selected from Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, and TiO2.

[0182] As an example, the intermediate film may be a metalloid-containing thin film, and preferably, may be a germanium-tellurium thin film or a germanium supporting film constituting the germanium-tellurium thin film.

[0183] As an example, the upper layer film may be a thin film containing a metalloid different from the metalloid, and preferably, may be an antimony-tellurium thin film.

[0184] Semiconductor Devices

[0185] According to the present invention, there can be provided a semiconductor device including the above-mentioned semiconductor substrate.

[0186] As an example, the semiconductor device may be a phase change memory device or the like.

[0187] Below, preferred embodiments and drawings are presented to help understand the present invention. The following embodiments and drawings are only used to illustrate the present invention. Those skilled in the art may make various changes and modifications within the scope of the scope of the present invention and technical ideas, and these deformations and modifications fall within the scope of the attached claims.

[0188] [Example]

[0189] A compound having a structure represented by the following Chemical Formula 2-8 and a compound having a structure represented by the following Chemical Formula 3-1 are prepared as precursor compounds.

[0190] [Chemical formula 2-8]

[0191]

[0192] [Chemical formula 3-1]

[0193]

[0194] 5N HBr and 5N HI were prepared as chalcogenide film modifiers, respectively.

[0195] The ALD deposition process is performed using the two precursor compounds and the chalcogenide-based film modifier and the deposition process of the present invention as one cycle.

[0196] Specific experimental methods of Examples and Comparative Examples are as follows.

[0197] Example 1

[0198] As a first step, 5N HI as a chalcogenide-based film modifier was charged into a tank and supplied into the chamber at 100 sccm / cycle using a mass flow controller (MFC) at room temperature.

[0199] The chalcogenide film modifier was introduced into the deposition chamber with the substrate for 2 seconds, and then argon gas was supplied at 3000 sccm for 8 seconds to perform argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0200] As a second step, a precursor compound having a structure represented by the above chemical formula 2-8 was charged into a tank maintained at 25° C. and supplied to another vaporizer heated to 150° C. at a flow rate of 0.05 g / min using a liquid mass flow controller (LMFC) at room temperature. After the precursor compound vaporized into a vapor phase in the vaporizer was put into the deposition chamber within 1 second using a mass flow controller (MFC), argon gas was supplied at 3000 sccm for 5 seconds to perform argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0201] As the third step, 5N HI was loaded into a tank as a chalcogenide film modifier and supplied to the chamber at 100 sccm / cycle using a mass flow controller (MFC) at room temperature. The chalcogenide film modifier vaporized in the vaporizer into a vapor phase was fed into the deposition chamber loaded with the substrate for 2 seconds, and then argon was supplied at 3000 sccm for 8 seconds to perform argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0202] As a fourth step, a precursor compound having a structure represented by the above chemical formula 3-1 was charged into a tank maintained at 25° C. and supplied to another vaporizer heated to 150° C. at a flow rate of 0.05 g / min using a liquid mass flow controller (LMFC) at room temperature. After the precursor compound vaporized into a vapor phase in the vaporizer was put into the deposition chamber within 1 second using a mass flow controller (MFC), argon gas was supplied at 3000 sccm for 5 seconds to perform argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0203] This process was repeated 200 to 400 times at a temperature of 130°C to produce Figure 1 Self-limiting atomic layer films.

[0204] like Figure 1 As shown, the deposition thickness of the above film is

[0205] The deposition rate of the film produced at the above deposition temperature of 130°C is

[0206] Furthermore, the impurity content of the above-mentioned film was measured.

[0207] Among them, impurities such as H, C, NH, OSi, Cl, and Ti were measured using secondary-ion mass spectrometry (SIMS) equipment.

[0208] Specifically, the impurity content (counts) was considered when the sputtering time was 50 seconds and the contamination in the substrate skin layer was less by digging into the thin film in the axial direction using ion sputtering, and the impurity value was confirmed in the SIMS graph.

[0209] The SIMS results confirmed that the average impurity content of carbon (C) in the film was calculated to be 151 counts / second. In addition, it was confirmed that not only carbon but also Cl remaining as a by-product of the process was reduced. - , O, Si, H, NH, metals, metal oxides.

[0210] Example 2

[0211] The same steps as in Example 1 were repeated except that the temperature condition of 130° C. was replaced with the temperature condition of 170° C. in Example 1.

[0212] The results, such as Figure 2As shown, the deposition thickness of the above film is

[0213] Furthermore, the impurity content of the above-mentioned film was measured.

[0214] Among them, impurities such as H, C, NH, Cl, and Ti were measured using a secondary-ion mass spectrometry (SIMS) device.

[0215] Specifically, the impurity content (counts) was considered when the sputtering time was 50 seconds and the contamination in the substrate skin layer was less by digging into the thin film in the axial direction using ion sputtering, and the impurity value was confirmed in the SIMS graph.

[0216] The SIMS results confirmed that the average impurity content of carbon (C) in the film was calculated to be 151 counts / second. In addition, it was confirmed that not only carbon but also Cl remaining as a by-product of the process was reduced. - , O, Si, H, NH, metals, metal oxides.

[0217] Comparative Example 1

[0218] The same procedures as those of the first embodiment are repeated except that the second step is performed without the first step, and then the fourth step is performed without the third step.

[0219] At this time, the above fourth step is as follows.

[0220] As a fourth step, a precursor compound having a structure represented by the above chemical formula 3-1 is loaded into a tank maintained at 25° C. and supplied to another vaporizer heated to 150° C. at a flow rate of 0.05 g / min using a liquid mass flow controller (LMFC) at room temperature. When the precursor compound vaporized into a vapor phase in the vaporizer is put into the deposition chamber within 1 second using a mass flow controller (MFC), ammonia is injected at 500 sccm, and then argon is supplied at 3000 sccm for 5 seconds to perform argon purge. At this time, the pressure in the reaction chamber is controlled to 2.5 Torr.

[0221] This process was repeated 200 to 400 times at a temperature of 130°C to produce Figure 3 Self-limiting atomic layer films.

[0222] like Figure 3 As shown, the deposition thickness of the above film is

[0223] The deposition rate of the film produced at the above deposition temperature of 130°C is

[0224] Furthermore, the impurity content of the above-mentioned film was measured.

[0225] Among them, impurities such as H, C, NH, O, Cl, and Ti were measured using secondary-ion mass spectrometry (SIMS) equipment.

[0226] Specifically, the impurity content (counts) was considered when the sputtering time was 50 seconds and the contamination in the substrate skin layer was less by digging into the thin film in the axial direction using ion sputtering, and the impurity value was confirmed in the SIMS graph.

[0227] The SIMS results confirmed that the average impurity content of carbon (C) in the film was calculated to be 1806 counts / second. In addition, it was confirmed that not only carbon but also Cl remaining as a by-product of the process was reduced. - , O, Si, H, NH, metals, metal oxides.

[0228] Comparative Example 2

[0229] The same procedure as in Comparative Example 1 was repeated except that the injection and purging steps of ammonia gas were omitted, but deposition did not occur smoothly.

[0230] Example 3

[0231] An antimony-tellurium-based thin film is stacked on the germanium-tellurium-based thin film produced in the above-mentioned Example 1. The above-mentioned antimony-tellurium-based thin film is produced using a SbTe3 precursor compound.

[0232] It can be confirmed from the above results that according to the present invention using a predetermined chalcogenide-based film modifier, compared with Comparative Example 1 in which ammonia is used instead of a chalcogenide-based film modifier, and Comparative Example 2 in which neither a chalcogenide-based film modifier nor ammonia is used, not only the deposition rate and deposition thickness are significantly improved, but also the content of by-product carbon compounds is excellent enough to meet the requirements of low-temperature deposition, thereby improving the phase change reliability.

[0233] In particular, it can be confirmed that even when Example 1 using the chalcogenide-based film modifier of the present invention is used to produce a film under low temperature conditions of 130°C, the deposition rate per cycle is improved by more than 10% and the content of by-product carbon compounds is reduced by more than 80% compared with Comparative Example 1 which does not use the chalcogenide-based film modifier of the present invention.

[0234] In addition, according to the embodiment 1 of the present invention Figure 1 According to Example 2 Figure 2 Compared with the comparative example 1 Figure 3 By comparison, it can be confirmed that hydrocarbon impurities are reduced, thereby depositing a film suitable for phase change.

[0235] Therefore, it can be confirmed that when a predetermined compound is used as the chalcogenide film modifier of the present invention when manufacturing a chalcogenide film, the thickness and deposition rate increase rate of the film are improved, and the impurity reduction characteristics are excellent. Therefore, it is possible to meet the low-temperature process requirements and form a film with excellent phase change reliability.

Claims

1. A chalcogenide film modifier, wherein: by activating the substrate adsorbed precursor to provide an activated substrate adsorbed precursor, The central metal of the substrate adsorption precursor is Ge, Sb, Te, Se or Sn, and the second ligand of the chalcogenide-based film modifier is used to replace the first ligand of the substrate adsorption precursor.

2. The chalcogenide-based thin film modifier according to claim 1, wherein The chalcogenide thin film is made of Ge, GeTe, GeSbTe, GeSbSe, SnTe, SnSbTe or GeSnSbTe.

3. The chalcogenide-based film modifier according to claim 1, wherein The second ligand has an activation energy lower than that of the first ligand of the precursor adsorbed on the substrate, and the activation energy is determined when reacting with a subsequently injected precursor compound.

4. The chalcogenide-based thin film modifier according to claim 1, wherein The substrate adsorption precursor does not contain halogen, and the chalcogenide-based film modifier contains one or more halogens selected from iodine and bromine.

5. The chalcogenide-based thin film modifier according to claim 1, wherein The chalcogenide-based film modifier is hydrogen iodide, hydrogen bromide, or a mixed gas of hydrogen iodide or hydrogen bromide mixed with an inert gas at a molar fraction of 1 to 99.

6. The chalcogenide-based thin film modifier according to claim 1, wherein The chalcogenide-based thin film is a germanium-tellurium thin film or a germanium supporting film constituting the germanium-tellurium thin film, and includes an antimony-tellurium thin film on the upper portion thereof.

7. The chalcogenide-based thin film modifier according to claim 1, wherein The chalcogenide thin film is a deposited film, which is deposited by atomic layer deposition, plasma enhanced atomic layer deposition, chemical vapor deposition, plasma enhanced chemical vapor deposition, organometallic chemical vapor deposition or low pressure chemical vapor deposition.

8. The chalcogenide-based thin film modifier according to claim 1, wherein The second ligand of the chalcogenide-based thin film modifier has an activation energy lower than that of the first ligand of the precursor adsorbed on the substrate, and the activation energy is determined when reacting with a precursor compound that is subsequently injected.

9. A semiconductor substrate, in, include: substrate, and film; The thin film is a film deposited using the chalcogenide-based thin film modifier according to any one of claims 1 to 8.

10. A semiconductor substrate, in, include: substrate, and film; The thin film includes a film formed by stacking an antimony-tellurium upper film and a germanium-tellurium lower film. The germanium-tellurium underlayer film or the germanium supporting film constituting the germanium-tellurium underlayer film is a film deposited by using the chalcogenide-based thin film modifier according to any one of claims 1 to 8 in a ligand replacement manner.

11. The semiconductor substrate according to claim 10, wherein The above-mentioned film is a multi-layer structure of more than two layers.

12. The semiconductor substrate according to claim 10, wherein: The carbon impurities of the above film measured by secondary ion mass spectrometry were less than 3,000 counts / second, and the deposition rate was / cycle or more, and the iodine atoms measured by SIMS are more than 50 counts / second.

13. A semiconductor device, wherein: Comprising the semiconductor substrate according to claim 10 or 12.

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