Deposition substance for metalloid nitride film, method for forming metalloid nitride film, semiconductor substrate manufactured thereby, and semiconductor device

Abstract

The present invention relates to a deposition material for a metalloid nitride film, a method for forming a metalloid nitride film, and a semiconductor substrate and a semiconductor device manufactured thereby, which have the effect of providing a low-temperature deposition material for a metalloid nitride film, a method for forming a metalloid nitride film, and a semiconductor substrate and a semiconductor device manufactured thereby. According to the present invention, a halogen-free precursor is deposited on a substrate by sequentially or simultaneously injecting a low-temperature deposition substance into a metalloid precursor compound that does not contain halogen as a ligand and by replacing the ligand of the halogen-free precursor with the low-temperature deposition substance, such that the reactivity with a reactive substance injected subsequently in the deposition process is improved, and thus the low-temperature deposition substance is deposited on the substrate. Therefore, the growth speed of the film is improved, and the density and refractive index of the deposited film are remarkably improved.

Description

TECHNICAL FIELD

[0001] The present invention relates to a deposition material for a metalloid nitride film, a metalloid nitride film forming method, a semiconductor substrate manufactured thereby, and a semiconductor device, and more particularly, to a deposition material for a metalloid nitride film, a metalloid nitride film forming method, a semiconductor substrate manufactured thereby, and a semiconductor device, in which a low-temperature deposition material is sequentially or simultaneously injected to a metalloid precursor compound free of halogen as a ligand to perform replacement between a ligand of the halogen-free precursor and the low-temperature deposition material, thereby being deposited on a substrate, and reactivity with a subsequent injected reactant is improved in a deposition process, so that thin film growth speed is improved, and density and refractive index of a deposited film are significantly improved. BACKGROUND

[0002] An ideal atomic layer deposition (ALD) process is based on self-limiting reactions, in which a ligand of a precursor adsorbed on a substrate prevents adsorption of a subsequently injected precursor.

[0003] However, in an actual process, a partial thermal decomposition can be included, which is a process in which a ligand is detached from a central metal due to thermal accumulation of a precursor. This process belongs to a kind of chemical vapor deposition (CVD) characteristics, and the greater the characteristics, the lower step-coverage, density, and thickness uniformity of a deposited film, and the like. In addition, when the detached ligand is easily adsorbed on a surface or is easily formed as a fluoride or a chloride, there can be a problem in which the ligand is left as an impurity in a deposited thin film (see J. Phys. Chem. B. 13491-8, “Surface chemistry in the atomic Layer deposition of TiN films from TiCl4 and ammonia” (2006)).

[0004] Density, thickness uniformity, and the like of the deposited film are factors that affect chemical characteristics, and there can be a problem in which a deposited film is contaminated by a by-product from the leaving group being absorbed, or a crystalline arrangement of the deposited film is destroyed, thereby further reducing density.

[0005] Therefore, it is very important to reduce thermal accumulation of a precursor so that a desired process can be implemented in an atomic layer deposition window (ALD window).

[0006] On the other hand, the metalloid nitride film is a deposition film manufactured by using a representative metalloid such as silicon and germanium. As one example, when a silicon nitride film is deposited using a precursor such as Si2Cl6 or SiCl2H2, which is represented by chlorosilane, NH3 or N2H2, which is represented by a nitrogen-based reactant, and the like, thermal deposition is generally performed at a high temperature of 600°C or higher to form a silicon nitride film (SiN x , the x is an integer of 0.8 to 1.2).

[0007] However, the application of the high-temperature process is limited due to the presence of the thermal budget and the like.

[0008] To solve this problem, a deposition process using plasma at 400°C has been reported, but the silicon nitride film formed at a low temperature is not dense and thus does not have corrosion resistance, and finally has a limitation in that it cannot form a structure for constituting a semiconductor device.

[0009] Thus, another method is to use a silicon precursor for a low-temperature process, which is represented by Bis(tertiarybutylamino)silane (BTBAS), Tris(dimethylamino)silane (TDMAS), Diisoprophylamino silane (DIPAS), Bis-Diethylamino Silane (BDEAS), Diiodosilane (DIS), and the like, as a precursor, but the silicon nitride film formed therefrom has low density and refractive index, resulting in insufficient corrosion resistance.

[0010] Therefore, there is a need to develop a deposition film manufacturing method, a semiconductor substrate and a semiconductor device manufactured thereby, and the like, which, on a substrate, replace the ligand of the adsorbed precursor with a second ligand having higher reactivity based on a self-limiting reaction, and react with a reactant to form a deposition film having a complex structure, not only improve the thickness uniformity and film growth rate of the deposition film, but also reduce the residual amount of impurities, and significantly improve the density and refractive index.

[0011] Prior Art Documents

[0012] Patent Document: Korean Patent Publication No. 2017-0089422 SUMMARY

[0013] Problems to be Solved by the Invention

[0014] To solve the problems of the prior art as described above, the present application aims to provide a deposition material for a metalloid nitride film, a metalloid nitride film formation method, a semiconductor substrate manufactured thereby, and a semiconductor device, which significantly improve a thin film growth rate, thickness uniformity and density and refractive index of a deposited film by replacing a ligand of a metalloid precursor compound with a compound having a prescribed structure as a second ligand before, during or after precursor injection.

[0015] The object and other objects of the present application can be achieved by the present application described below.

[0016] Means for solving the problem

[0017] To achieve the above object, the present application provides a deposition material for a metalloid nitride film, which includes an alkyl halide-free compound for replacing part or all of ligands of a group 14 metalloid precursor compound.

[0018] The halogen constituting the alkyl halide-free compound can be one or more selected from iodine and bromine.

[0019] The group 14 metalloid can be one or more selected from silicon (Si), germanium (Ge) and tin (Sn).

[0020] The alkyl halide-free compound can be an alkyl iodide-free compound, hydrogen iodide, hydrogen bromide, an iodine ion-containing compound or an iodine radical-containing compound.

[0021] Further, the present application can be performed by a process of replacing part or all of ligands of the metalloid precursor compound with part or all of the deposition material for a metalloid nitride film on a substrate.

[0022] The metalloid precursor compound can be a precursor compound having a group 14 metalloid as a central metal.

[0023] The group 14 metalloid can be one or more selected from silicon (Si), germanium (Ge) and tin (Sn).

[0024] The ligand L can be -guanidiate, -amidinate, -triazenide, -iPr, -tBu, -Cp, -Ph, -OR1, -OH, -H or -NR2R3, wherein R1, R2 and R3 can be independently -CH3, -CH2CH3, -iPr, -tBu or -H.

[0025] The deposition can be 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).

[0026] Further, the present application provides a semiconductor substrate including the above-mentioned metalloid nitride film on a substrate, wherein when a precursor adsorption state before ligand replacement is substrate-M-Ln (n = an integer of 1 to 3, M = Si, Ge, Sn, L = halogen-free ligand), a precursor adsorption state after ligand replacement is substrate-M-LnXm (L = halogen-free ligand, X = Br, I, n = an integer of 1 to 3, m = an integer of 1 to 3, and n + m = 3 is satisfied).

[0027] Further, the present application provides a semiconductor substrate including the above-mentioned metalloid nitride film on a substrate, wherein when a precursor adsorption state before ligand replacement is substrate-M-Ln (n = an integer of 1 to 3, M = Si, Ge, Sn, L = halogen-free ligand), a precursor adsorption state after ligand replacement is substrate-M-LnXm (L = halogen-free ligand, X = Br, I, n = an integer of 1 to 3, m = an integer of 1 to 3, and n + m = 3 is satisfied).

[0028] The ligand L can be guanidiate, -amidinate, -triazenide, -iPr, -tBu, -Cp, -Ph, -OR1, -OH, -H, or -NR2R3, wherein R1, R2, and R3 can be independently -CH3, -CH2CH3, -iPr, -tBu, or -H, and the state change of the precursor before and after the ligand replacement can be formed by a process of moving the precursor toward the substrate, and a reaction of alkyl halide-free halogen of a deposition material with a ligand of a group 14 metalloid precursor on the substrate.

[0029] The semiconductor substrate can have a multilayer structure of two or more layers.

[0030] A film growth rate of the metalloid nitride film, which is a thickness of the metalloid nitride film measured by an Ellipsometer divided by a number of deposition cycles, can be 0.1 A / cycle or more. The above.

[0031] A refractive index (at a wavelength of 350 nm) of the metalloid nitride film measured by an Ellipsometer can be 2 or less.

[0032] Further, the present application provides a semiconductor device characterized by comprising the semiconductor substrate.

[0033] Effects of the Invention

[0034] According to the present application, the partial or entire ligand of the precursor adsorbed to the substrate is exchanged with halogen to improve the thin film growth rate, and appropriately improve the thickness uniformity and density of the deposited film, thereby having an activation effect of improving the productivity of the deposited film.

[0035] Further, when the deposited film is formed, the refractive index is improved with the improvement of the density, thereby having an effect of providing the etching resistance required for the structure formation of the semiconductor device.

[0036] Further, there is an effect of providing a deposited film manufacturing method and a semiconductor substrate and a semiconductor device manufactured thereby, by which the thickness uniformity of the deposited film can be improved even if having a more complicated structure. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 is a graph comparing the thin film growth rates of three deposited films of Examples 1 to 3 using the deposition material for a nitride film of a quasi-metal according to the present application, according to different deposition temperatures

[0038] Figure 2 is a graph confirming the cycle linearity by increasing the deposition cycle of Example 2 using the deposition material for a nitride film of a quasi-metal according to the present application from 100 cycles to 1000 cycles.

[0039] Figure 3 is a comparison graph of the refractive index (at a wavelength of 350 nm) of the deposited film of Example 1 using the deposition material for a nitride film of a quasi-metal according to the present application and the refractive index (at a wavelength of 350 nm) of the deposited film obtained from Comparative Examples 4, 7, 8.

[0040] Figure 4 is a comparison graph of the X-Ray Reflectometer (XRR) thin film density of the deposited film of Examples 1 to 3 using the deposition material for a nitride film of a quasi-metal according to the present application and the XRR thin film density of the deposited film of Comparative Examples 4 to 6 not using the same. DETAILED DESCRIPTION

[0041] Hereinafter, the deposition material for a nitride film of a quasi-metal, the method for forming a nitride film of a quasi-metal, the semiconductor substrate and the semiconductor device manufactured thereby according to the present application will be described in detail.

[0042] Unless otherwise specifically defined, the quasi-metal used in the present specification refers to a Group 14 element represented by silicon (Si) and germanium (Ge).

[0043] The present inventors have confirmed that by providing a prescribed compound (deposition material for a metalloid nitride film) that can replace a halogen-free ligand of a metalloid precursor compound used to form a deposition film on the surface of a substrate loaded inside a chamber, an improvement in film growth rate, assurance of thickness uniformity of a deposition film, a significant increase in density and refractive index of a deposition film, and a reduction in H, C, N, Cl, etc. remaining as a process by-product are achieved. Based on this, further efforts were made to research a deposition material for a metalloid nitride film, thereby completing the present invention.

[0044] Hereinafter, a deposition material for a metalloid nitride film, a semiconductor substrate including a deposition film manufactured using the same, and a semiconductor device will be described in detail.

[0045] Deposition material for a metalloid nitride film

[0046] The deposition material for a metalloid nitride film, which is a deposition additive compound used in the present invention to better form a deposition film on the surface of a substrate loaded inside a chamber, can be a prescribed compound capable of replacing a ligand to be detached from a precursor.

[0047] As one example, the metalloid precursor compound can be a compound in which a ligand is combined with a Group 14 metalloid, and the ligand combined with the central metal is easily replaced with the deposition material for a metalloid nitride film by a portion or all of the ligand.

[0048] In the case where the deposition material for a metalloid nitride film used in the present invention is an alkyl halide-free compound, a substitution effect can be appropriately exerted by replacement with a halogen-free ligand of the precursor.

[0049] Unless specifically defined otherwise, the term "free of alkyl" refers not only to the exclusion of an alkyl group but also to the exclusion of an alkenyl group or an alkynyl group.

[0050] The halogen constituting the alkyl halide-free compound can be selected from one or more of iodine and bromine.

[0051] Preferably, the deposition material for a metalloid nitride film can be a compound having a purity of 99.99% or more, a compound having a purity of 99.999% or more, or a compound having a purity of 99.9999% or a purity of 99.99999% or more. As a reference, when a compound having a purity of less than 99% is used, impurities can remain in a deposition film or can cause a side reaction with a precursor or a reactant, and thus a substance having a purity of 99% or more is used as much as possible.

[0052] Preferably, the density of the deposition material for the nitride film of the metalloid is 1.0 g / cm 3 to 4.0 g / cm 3 or 2.0 g / cm 3 to 3.4 g / cm 3 and the vapor pressure can reach 1 atmosphere at a temperature of 180 K to 240 K, in which range, the effects of excellent step coverage, thickness uniformity of the deposited film, and film quality are excellent.

[0053] As the deposition material for the nitride film of the metalloid, the alkyl halide-free compound can form an intermediate for providing a deposited film having a structure in which the Group 14 metalloid is combined with a reactant derivative material.

[0054] The intermediate can refer to a state in which a ligand of a metalloid precursor compound is replaced by providing a compound having a prescribed structure as a second ligand.

[0055] The reactant can be a gaseous compound including H2O, H2O2, O2, O3, O radical, D2, H2, H radical, NH3, NO2, N2O, N2, N radical, H2S, or S. Here, D represents deuterium.

[0056] The alkyl halide-free compound is characterized in that it is one or more selected from the group consisting of alkyl iodide-free, hydrogen iodide, hydrogen bromide, iodine ion, or iodine radical, in which case, by suppressing side reactions and adjusting the growth rate of the deposited film, process by-products in the deposited film are reduced to reduce corrosion or deterioration, the crystallinity of the deposited film is improved, stoichiometric composition ratios are achieved when forming a metal oxide film, and even in the case of forming a deposited film on a substrate having a complex structure, the effects of significantly improving step coverage and thickness uniformity of the deposited film are achieved.

[0057] As a specific example, the deposition material for the nitride film of the metalloid can be a gas mixture of 3N to 15N hydrogen iodide, 0.01 wt% to 99.99 wt% of 3N to 15N hydrogen iodide, and an inert gas making up the balance to 100 wt%, or a water solution mixture of 0.5 wt% to 70 wt% of 3N to 15N hydrogen iodide and water making up the balance to 100 wt%, in which case, when the inert gas is nitrogen gas, helium gas, or argon gas having a purity of 4N to 9N, the process by-product reduction effect is excellent, the step coverage is excellent, and the deposited film density improvement effect can be more excellent. Here, N represents normality.

[0058] Preferably, the deposition material for a metalloid nitride film can be a gas mixture of 3N to 7N hydrogen iodide, 1 to 99 weight% of 5N to 6N hydrogen iodide, and the balance of an inert gas to make the total amount 100 weight%, or a water solution mixture of 0.5 to 70 weight% of 5N to 6N hydrogen iodide and the balance of water to make the total amount 100 weight%, wherein the inert gas can be nitrogen, helium, or argon with a purity of 4N to 9N, in which case, a replacement area that does not remain in the deposited film is formed when the deposited film is formed, a relatively sparse deposited film is formed, while inhibiting side reactions and adjusting the growth rate of the deposited film, to reduce process by-products in the deposited film, to reduce corrosion or deterioration, to improve the crystallinity of the deposited film, and even in the case of forming a deposited film on a substrate with a complex structure, the step coverage and thickness uniformity of the deposited film can be significantly improved.

[0059] In the present application, a step of performing plasma post-processing before and after deposition can be included after the deposition material for a metalloid nitride film or the metalloid precursor compound is vaporized and injected, in which case, the growth rate of the deposited film can be improved while reducing process by-products.

[0060] The deposition can be 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).

[0061] Metalloid precursor compound

[0062] In the present application, the metalloid precursor compound for forming a deposited film can be a molecule having a Group 14 metalloid as a central metal atom (M) and having one or more ligands composed of C, N, O, H, etc., in the case of a precursor having a vapor pressure of 1 mTorr to 100 Torr at 25°C, the effect of filling leaving sites with the deposition material for a metalloid nitride film described later can be maximized.

[0063] As one example, a compound having a structure in which a Group 14 metalloid is bonded to one or more ligands L can be used as the metalloid precursor compound.

[0064] The ligand L can be -guanidiate, -amidinate, -triazenide, -iPr, -tBu, -Cp, -Ph, -OR1, -OH, -H, or -NR2R3, where R1, R2, and R3 can each independently be -CH3, -CH2CH3, -iPr, -tBu, or -H, in which case the state change of the precursor before and after the replacement of the ligand can be formed by a process of moving the substrate, and a reaction of substituting the halogen of the deposition material on the substrate for the alkyl halide-free ligand of the group 14 metalloid precursor.

[0065] As one specific example, in the case of silicon, a compound represented by the following Chemical Formula 1-1 or 1-2 can be used.

[0066] In the following Chemical Formula 1-1, silicon can be replaced by other group 14 elements such as germanium (Ge), in which case the effects of excellent process by-product reduction, excellent step coverage, and excellent deposition film density are exhibited.

[0067] [Chemical Formula 1-1]

[0068]

[0069] [Chemical Formula 1-2]

[0070]

[0071] In the case of the following Chemical Formula 1-1 or 1-2, the effects of excellent process by-product reduction, excellent step coverage, and excellent deposition film density improvement, and the like are more outstanding.

[0072] In the Chemical Formula 1-1, L1, L2, L3, and L4 may be the same as or different from each other.

[0073] As one example, in the Chemical Formula 1-1, L1 is -guanidiate, -amidinate, -triazenide, -iPr, -tBu, -Cp, -Ph, or -OR1, and L2, L3, and L4 can each independently be -H, -CH3, -CH2CH3, -OH, -NR2R3, where R1, R2, and R3 can each independently be -CH3, -CH2CH3, -iPr, or -tBu.

[0074] As another example, in the chemical formula 1-1, L1, L2may be independently -iPr, -tBu, -Cp, -Ph or -OR1, L3, L4may be independently -H, -CH3, -CH2CH3, -OH, -NR2R3, wherein R1, R2and R3may be independently -CH3, -CH2CH3, -iPr or -tBu.

[0075] As another example, in the chemical formula 1-1, L1, L2, L3may be independently -iPr, -tBu, -Cp, -Ph or -OR1, L4may be -H, -CH3, -CH2CH3, -OH, -NR2R3, wherein R1, R2and R3may be independently -CH3, -CH2CH3, -iPr or -tBu.

[0076] As another example, in the chemical formula 1-1, L1', L2', L3', L4'may be independently -iPr, -tBu, -Cp, -Ph or -OR1, R1may be -H, -CH3, -CH2CH3, -iPr or -tBu.

[0077] In the chemical formula 1-1, the ligand can form a symmetrical or asymmetrical structure.

[0078] In the chemical formula 1-1, L1, L2, L3and L4may also be the same as or different from each other.

[0079] As another example, in the chemical formula 1-1, L1, L2may be independently -iPr, -tBu, -Cp, -Ph or -OR1, L3, L4may be independently -H, -CH3, -CH2CH3, -OH, -NR2R3, wherein R1, R2and R3may be independently -CH3, -CH2CH3, -iPr or -tBu.

[0080] As another example, in the chemical formula 1-1, L1, L2may be independently -iPr, -tBu, -Cp, -Ph or -OR1, L3, L4may be independently -H, -CH3, -CH2CH3, -OH, -NR2R3, wherein R1, R2and R3may be independently -CH3, -CH2CH3, -iPr or -tBu.

[0081] As still another example, in the Chemical Formula 1-2, L1', L2', L3' can be independently -iPr, -tBu, -Cp, -Ph, or -OR1, and L4 can be -H, -CH3, -CH2CH3, -OH, -NR2R3, where R1, R2, and R3 can be independently -CH3, -CH2CH3, -iPr, or -tBu.

[0082] As still another example, in the Chemical Formula 1-2, L1', L2', L3', L4' can be independently -iPr, -tBu, -Cp, -Ph, or -OR1, and R1 can be -H, -CH3, -CH2CH3, -iPr, or -tBu.

[0083] In the present specification, unless otherwise specified, Pr denotes propyl, Bu denotes butyl, and Ph denotes phenyl.

[0084] As one example, the structure represented by the Chemical Formula 1-1 or 1-2 can be diphenylsilane (DPS), diiodo silane (DIS), hexachloro disilane (HCDS), dichloro silane (DCS), or the like.

[0085] In the present application, as one example, the metalloid precursor compound can be mixed with a non-polar solvent to be introduced into the chamber, in which case there is an advantage that the viscosity or vapor pressure of the metalloid precursor compound can be easily adjusted.

[0086] Preferably, the non-polar solvent can be one or more selected from the group consisting of alkanes and cycloalkanes, in which case there is an advantage that not only an organic solvent having low reactivity and easy moisture management is included, but also step coverage is improved even when the deposition temperature is increased in the deposition film formation process.

[0087] As a more preferred example, the non-polar solvent can include C1 to C10 alkanes or C3 to C10 cycloalkanes, preferably C3 to C10 cycloalkanes, in which case there is an advantage that reactivity is low and moisture management is easy.

[0088] In the present specification, C1, C3, and the like denote the number of carbon atoms.

[0089] Preferably, the cycloalkane can be a C3 to C10 monocycloalkane, among which cyclopentane is liquid at normal temperature and has the highest vapor pressure, thus becoming preferable in the vapor deposition process, but is not limited thereto.

[0090] As one example, the non-polar solvent has a solubility in water (25°C) of 200 mg / L or less, preferably 50 mg / L to 400 mg / L, more preferably 135 mg / L to 175 mg / L, and within this range, has the advantages of low reactivity to the metalloid precursor compound and easy management of moisture.

[0091] In the present specification, the solubility is not particularly limited as long as it is measured according to the measurement method or criteria generally used in the technical field to which the present application pertains, and as one example, can be measured according to high performance liquid chromatography (HPLC) for a saturated solution.

[0092] Preferably, the content of the non-polar solvent can be 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, most preferably 70 to 90% by weight, based on the total weight of the metalloid precursor compound and the non-polar solvent.

[0093] When the content of the non-polar solvent to be introduced exceeds the upper limit value, impurities are induced, so that the number of impurities in the deposited film increases, and when the content of the organic solvent to be introduced is less than the lower limit value, there is a disadvantage that the effect of improving step coverage and the effect of reducing impurities due to the addition of the solvent are low.

[0094] Further, the metalloid precursor compound can be simultaneously introduced into the deposition chamber with the above-described low-temperature deposition material, or the metalloid precursor compound can be introduced into the deposition chamber first, and then the low-temperature deposition material can be introduced.

[0095] Metalloid nitride film

[0096] A deposited film obtained using the deposition material for a metalloid nitride film.

[0097] When the precursor adsorption state before ligand replacement of the metalloid nitride film is a substrate-M-Ln (n = an integer of 1 to 3, M = Si, Ge, Sn, L = a halogen-free ligand), the precursor adsorption state after ligand replacement can be a substrate-M-LnXm (L = a halogen-free ligand, X = Br, I, n = an integer of 1 to 3, m = an integer of 1 to 3, and n + m = 3 is satisfied), or when the precursor before ligand replacement moving to the substrate is M-Ln (n = an integer of 1 to 4, M = Si, Ge, Sn, L = a halogen-free ligand), the precursor state after ligand replacement can be M-LnXm (L = a halogen-free ligand, X = Br, I, n = an integer of 1 to 3, m = an integer of 1 to 4, and n + m = 4 is satisfied).

[0098] The ligand L can be -guanidiate, -amidinate, -triazenide, -iPr, -tBu, -Cp, -Ph, -OR1, -OH, -H, or -NR2R3, where R1, R2, and R3 can each independently be -CH3, -CH2CH3, -iPr, -tBu, or -H. In this case, the state change of the precursor before and after the ligand replacement can be formed by a process of moving the substrate, and a reaction of substituting an alkyl halide of the ligand of the Group 14 metalloid precursor with a halogen of the deposited substance on the substrate.

[0099] As one example, the metalloid nitride film can have a structure represented by the following Chemical Formula 2.

[0100] [Chemical Formula 2]

[0101] M a A d

[0102] (In the Chemical Formula 2, M is a Group 14 metalloid, A is one or more of N and S, a is an integer of 1 or more, and d is 0.8 to 2.2.)

[0103] The deposited film can include only a nitride film, or can include a sulfide film or a chalcogenide in a nitride film, in which case the purposes intended to be achieved by the present application can be achieved.

[0104] It is indicated that the deposited film can include the above-described film components in a single or selective area manner, but is not limited thereto, and can include SiH, SiOH, and the like.

[0105] The deposited film can be used as a diffusion prevention film, an etching stop film, an electrode film, a dielectric film, a gate insulating film, a barrier oxide film, or a charge trap, which are commonly used in semiconductor devices.

[0106] The deposition film can be manufactured by various methods, as one example, can be manufactured by the following method:

[0107] As a first step, a metallocene precursor compound including a Group 14 metalloid and a ligand can be injected onto a substrate loaded in a chamber.

[0108] As one example, the ligand can be L1, L2, L3, L4, L1', L2', L3', L4' represented by the Chemical Formula 1-1, 1-2, wherein the repeated description is omitted.

[0109] In the present specification, as one example, the way in which the metallocene precursor compound is delivered to the deposition chamber can use: a vapor flow control method (VFC) that delivers a volatilized gas using a mass flow controller (MFC); a liquid delivery system (LDS) including a flow control method (MFC) using a liquid mass flow controller (LMFC).

[0110] At this time, as a carrier gas or a dilution gas for moving the metallocene precursor compound to the substrate, one or more than two mixed gases selected from the group consisting of argon (Ar), nitrogen (N2), helium (He) can be used, but are not limited thereto.

[0111] In the present specification, as one example, an inert gas can be used as a purge gas, and preferably the carrier gas or the dilution gas can be used.

[0112] The 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, a metal organic chemical vapor deposition (MOCVD) chamber, or a low pressure chemical vapor deposition (LPCVD) chamber.

[0113] The chamber can perform a purge pretreatment after loading the substrate.

[0114] In the present specification, the purge can preferably be 1000 to 50000 sccm (Standard Cubic Centimeter per Minute), more preferably 2000 to 30000 sccm, and even more preferably 2500 to 15000 sccm, and within this range, the deposition film growth rate per cycle is properly controlled, and deposition is performed in a single atomic mono-layer or close thereto, thereby having an advantage in terms of film quality.

[0115] The substrate loaded in the chamber can include a semiconductor substrate such as a silicon substrate, a silicon oxide substrate, etc.

[0116] The substrate can further include an electrically conductive layer or an insulating layer on an upper portion thereof.

[0117] The substrate can be maintained at 50 to 500°C or 80 to 500°C in the chamber.

[0118] As one example, the substrate can be heated to 50 to 500°C, and as a specific example, can be heated to 80 to 500°C, 100 to 800°C, or 200 to 500°C, and the metalloid precursor compound and the deposition material for a metalloid nitride film described later can be injected onto the substrate in an unheated state or a heated state, or can be injected in an unheated state according to the deposition efficiency, and the heating conditions can be adjusted in the deposition process sequence. As one example, the substrate can be heated to 300 to 600°C, and the metalloid precursor compound can be injected thereon for 1 to 30 seconds.

[0119] As one example, the ratio of the deposition material for a metalloid nitride film used in the second step described later to the amount of the metalloid precursor compound introduced into the chamber (mg / cycle) is 1:1 to 1:20, preferably 1:1 to 1:15, and more preferably 1:1 to 1:10, and within this range, the step coverage improvement effect and the process by-product reduction effect are significant.

[0120] The first step can include a step of purging using an inert gas 1 or more times. The inert gas can use the carrier gas or the dilution gas described above.

[0121] The amount of purge gas fed into the inside of the chamber in the step of purging the non-adsorbed metalloid precursor compound is not particularly limited as long as it is an amount sufficient to remove the non-adsorbed metalloid precursor compound, and can be, for example, 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, the volume of the metalloid precursor compound fed into the inside of the chamber, and within this range, the non-adsorbed metalloid precursor compound can be sufficiently removed to uniformly form a deposition film and prevent deterioration of film quality. Here, the amounts of the purge gas and the metalloid precursor compound fed are based on one cycle, and the volume of the metalloid precursor compound represents the volume of the vapor of the vaporized metalloid precursor compound.

[0122] In the present specification, the purge can preferably be 1,000 to 50,000 seem (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 seem, and even more preferably 2,500 to 15,000 seem, and within this range, the deposition film growth rate per cycle is appropriately controlled, and deposition is performed in a single atomic mono-layer or close thereto, thereby having an advantage in terms of film quality.

[0123] As the second step, an alkyl halide-free substance is injected as a low-temperature deposition substance to convert the ligand leaving site to halogen. In this case, by effectively removing the ligand of the precursor adsorbed to the substrate, the reaction speed is increased, and the deposition film growth rate is appropriately reduced, thereby having an effect of significantly improving the step coverage and thickness uniformity of the deposition film even when a deposition film is formed on a substrate having a complex structure.

[0124] As an example, the halogen can be one or more selected from iodine and bromine, and iodine is preferably used.

[0125] The feeding time (sec) of the deposition substance for a metalloid nitride film to the surface of the substrate is preferably 0.001 to 30 seconds per cycle, more preferably 0.02 to 30 seconds, even more preferably 0.04 to 30 seconds, and further preferably 0.05 to 30 seconds, and within this range, there are advantages in that the deposition film growth rate is high and the step coverage and economy are excellent.

[0126] In the present specification, the feeding time of the deposition material for the metalloid nitride film is 1 to 500 seem based on the volume of the chamber of 15 to 20 L, more specifically, 10 to 200 seem based on the volume of the chamber of 18 L.

[0127] In the present specification, as an example of the method of transferring the deposition material for the metalloid nitride film to the deposition chamber, a vapor flow control method (VFC) in which the vaporized gas is delivered by a mass flow controller (MFC) can be used.

[0128] The second step can include a step of purging using an inert gas 1 or more times. In the present specification, as an example, the purge gas can use the carrier gas or the dilution gas.

[0129] In the present specification, the purge can be preferably 1000 to 50000 seem, more preferably 2000 to 30000 seem, and even more preferably 2500 to 15000 seem, and within this range, the deposition film growth rate per cycle is appropriately controlled, and deposition is performed in a single atomic mono-layer or close thereto, thereby having an advantage in terms of film quality.

[0130] In the step of purging the deposition material for the non-adsorbed metalloid nitride film, the amount of the purge gas introduced into the inside of the chamber is not particularly limited as long as it is an amount sufficient to remove the deposition material for the non-adsorbed metalloid nitride film, and as an example, it can be 10 to 100000 times, preferably 50 to 50000 times, and more preferably 100 to 10000 times, and within this range, the deposition material for the non-adsorbed metalloid nitride film can be sufficiently removed to uniformly form a deposition film and prevent deterioration of the film quality. Here, the amounts of the purge gas and the deposition material for the metalloid nitride film are based on one cycle, respectively, and the volume of the deposition material for the metalloid nitride film indicates the volume of the vapor of the deposition material for the metalloid nitride film that is vaporized.

[0131] As a specific example, in the case of the conditions of 100 seem flow rate and 0.5 seconds of injection time for the injection of the deposition material for the metalloid nitride film (on a one-cycle basis), in the step of purging the non-adsorbed deposition material for the metalloid nitride film, the injection amount of the purge gas is 300 times the injection amount of the deposition material for the metalloid nitride film when the purge gas is injected under the conditions of 3000 seem flow rate and 5 seconds of injection time (on a one-cycle basis).

[0132] The first step and the second step can be combined or changed in order as needed.

[0133] That is, the metalloid precursor compound and the low-temperature deposition material can be injected into the deposition chamber at the same time and then purged, whereby the ligand of the precursor is replaced with all or a part of the low-temperature deposition material, so that adsorption to the substrate can be more efficient.

[0134] Further, the low-temperature deposition material can be injected into the deposition chamber sequentially, purged, and then the metalloid precursor compound can be injected into the deposition chamber and then purged, whereby the ligand of the precursor is replaced with all or a part of the low-temperature deposition material, so that adsorption to the substrate can be more efficient.

[0135] The chemical structure of the ligand of the metalloid precursor compound that has changed can be formed by a "pre-injection process in which an alkyl halogen-free compound is injected (sequentially injected) earlier than the precursor injection process" or a "middle injection process in which an alkyl halogen-free compound is injected (co-injected) at the same time as the precursor" or a "post-injection process in which an alkyl halogen-free compound is injected after the precursor injection process". As a result, it can be formed by the reaction of part or all of the ligand of the metalloid precursor compound adsorbed on the substrate with the alkyl halogen-free compound containing halogen.

[0136] The ligand of the metalloid precursor compound adsorbed on the substrate and replaced with the alkyl halogen-free ligand is removed by reacting with a hydrogen (H) atom derived from a reaction material (reactant), as a result, the group 14 metalloid adsorbed on the substrate can be combined with nitrogen (N) derived from the reaction material (reactant) to form a thin film.

[0137] Next, as a third step, a reaction material (reactant) can be injected to the substrate to form a deposition film derived from the group 14 metalloid.

[0138] As an example, the reaction material (reactant) can be a gaseous compound including H2O, H2O2, O2, O3, O radical, D2, H2, H radical, NH3, N2H2, N2O, N2, N radical, H2S, or S.

[0139] The deposition film intermediate can have a structure in which a reactant derivative and halogen are combined with the Group 14 metalloid.

[0140] The deposition film can have a structure in which a reactant derivative is combined with the Group 14 metalloid.

[0141] As one example, the deposition film formation method can be performed at a deposition temperature in the range of 50°C to 800°C, preferably in the range of 100°C to 700°C, more preferably in the range of 200°C to 650°C, further preferably in the range of 220°C to 500°C, and even further preferably in the range of 220°C to 450°C, and within this range, there is an effect of achieving process characteristics while growing a deposition film of excellent film quality.

[0142] As one example, the deposition film formation method can be performed at a deposition pressure in the range of 0.01 Torr to 20 Torr, preferably in the range of 0.1 Torr to 20 Torr, and more preferably in the range of 0.1 Torr to 10 Torr, and within this range, there is an effect of obtaining a deposition film of uniform thickness.

[0143] In the present specification, the deposition temperature and the deposition pressure can be measured as the temperature and the pressure in the deposition chamber, or can be measured as the temperature and the pressure applied to the substrate in the deposition chamber (measured in accordance with the temperature and the pressure applied to the substrate in the deposition chamber).

[0144] Preferably, the second step can further include a step of raising the temperature in the chamber to the deposition temperature before the deposition material for the metalloid nitride film is introduced into the chamber, and / or a step of injecting an inert gas into the chamber to perform a purge before the deposition material for the metalloid nitride film is introduced into the chamber.

[0145] The third step can include a step of performing a purge using an inert gas.

[0146] As one example, in the purge step performed immediately after the reaction gas supply step, the amount of purge gas introduced into the inside of the chamber can be 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, the volume of the reaction gas introduced into the inside of the chamber, and within this range, the intended purpose can be achieved. Here, the amounts of the purge gas and the reaction gas introduced are each based on one cycle.

[0147] In the present specification, the purge can preferably be 1000 to 50000 seem, more preferably 2000 to 30000 seem, and even more preferably 2500 to 15000 seem, and within this range, the deposition film growth rate per cycle is properly controlled, and deposition is performed in a single atomic mono-layer or close thereto, thereby having an advantage in terms of film quality.

[0148] The deposition film forming method can be repeated 1 to 99999 times, preferably 10 to 10000 times, more preferably 50 to 5000 times, and even more preferably 100 to 2000 times per unit cycle as needed, and within this range, the thickness of the deposition film required can be obtained, and the object to be achieved by the present application can be achieved.

[0149] As a specific example of the deposition film manufacturing method, in order to deposit a deposition film on a substrate located in the chamber, the above-mentioned deposition material for a metalloid nitride film, a metalloid precursor compound, or a mixture thereof with a non-polar solvent is prepared, respectively.

[0150] Subsequently, the prepared metalloid precursor compound or a mixture thereof with a non-polar solvent is injected into a vaporizer, then converted into a vapor phase, and delivered to the deposition chamber, so as to be adsorbed on the substrate, and the ligand of the above-mentioned metalloid precursor compound is replaced with the deposition material for a metalloid nitride film injected in advance, and the unadsorbed metalloid precursor compound is purged.

[0151] Next, the prepared deposition material for a metalloid nitride film is injected into a vaporizer, then converted into a vapor phase, and delivered to the deposition chamber, so as to be adsorbed on the substrate, and purged to remove the unadsorbed deposition material for a metalloid nitride film.

[0152] In the present specification, as an example, the method of transferring the deposition material for a metalloid nitride film and the metalloid precursor compound, etc. to the deposition chamber can use a vapor flow control method (VFC) that delivers the volatilized gas using a mass flow controller (MFC), or a liquid delivery system (LDS) that delivers a liquid using a liquid mass flow controller (LMFC).

[0153] At this time, as a carrier gas or diluent gas for moving the deposition material for the nitride film of a metalloid and the metalloid precursor compound and the like to the substrate, one or more mixed gases selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He) can be used, but the present application is not limited thereto.

[0154] In the present specification, as one example, an inert gas can be used as a purge gas, and preferably the carrier gas or diluent gas can be used.

[0155] Next, a reactant is supplied.

[0156] As the reactant, any reaction gas commonly used in the technical field to which the present application pertains can be used without particular limitation, and preferably a nitriding agent can be included. The nitriding agent reacts with the metalloid precursor compound adsorbed on the substrate to form a nitride film.

[0157] Preferably, the nitriding agent can be nitrogen (N2), hydrazine gas (N2H4), or a mixture of nitrogen and hydrogen.

[0158] Next, an inert gas is used to purge the unreacted residual reaction gas. Thereby, not only excess reaction gas can be removed, but also the generated by-products can be simultaneously removed.

[0159] As described above, as one example, the deposition film forming method can repeat a unit cycle to form a deposition film having a desired thickness, wherein the unit cycle includes the steps of: a step of adsorbing a metalloid precursor compound on a substrate; a step of purging unadsorbed metalloid precursor compound; a step of supplying a deposition material for a nitride film of a metalloid to the substrate; a step of purging unadsorbed deposition material for a nitride film of a metalloid; a step of supplying a reaction gas; and a step of purging residual reaction gas.

[0160] As another example, the deposition film forming method can repeat a unit cycle to form a deposition film having a desired thickness, wherein the unit cycle includes the steps of: a step of delivering a metalloid precursor compound and a low-temperature deposition material to a substrate and reacting to replace a ligand; a step of adsorbing the replaced precursor compound on the substrate; a step of purging unadsorbed metalloid precursor compound, replaced precursor compound, and unreacted low-temperature deposition material; a step of supplying a reaction gas; and a step of purging residual reaction gas.

[0161] As an example, the unit cycle can be repeated 1 to 99999 times, preferably 10 to 1000 times, more preferably 50 to 5000 times, and even more preferably 100 to 2000 times, within which range there is a good effect of expressing the desired properties of the deposited film.

[0162] When the injection time and the purge time of the metalloid precursor compound are set to a and b, respectively, in the first step, the injection time and the purge time of the alkyl halide-free compound are set to c and d, respectively, in the second step, and the injection time and the purge time of the reactant are set to e and f, respectively, in the third step, the following conditions can be satisfied simultaneously: 0.1 ≤ a ≤ 30, a ≤ b ≤ 3a, 0.1 ≤ c ≤ 30, c ≤ d ≤ 4c, 2 ≤ e ≤ 60, and e ≤ f ≤ 3e.

[0163] When the injection and purge steps of the metalloid precursor compound and the alkyl halide-free compound, and the injection and purge steps of the reactant are taken as one cycle, the following four conditions can be satisfied: 1) the deposition thickness of the metalloid nitride film measured using an Ellipsometer is 500 or less; 2) the film growth rate is 0.1 to 5.5 A / min, preferably 0.2 to 5 A / min, more preferably 0.5 to 4 A / min, and even more preferably 1 to 3 A / min; 3) the density of the deposited film is 2 g / cm or more; and 4) the refractive index (at a wavelength of 350 nm) of the deposited film is 2 or more. 3

[0164] The deposition thickness of the metalloid nitride film measured using an Ellipsometer can be 500 or less, or 2 to 300, and more preferably, 5 to 250.

[0165] The density of the deposited film can be 2 g / cm 3 to 5.5 g / cm 3 or 2 g / cm 3 to 5 g / cm 3 .

[0166] The refractive index (at a wavelength of 350 nm) of the metalloid nitride film measured using an Ellipsometer can be 2 or less, or 1 to 2.

[0167] ​As one example, the deposition film manufacturing method can be performed using a deposition film manufacturing apparatus including an ALD chamber, a first vaporizer for vaporizing a deposition material for a metalloid nitride film, a first delivery device for delivering the vaporized deposition material for the metalloid nitride film into the ALD chamber, a second vaporizer for vaporizing a deposition film precursor, and a second delivery device for delivering the vaporized deposition film precursor into the ALD chamber. The vaporizers and the delivery devices are not particularly limited as long as they are commonly used in the technical field to which the present application pertains, and the vaporizers can be omitted when the gas mixture or the vapor pressure is 0.1 Torr or more at normal temperature.

[0168] semiconductor substrate

[0169] Further, the present application provides a semiconductor substrate characterized by being manufactured by the deposition film manufacturing method of the present application or including the deposition film, in which case, the step coverage of the deposition film and the thickness uniformity of the deposition film are remarkably excellent, and the density of the deposition film is excellent.

[0170] As described above, the adsorption state of the metalloid precursor before and after the ligand replacement changes, and can be formed by a reaction of the alkyl halide-free halogen-containing compound, in which the halogen is used to fill the ligand leaving site of the Group 14 metalloid precursor compound and the metal precursor compound on the substrate.

[0171] As one example, the semiconductor substrate can include a metalloid nitride film formed by a process in which a ligand combined with a Group 14 metalloid is replaced by a halogen atom (Br or I) constituting an alkyl halide-free compound, and then the ligand leaving site of the halogen atom (Br or I) is replaced by nitrogen (N).

[0172] As one example, a semiconductor substrate can be provided in which, when the precursor adsorption state before the ligand replacement on the substrate is represented as substrate-M-Ln (n is an integer of 1 to 3, M = Si, Ge, Sn, and L = halogen-free ligand), the precursor adsorption state after the ligand replacement is represented as substrate-M-LnXm (L = halogen-free ligand, X = Br, I, and n + m = 3 when n is an integer of 1 to 3 and m is an integer of 1 to 3).

[0173] As another example, a semiconductor substrate can be provided, wherein when a precursor before replacement of a ligand moving on the substrate is set as M-Ln (n = an integer of 1 to 4, M = Si, Ge, Sn, L = halogen-free ligand), a state of the precursor after replacement of the ligand is M-LnXm (L = halogen-free ligand, X = Br, I, n = an integer of 1 to 3, m = an integer of 1 to 4, and n + m = 4 is satisfied).

[0174] As one example, the metalloid nitride film can have a two-layer or more multilayer structure, a three-layer or more multilayer structure, or a two-layer or three-layer multilayer structure, as needed. As one specific example, the two-layer multilayer film can have a lower film-middle film structure, and as one specific example, the three-layer multilayer film can have a lower film-middle film-upper film structure.

[0175] As one specific example, the middle film can be a TiN electrode for a Dynamic Random Access Memory (DRAM) or a barrier film for a NAND flash memory.

[0176] As one example, the lower film can be a metal film, a nitride film, an oxide film having a composition different from that of the metalloid nitride film, and can include one or more selected from the group consisting of Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, and TiO2.

[0177] As one example, the upper film can be a metal film, a nitride film, an oxide film having a composition different from that of the metalloid nitride film, and can include one or more selected from the group consisting of Si, SiO2, TiN, TiSiN, W, Mo, and MoN.

[0178] Semiconductor device

[0179] According to the present application, a semiconductor device including the above semiconductor substrate can be provided.

[0180] As an example, the semiconductor device can be a low resistive metal gate interconnect, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a three-dimensional Gate-All-Around (GAA) or 3D NAND flash, etc.

[0181] Hereinafter, preferred embodiments and drawings are proposed to help understand the present application, and it is obvious to those skilled in the art that the following embodiments and drawings are only used to exemplify the present application, and various changes and modifications can be made within the scope and technical idea of the present application, and of course these changes and modifications also belong to the scope of the appended patent claims.

[0182] [Embodiments]

[0183] As a metalloid precursor compound, diphenyl silane (DPS), diiodo silane (DIS), hexachloro disilane (HCDS), and dichloro silane (DCS) were prepared, respectively.

[0184] As a deposition material for a metalloid nitride film, 6N-purity HI was prepared.

[0185] The metalloid precursor compound and the deposition material for a metalloid nitride film were used to perform an ALD deposition process as one cycle according to the deposition process sequence of the present application.

[0186] The specific experimental methods of Examples 1 to 6 and Comparative Examples 1 to 8 are as follows.

[0187] Examples 1 to 3

[0188] Through a mass flow controller (MFC), argon gas was injected into the inside of the chamber at a flow rate of 3000 seem to form the internal atmosphere of the deposition chamber until the working pressure reached 1.2 Torr.

[0189] Then, a silicon wafer was placed, and the heating block was heated to reach the deposition temperature.

[0190] Next, the tank filled with the metalloid precursor was heated or cooled to make the vapor pressure of the metalloid precursor shown in Table 1 below at the time of injection into the chamber reach 0.01 to 10 Torr, and the metalloid precursor was injected into the inside of the chamber in a vapor state while hydrogen iodide was injected into the inside of the chamber at a flow rate of 100 seem as a low-temperature deposition material for 1 to 30 seconds. Subsequently, purging was performed for a time twice as long as the injection time of the metalloid precursor and the low-temperature deposition material.

[0191] Subsequently, ammonia was used as a reactant, and was injected into the inside of the chamber at a flow rate of 500 seem for 3 to 60 seconds under a plasma power of 100 W, and then purging was performed for a time twice as long as the injection time of the ammonia. The specific experimental conditions are shown in Table 1 below.

[0192] The process as described above was repeated 200 to 400 times to form three kinds of self-limiting atomic layer deposition films.

[0193] Comparative Examples 1 to 3

[0194] The same process as in Examples 1 to 3 was repeated except that the low-temperature deposition material in Examples 1 to 3 was not used.

[0195] Examples 4 to 6

[0196] Argon gas was injected into the inside of the chamber at a flow rate of 3000 seem by a mass flow controller (MFC) to form the internal atmosphere of the deposition chamber until the working pressure reached 1.2 Torr.

[0197] Then, a silicon wafer was placed, and the heating block was heated to reach the deposition temperature.

[0198] Next, the tank filled with the metalloid precursor was heated or cooled to make the vapor pressure of the metalloid precursor shown in Table 1 below at the time of injection into the chamber reach 0.01 to 10 Torr, and the metalloid precursor was injected into the inside of the chamber in a vapor state for 1 to 30 seconds. Subsequently, purging was performed for a time twice as long as the injection time of the metalloid precursor.

[0199] Next, the tank filled with the low-temperature deposition material was heated or cooled, and hydrogen iodide was injected into the inside of the chamber at a flow rate of 100 seem for 1 to 30 seconds. Subsequently, purging was performed for a time twice as long as the injection time of the low-temperature deposition material.

[0200] Subsequently, ammonia was used as a reactant, and was injected into the inside of the chamber at a flow rate of 500 seem for 3 to 60 seconds under a plasma power of 100 W, after which purging was performed for twice the ammonia injection time. The specific experimental conditions are shown in Table 1 below.

[0201] The process as described above was repeated 200 to 400 times to additionally form three kinds of self-limiting atomic layer deposition films.

[0202] Comparative Examples 4 to 6

[0203] The same process as in Examples 4 to 6 was repeated except that the low-temperature deposition material in Examples 4 to 6 was not used.

[0204] Comparative Examples 7 to 8

[0205] The same process as in Comparative Example 4 was repeated except that the metalloid precursor was replaced with the material shown in Table 1 below, and the deposition temperature was increased to 600°C.

[0206] [Experimental Examples]

[0207] *Film growth rate: The thickness of the deposited film having a thickness of 1 nm to 30 nm was measured at normal temperature and pressure using an ellipsometer device, and the value obtained by dividing the thickness by the number of cycles was used with the unit of nm / cycle. The measurement results are shown in Table 1 below and Figure 2 .

[0208] *Cycle linearity: In Example 2, the film thickness was measured while increasing the number of cycles from 100 cycles to 1000 cycles, and the results are shown in Figure 2 .

[0209] *Refractive index: The refractive index (at a wavelength of 350 nm) was measured using an ellipsometer with respect to the deposited film manufactured, and the results are shown in Table 1 below, Figure 2 and Figure 3 , respectively.

[0210] *Film density: The film density was measured using an X-ray reflection measurement (XRR) device with respect to the deposited film manufactured, and the results are shown in Table 1 below and Figure 4 .

[0211] [Table 1]

[0212]

[0213]

[0214] As shown in Table 1, it can be confirmed that Examples 1 to 6 of the present invention, which use precursor ligands and other types of deposition materials for metalloid nitride films, have significantly improved film growth rate, refractive index and film density compared to Comparative Examples 1 to 8, which do not use low-temperature deposition materials.

[0215] In particular, the following Figure 1 It was confirmed that in Comparative Examples 1 to 3, which did not use the deposition material for metalloid nitride films according to the present invention, thin film growth could not be achieved; whereas in Examples 1 to 3, which used the same, thin film growth was achieved and a significantly reduced and controllable thin film growth rate was shown. For reference, the following Figure 1 FIG. 4 is a graph comparing the film growth rates of three deposited films of Examples 1 to 3 using the deposition material for metalloid nitride films according to the present invention at different deposition temperatures.

[0216] as follows Figure 2 As shown in FIG. 1 , in Example 2 using the deposition material for a metalloid nitride film according to the present invention, the film thickness was measured while increasing the number of cycles from 100 cycles to 1000 cycles, confirming the cycle linearity.

[0217] In addition, in Example 1 using the deposition material for metalloid nitride film according to the present invention, the refractive index value is higher than that of Comparative Examples 4, 7, and 8 in which the deposition material is not used, as can be seen from the following example: Figure 3 Confirm the result. For reference, Figure 3 This is a comparison graph of the refractive index (at a wavelength of 350 nm) of the deposited film of Example 1 using the deposition material for metalloid nitride films according to the present invention and the refractive index (at a wavelength of 350 nm) of the deposited films obtained from Comparative Examples 4, 7, and 8.

[0218] In addition, you can Figure 4 It was confirmed that Examples 1 to 3 using the deposition material for metalloid nitride film according to the present invention had a higher film density than Comparative Examples 4 to 6 not using the same. Figure 4 FIG2 is a graph comparing XRR (X-ray diffraction) film densities of deposited films of Examples 1 to 3 using the deposition material for metalloid nitride films according to the present invention and those of deposited films of Comparative Examples 4 to 6 not using the same.

[0219] Accordingly, it can be confirmed that, according to the present application, a low-temperature deposition material is sequentially or simultaneously injected to a quasi-metal precursor compound (halogen free precursor) having no halogen as a ligand to perform replacement between the ligand of the halogen free precursor and the low-temperature deposition material and to be deposited on a substrate, and reactivity with a subsequent injected reactant is improved in a deposition process, thereby improving a thin film growth speed and significantly improving density and refractive index of a deposited film, and thus, a deposited film is uniformly formed even on a substrate having a complex pattern.

Claims

1. A deposition material for a metalloid nitride film, characterized in that: Included are alkyl-free halides for substituting some or all of the ligands of the Group 14 metalloid precursor compound.

2. The deposition material for metalloid nitride film according to claim 1, characterized in that: The halogen constituting the alkyl-free halide is one or more selected from iodine and bromine.

3. The deposition material for metalloid nitride film according to claim 1, characterized in that: The Group 14 metalloid is one or more selected from silicon, germanium, and tin.

4. The deposition material for metalloid nitride film according to claim 1, characterized in that: The alkyl-free halide is alkyl-free iodide, hydrogen iodide, hydrogen bromide, iodide ion or iodine free radical.

5. A method for forming a metalloid nitride film, characterized in that: The method for forming the metalloid nitride film comprises the following steps: A part or all of the ligands of the metalloid precursor compound are replaced on a substrate with a part or all of the deposition material for a metalloid nitride film comprising the alkyl halide-free material according to any one of claims 1 to 4.

6. The method for forming a metalloid nitride film according to claim 5, wherein: The metalloid precursor compound is a precursor compound centered around a Group 14 metalloid, and the Group 14 metalloid is at least one selected from silicon, germanium, and tin.

7. The method for forming a metalloid nitride film according to claim 5, wherein: The ligand L is -guanidine, -amidine, -triazene, -iPr, -tBu, -Cp, -Ph, -OR1, -OH, -H or -NR2R3, wherein R1, R2 and R3 are independently -CH3, -CH2CH3, -iPr, -tBu or -H.

8. The metalloid nitride film according to claim 5, wherein The deposition is carried out by atomic layer deposition, plasma enhanced atomic layer deposition, chemical vapor deposition, plasma enhanced vapor deposition, metal organic chemical vapor deposition or low pressure vapor deposition.

9. A semiconductor substrate, characterized in that The method comprises forming a metalloid nitride film on a substrate by the method for forming a metalloid nitride film according to claim 5, wherein when the precursor adsorption state of the metalloid nitride film before ligand replacement is referred to as substrate-M-Ln, the precursor adsorption state after ligand replacement is referred to as substrate-M-LnXm. In the substrate-M-Ln, n=an integer of 1 to 3, M=Si, Ge, Sn, L=a halogen-free ligand, In the substrate-M-LnXm, L=halogen-free ligand, X=Br, I, and when n=an integer of 1 to 3 and m=an integer of 1 to 3, n+m=3 is satisfied.

10. A semiconductor substrate, characterized in that: A metalloid nitride film formed on a substrate by the metalloid nitride film forming method according to claim 5, wherein, in the metalloid nitride film, when the precursor before the ligand replacement moving onto the substrate is M-Ln, the precursor state after the ligand replacement is M-LnXm, In the M-LnXm, n=an integer of 1 to 4, M=Si, Ge, Sn, and L=a halogen-free ligand, In the M-LnXm, L=halogen-free ligand, X=Br, I, and when n=an integer of 1 to 3 and m=an integer of 1 to 4, n+m=4 is satisfied.

11. The semiconductor substrate according to claim 9, wherein The ligand L is -guanidine, -amidine, -triazene, -iPr, -tBu, -Cp, -Ph, -OR1, -OH, -H or -NR2R3, wherein R1, R2 and R3 are independently -CH3, -CH2CH3, -iPr, -tBu or -H, and the change in the state of the precursor before and after the ligand replacement is formed by the following methods: a process of moving to the substrate; and a reaction of an alkyl-free halide for replacing the ligand of the Group 14 metalloid precursor with the halogen of the deposited material on the substrate.

12. The semiconductor substrate according to claim 9, wherein The semiconductor substrate has a multi-layer structure with more than two layers.

13. The semiconductor substrate according to claim 9, wherein The film growth rate is obtained by dividing the thickness of the metalloid nitride film measured by ellipsometry by the deposition cycle. above.

14. The semiconductor substrate according to claim 9, wherein The refractive index of the metalloid nitride film at a wavelength of 350 nm measured by spectroscopic ellipsometer is 2 or less.

15. A semiconductor device, characterized in that: Comprising the semiconductor substrate according to claim 9.

Images