Brittleness and resistivity improver, method for forming heterogeneous film using same, and semiconductor substrate and semiconductor device manufactured therefrom

Abstract

The present invention relates to a brittleness and resistivity improver, a method for forming a heterogeneous film using same, and a semiconductor substrate and a semiconductor device manufactured therefrom. According to the present invention, a compound having a predetermined structure is provided, thus having the effect of providing: a brittleness and resistivity improver that can simultaneously improve the brittleness and resistivity, which are in a trade-off relationship, of a heterogeneous film; a method for forming a heterogeneous film using the brittleness and resistivity improver; and a semiconductor substrate and the like manufactured from the brittleness and resistivity improver are provided.

Description

Brittle resistivity improving agent, method for forming a heterogeneous film using the same, semiconductor substrate and semiconductor device manufactured therefrom

[0001] The present invention relates to a brittle resistivity improver, a method for forming a heterogeneous film using the same, and a semiconductor substrate and semiconductor device manufactured therefrom. More specifically, the present invention relates to a brittle resistivity improver capable of simultaneously improving resistivity, which is a trade-off relationship with brittleness of a heterogeneous film, by providing a compound having a predetermined structure as a brittle resistivity improver, a method for forming a heterogeneous film using the same, and a semiconductor substrate manufactured therefrom.

[0002] The ideal atomic layer deposition (ALD) process is based on a self-limiting reaction, where the ligands of the precursor adsorbed on the substrate prevent the deposition of subsequently injected precursors.

[0003] However, since the actual process is usually performed at high temperatures, this may include some thermal decomposition, in which the precursor undergoes thermal history and the ligand is detached from the central metal. The more this phenomenon occurs, the lower the step coverage. If low-temperature deposition is used to solve this, the density of the heterolayer decreases, the volatilization of the reaction product is insufficient, so impurities remain on the reaction surface, and especially, there is a problem that the electrical characteristics are deteriorated due to complex mutual causes.

[0004] Meanwhile, the electrode or conductive barrier of a semiconductor device requires high electrical conductivity characteristics, and the migration of electrode materials such as Al and Cu to silicon must be effectively restricted. In consideration of the problem of poor barrier characteristics, a heterogeneous film was applied.

[0005] In Korean Patent Publication No. 10-2009-0048523, a nitride film of titanium (Ti) and silicon (Si) was formed through chemical vapor deposition (CVD), but the resulting heterogeneous film contained a large amount of impurities such as chlorine and oxygen, resulting in poor resistivity. In a 2004 paper (Science and Technology of Advanced Materials 5, 549-554), a resistivity of 8100 μΩ·cm was reported when the Si content was approximately 30 at% in a heterogeneous film formed through a CVD process, which also resulted in poor resistivity.

[0006] Furthermore, there have been attempts to remove reaction byproducts on the substrate through purge iteration, but there is a problem in that it is difficult to chemically remove the ligands that have not been removed from the substrate-adsorbed precursor species.

[0007] Accordingly, as a technology for implementing a high-purity target element species heterogeneous film, it is necessary to develop a technology that can simultaneously improve brittleness and resistivity, which are in a trade-off relationship, while preventing impurity residue in the heterogeneous film by ideally removing the ligand of the substrate-adsorbed precursor species and allowing the target element species to be densely positioned, thereby improving the heterogeneous film density.

[0008] In order to solve the problems of the prior art as described above, the present invention provides a brittle resistivity improving agent for a heterogeneous film having both excellent brittleness and resistivity.

[0009] In addition, the present invention aims to provide a method for manufacturing a high-purity heterofilm by introducing the brittle resistivity improving agent during the formation of a heterofilm, particularly a nitride heterofilm, so that the ligand of a substrate-adsorbed precursor species is chemically and smoothly removed, thereby realizing an ideal atomic layer deposition process, and a semiconductor substrate and semiconductor device manufactured thereby.

[0010] In addition, the present invention aims to provide a method for forming a high-purity heterogeneous film by improving the crystallinity of the heterogeneous film, thereby improving the density of the heterogeneous film, and reducing the content of impurities in the heterogeneous film, and a semiconductor substrate and semiconductor device manufactured thereby.

[0011] The above and other objects of the present invention can all be achieved by the present invention described below.

[0012] In order to achieve the above object, the present invention provides a brittle resistivity improver characterized in that I) a brittle resistivity improver for a heterogeneous film, wherein the heterogeneous film includes at least one selected from Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga; and at least one selected from Si, Y, Nb, La, and Ce, and the brittle resistivity improver is a compound including an element having an electronegativity in the range of 2.2 to 2.8.

[0013] II) In the above I), the element having an electronegativity within the range of 2.2 to 2.8 may be iodine.

[0014] III) In the above I) to II), the compound including an element having an electronegativity within the range of 2.2 to 2.8 may be a compound having an iodine ligand.

[0015] IV) In the above I) to III), the compound including an element having an electronegativity within the range of 2.2 to 2.8 may be provided from at least one ligand exchange compound selected from a compound having a direct bond between hydrogen (H) and iodine, a compound having a direct bond between carbon (C) and iodine, and a compound having a direct bond between a halogen element (F, Cl, Br) and iodine.

[0016] V) In the above I) to IV), the compound having a direct bond between hydrogen (H) and iodine may have a total binding energy of the compound calculated using the basis set (iodine: LanL2DZ, carbon, hydrogen element: 6-31+G(dp)) of the Gaussian 16 program (DFT-D3 / B3LYP) within the range of 305 to 325 kJ / mol.

[0017] VI) In the above I) to V), the compound having a direct bond between carbon (C) and iodine can exhibit a tertiary structure while the total binding energy of the compound calculated using the basis set (iodine: LanL2DZ, carbon, hydrogen element: 6-31+G(dp)) of the Gaussian 16 program (DFT-D3 / B3LYP) is 165 to 242 kJ / mol.

[0018] VII) In the above I) to VI), the compound having a direct bond between the halogen element (F, Cl, Br) and iodine may have a total binding energy of the compound calculated using the basis set (iodine: LanL2DZ, carbon, hydrogen element: 6-31+G(dp)) of the Gaussian 16 program (DFT-D3 / B3LYP) within the range of 50 to 160 kJ / mol.

[0019] VIII) In the above I) to VII), the compound including an element having an electronegativity within the range of 2.2 to 2.8 may be at least one selected from compounds represented by the following chemical formulas 1-1 to 1-8.

[0020] [Chemical Formulas 1-1 to 1-8]

[0021]

[0022] IX) In the above I) to VIII), the heterofilm can be provided from an iodine-free precursor compound.

[0023] X) In the above I) to IX), the iodine-free precursor compound may be a compound having at least one selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga as a central metal atom (M) and at least one halogen (F, Cl, Br) as a ligand, and a compound having at least one selected from the group consisting of Si, Y, Nb, La, and Ce as a central metal atom (M) and at least one halogen (F, Cl, Br) as a ligand.

[0024] XI) In the above I) to X), the iodine-free precursor compound may be a compound in which the bond dissociation energy between the central metal atom and the ligand, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (central metal, iodine: LanL2DZ, C, N, O, H, X: 6-31+G(dp)) to reduce the central metal atom at a low process temperature of 400°C or less, is each within 350 kJ / mol.

[0025] XII) In the above I) to XI), the precursor compound may be a compound composed of at least one selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga as a central metal atom (M) and a compound composed of silicon as a center, each having a vapor pressure of more than 0.01 mTorr and less than 100 Torr at 25°C.

[0026] XIII) In the above I) to XII), the heterofilm can be represented by TixSiyNz (wherein x is an integer from 0.2 to 0.8, y is an integer from 0.001 to 0.3, and z is an integer from 0.3 to 0.7).

[0027] XIV) In the above I) to XIII), the heterogeneous film is characterized by having a low resistance of 10,000 μΩ·cm or less.

[0028]

[0029] In addition, the present invention provides a method for forming a heterofilm, characterized by comprising the steps of: pre-depositing at least one precursor compound selected from Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga, each having at least one halogen (F, Cl, Br) as a ligand, onto a substrate loaded inside a chamber; and post-depositing at least one precursor compound selected from Si, Y, Nb, La, and Ce, each having at least one halogen (F, Cl, Br) as a ligand.

[0030] XVI) In the above XV), the method for forming the heterofilm may further include one or more steps selected from a pretreatment step of purging the inside of a chamber where pre-deposition and post-deposition are performed with a purge gas in advance; a ligand exchange reaction step of exchanging a ligand of a central metal deposited on a substrate after the pre-deposition; a post-treatment step of purging the inside of the chamber with a purge gas after the pre-deposition; a ligand exchange reaction step of exchanging a ligand of a central metal deposited on a substrate after the post-deposition; a post-treatment step of purging the inside of the chamber with a purge gas after the post-deposition; a step of forming a deposition film through a reduction reaction; and a post-treatment step of purging the inside of the chamber with a purge gas after forming the deposition film.

[0031] XVII) In the above XV) to XVI), the brittle resistivity improving agent described above can be added to the ligand exchange reaction step.

[0032] XVIII) In the above XV) to XVII), the chamber may be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0033] XIX) In the above XV) to XVIII), the substrate can be heated to 300 to 700°C.

[0034] XX) In the above XV) to XIX), the process temperature of the pre-deposition step and the air temperature of the post-deposition step can independently be within the range of 300 to 700°C.

[0035] XXI) In the above XV) to XX), the ligand exchange reaction temperature may be in the range of 300 to 700°C.

[0036] XXII) In the above XV) to XXI), the brittle resistivity improving agent and the precursor compound can be transferred into the chamber by the VFC method, the DLI method or the LDS method.

[0037] XXIII) In the above XV) to XXII), the ratio of the amount (mg / cycle) of the brittle resistivity improver and the precursor compound injected into the chamber may be 1:1 to 1:20.

[0038]

[0039] In addition, the present invention provides a semiconductor substrate characterized in that it includes a heterogeneous film manufactured by the heterogeneous film forming method described above (XXIV).

[0040] XXV) In the above XXIV), the heterogeneous film may have a multilayer structure of two or three or more layers.

[0041] XXVI) In the above XXIV) to XXV), the heterogeneous film can be used for purposes such as a diffusion barrier film, a dielectric film, a gate insulating film, a block heterogeneous film, or a charge trap.

[0042]

[0043] In addition, the present invention provides a semiconductor device including the semiconductor substrate described above in XXVII).

[0044] XXVIII) In the above XXVII), the semiconductor substrate may be a low resistive metal gate interconnect, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a 3D Gate-All-Around (GAA), or a 3D NAND flash memory.

[0045] According to the present invention, when forming a heterogeneous film, the ligand of the substrate-adsorbed precursor species is chemically and smoothly removed, thereby providing a high-purity heterogeneous film while implementing an ideal atomic layer deposition process.

[0046] In addition, there is an effect of providing a brittle resistivity improving agent, a method for forming a heterogeneous film, and a semiconductor substrate and semiconductor device including the same, which can be applied to materials such as electrodes or barriers with high quality by simultaneously improving the brittleness and resistivity of a heterogeneous film that exhibits a conventional trade-off relationship.

[0047] In addition, the present invention has the effect of providing a method for forming a high-purity heterogeneous film by improving the crystallinity of the heterogeneous film, thereby improving the density of the heterogeneous film, and reducing the content of impurities in the heterogeneous film, and a semiconductor substrate and semiconductor device manufactured thereby.

[0048] Figure 1 is a drawing comparing the resistivity measured for a heterogeneous film of Example 1 according to the present invention and a heterogeneous film of Comparative Example 1.

[0049] Figure 2 is a diagram comparing the composition ratio of the contents of Ti, Si, and N elements divided by the diffused contents of Ti and Si.

[0050] Figures 3 to 4 are drawings comparing the H element contents between the heterogeneous films of Examples 1 to 4 and the heterogeneous films of Comparative Examples 1 to 4.

[0051] Figures 5 to 6 are drawings comparing the Cl element contents between the heterogeneous films of Examples 1 to 4 and the heterogeneous films of Comparative Examples 1 to 4.

[0052] Figures 7 to 8 are drawings comparing the iodine doping content between the heterogeneous films of Examples 1 to 4 and the heterogeneous films of Comparative Examples 1 to 4.

[0053] Hereinafter, the brittle resistivity improving agent of the present invention, the method for forming a heterogeneous film using the same, and the semiconductor substrate manufactured therefrom are described in detail.

[0054] In this description, unless otherwise specified, the term “heterogeneous film” refers to a film formed by deposition, which comprises a central metal atom (M) used for electrode or barrier purposes and a central atom (an atom that does not overlap with the M) that can improve the continuity of the film to provide a smooth film.

[0055] In this description, the term “improvement in brittle resistivity” includes, unless otherwise specified, simultaneous improvement in brittleness and resistivity, which exhibit a trade-off relationship in the heterogeneous film.

[0056] As used herein, the term “shielding” means reducing, inhibiting or blocking not only the adsorption of precursor compounds for forming a heterofilm onto a substrate, but also reducing, inhibiting or blocking the adsorption of process byproducts onto the substrate, unless otherwise specified.

[0057]

[0058] The present inventors confirmed that when a heterofilm is formed by including a compound containing an element having a predetermined electronegativity as a brittle resistivity improving agent, both brittleness and resistivity, which are in a trade-off relationship, are improved, and based on this, they devoted themselves to further research and completed the present invention.

[0059]

[0060] The brittle resistivity improving agent of the present invention simultaneously controls the brittleness and resistivity of a heterogeneous film formed on a substrate.

[0061] The above heterofilm can be provided from, for example, one or more precursors selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga and one or more precursors selected from the group consisting of Si, Y, Nb, La, and Ce, and the heterofilm can be provided on the entire substrate or a selective area, and in this case, the desired brittleness and resistivity improvement effects can be sufficiently obtained.

[0062] The above heterofilm can be represented as TixSiyNz (wherein x is an integer from 0.2 to 0.8, y is an integer from 0.001 to 0.3, and z is an integer from 0.3 to 0.7).

[0063] For example, the above x may be an integer from 0.2 to 0.5.

[0064] As another example, the above x may be an integer from 0.3 to 0.499.

[0065] For example, the above y may be an integer from 0.001 to 0.25.

[0066] As another example, the above y may be an integer from 0.001 to 0.2.

[0067] For example, the above z may be an integer from 0.3 to 0.6.

[0068] As another example, the z may be an integer from 0.4 to 0.6.

[0069]

[0070] The above heterofilm can be used in semiconductor devices not only as a commonly used diffusion barrier film, but also as a diffusion barrier film, a dielectric film, a gate insulating film, a block heterofilm, or a charge trap.

[0071]

[0072] The precursor compound used to form the heterofilm in the present invention may be an iodine-free precursor compound.

[0073] For example, the iodine-free precursor compound may be a compound having at least one selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga as a central metal atom (M) and at least one halogen (F, Cl, Br) as a ligand, and a compound having at least one selected from the group consisting of Si, Y, Nb, La, and Ce as a central metal atom (M) and at least one halogen (F, Cl, Br) as a ligand.

[0074] As a specific example, the iodine-free precursor compound may be a compound having at least one selected from the group consisting of Mo, W, Ru, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga as a central metal atom (M) and at least one halogen (F, Cl, Br) as a ligand, and a compound having at least one selected from the group consisting of Si and Nb as a central metal atom (M) and at least one halogen (F, Cl, Br) as a ligand.

[0075] The above iodine-free precursor compound may have a vapor pressure of 1 mTorr to 100 Torr at 25°C.

[0076] The above iodine-free precursor compound may be a compound in which the bond dissociation energy between the central metal atom and the ligand is each within 350 kJ / mol, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (central metal, iodine: LanL2DZ, C, N, O, H, X: 6-31+G(dp)) to reduce the central metal atom at a low process temperature of 400°C or less.

[0077] The above precursor compound may be a compound composed of a central metal atom (M) of at least one selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga, and a compound composed of silicon as the center, each having a vapor pressure of more than 0.01 mTorr and less than 100 Torr at 25°C.

[0078] As a specific example, the above precursor compounds may be compounds represented by the following chemical formula 1.

[0079] [Chemical Formula 1]

[0080]

[0081] (In the above chemical formula 1, M is at least one selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce and Nd, and L1, L2, L3 and L4 may be the same or different as -H, -X, -R, -OR, -NR2 or Cp(cyclopentadiene), wherein -X is F, Cl or Br, and -R may be linear or cyclic as C1-C10 alkyl, C1-C10 alkene, or C1-C10 alkane, and L1, L2, L3 and L4 may be formed from 2 to 6 depending on the oxidation number of the central metal.)

[0082] The above L1, L2, L3 and L4 may include, for example, one or more -X.

[0083] The above L1, L2, L3 and L4 may each include one or more of -H and -X, as another example.

[0084] For example, if the central metal is divalent, L1 and L2 may be attached to the central metal as ligands, and if the central metal is hexavalent, L1, L2, L3, L4, L5, and L6 may be attached to the central metal, and the ligands corresponding to L1 to L6 may be the same or different.

[0085] The above M is at least one selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga, or at least one selected from the group consisting of Si, Y, Nb, La, and Ce, and in this case, there is a large effect of reducing process by-products, an effect of improving the density of the heterogeneous film, and excellent electrical properties and brittleness of the heterogeneous film.

[0086] Specifically, examples of titanium precursor compounds include TiCl4, TiBr4, etc.

[0087] Examples of silicon precursor compounds that can be used include 3DMAS (Tris(dimethylamino)silane), DIPAS (Di(isopropylamino)silane), BDEAS (Bis(diethylamino)silane), BTBAS (Bis(t-butylamino)silane), SiH4, SiH3Cl, SiH2Cl2, SiHCl3, SiCl4, and Si2Cl6.

[0088] For reference, the above BDEAS, DIPAS, and 3DMAS are as follows, respectively.

[0089] (BDEAS, Bis-Diethylamino Silane)

[0090]

[0091] (DIPAS, Di-isopropylamino Silane)

[0092] (3DMAS, Tris(dimethylamino)silane)

[0093]

[0094] The brittle resistivity improving agent of the present invention can improve the crystallinity of a heterofilm by chemically and smoothly removing the ligand of the substrate-adsorbed precursor species of the bilayer, thereby realizing an ideal atomic layer deposition process, thereby improving the density of the heterofilm, and at the same time forming a high-purity heterofilm with reduced impurity content within the heterofilm.

[0095] The above ligand exchange region can be formed, for example, on the entire substrate or a portion of the substrate on which the heterofilm is formed.

[0096] Furthermore, the ligand exchange region may occupy, for example, 10 to 95% of the total area of ​​the entire substrate or a portion of the substrate, when the total area of ​​the substrate is 100%, the ligand exchange region may occupy, for example, 15 to 90% of the area, preferably 20 to 85% of the area, more preferably 30 to 80% of the area, even more preferably 40 to 75% of the area, and even more preferably 40 to 70% of the area, and the myrigand exchange region may occupy the remaining area.

[0097] Furthermore, the ligand exchange region may be such that the first ligand exchange region occupies 10 to 95% of the total area of ​​the entire substrate or a portion of the substrate, specifically 15 to 90% of the area, preferably 20 to 85% of the area, more preferably 30 to 80% of the area, more preferably 40 to 75% of the area, and even more preferably 40 to 70% of the area, and the second ligand exchange region occupies 10 to 95% of the remaining area, specifically 15 to 90% of the area, preferably 20 to 85% of the area, more preferably 30 to 80% of the area, more preferably 40 to 75% of the area, and even more preferably 40 to 70% of the area, and the remaining area may be occupied by the myrigand exchange region.

[0098] The above brittle resistivity improving agent may include a compound including an element having an electronegativity within a range of 2.2 to 2.8.

[0099] The element having the electronegativity within the range of 2.2 to 2.8 may be iodine.

[0100] The compound containing an element having an electronegativity within the range of 2.2 to 2.8 may be a compound having an iodine ligand, in which case the ligand of the substrate-adsorbed precursor species of the bilayer is chemically and smoothly removed, thereby realizing an ideal atomic layer deposition process, thereby improving the crystallinity of the heterolayer, thereby improving the density of the heterolayer, and at the same time forming a high-purity heterolayer with a reduced impurity content in the heterolayer, and at the same time improving the brittleness and resistivity of the bilayer.

[0101] The compound containing an element having an electronegativity within the range of 2.2 to 2.8 may be provided from at least one ligand exchange compound selected from a compound having a direct bond between hydrogen (H) and iodine, a compound having a direct bond between carbon (C) and iodine, and a compound having a direct bond between a halogen element (F, Cl, Br) and iodine.

[0102] The compound having the direct bond between hydrogen (H) and iodine may have a total binding energy of 305 to 325 kJ / mol calculated using the basis set (iodine: LanL2DZ, carbon, hydrogen element: 6-31+G(dp)) of the Gaussian 16 program (DFT-D3 / B3LYP).

[0103] The compound having the direct bond between the above carbon (C) and iodine can exhibit a three-dimensional structure while the total binding energy of the compound is 165 to 242 kJ / mol, calculated using the basis set (iodine: LanL2DZ, carbon, hydrogen element: 6-31+G(dp)) of the Gaussian 16 program (DFT-D3 / B3LYP).

[0104] Compounds having a direct bond between the above halogen elements (F, Cl, Br) and iodine may have a total binding energy of 50 to 160 kJ / mol calculated using the basis set (iodine: LanL2DZ, carbon, hydrogen elements: 6-31+G(dp)) of the Gaussian 16 program (DFT-D3 / B3LYP).

[0105] The compound containing an element having an electronegativity within the range of 2.2 to 2.8 is characterized in that it is at least one selected from compounds represented by the following chemical formulas 1-1 to 1-8, and in this case, the ligand of the substrate-adsorbed precursor species of the bilayer is chemically and smoothly removed, thereby realizing an ideal atomic layer deposition process, thereby improving the crystallinity of the heterolayer, thereby improving the density of the heterolayer, and at the same time forming a high-purity heterolayer with a reduced impurity content in the heterolayer, and at the same time improving the brittleness and resistivity of the bilayer.

[0106] [Chemical Formulas 1-1 to 1-8]

[0107]

[0108] These brittle resistivity improvers can be provided singly or in a mixed gas phase to significantly reduce process byproducts, improve the density of the heterogeneous film, and provide superior electrical properties of the heterogeneous film.

[0109] The above brittle resistivity improving agent may have a boiling point of 100 ˚C or more and 230 ˚C or less at atmospheric pressure. In this case, the ligand of the substrate-adsorbed precursor species of the bilayer is chemically and smoothly removed, thereby realizing an ideal atomic layer deposition process, thereby improving the crystallinity of the heterolayer, thereby improving the density of the heterolayer, and at the same time forming a high-purity heterolayer with a reduced impurity content within the heterolayer, and has the advantage of simultaneously improving the brittleness and resistivity of the bilayer.

[0110] The above reaction gas may include O2, O3, N2O, NO2, N2O, NH3, H2O, H2O2, CO or CO2.

[0111] The above heterofilm may be a heterofilm in which one or more metals selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce and Nd and silicon (S) are laminated together in one or two or more layers.

[0112] The above brittle resistivity improving agent can remain uniformly in the heterogeneous film.

[0113] Here, uniform residue refers to the concentration distribution in the growth direction (depth direction) of the thin film, unless otherwise specified. In this case, by controlling the reaction surface that is intended to provide a heterogeneous film on the substrate surface, the reaction rate is improved, and even when forming a heterogeneous film on a substrate with a complex structure, the thickness uniformity of the thin film is greatly improved, and not only the thin film precursor but also the process by-products are effectively protected by preventing adsorption, and there is an advantage in effectively removing the process by-products.

[0114] The above heterofilm may, for example, contain iodine (I) content 10 to 10,000 times higher than that of the substrate layer, based on the SIMS sensitivity comparison between the intermediate region of the heterofilm and the substrate. For reference, according to the present invention, there is an advantage in that only the heterofilm layer contains iodine in a trace amount ranging from an extremely small amount (1,000 counts / s) to a small amount (10,000 counts / s).

[0115] The above heterogeneous film can be used for purposes such as a diffusion barrier film, a dielectric film, a gate insulating film, a block heterogeneous film, or a charge trap, but is not limited thereto.

[0116] The above brittle resistivity improving agent and precursor compound may preferably be a compound having a purity of 99.9% or more, a compound having a purity of 99.95% or more, or a compound having a purity of 99.99% or more. For reference, when using a compound having a purity of less than 99%, impurities may remain in the heterofilm or cause a side reaction with the precursor or reactant, so it is recommended to use a substance having a purity of 99% or more if possible.

[0117]

[0118] The above brittle resistivity improving agent is preferably used in an atomic layer deposition (ALD) process, and in this case, the ligand of the substrate-adsorbed precursor species of the bilayer is chemically and smoothly removed, thereby realizing an ideal atomic layer deposition process, while improving the crystallinity of the heterolayer, thereby improving the density of the heterolayer, and at the same time forming a high-purity heterolayer with a reduced impurity content in the heterolayer, and has the advantage of simultaneously improving the brittleness and resistivity of the bilayer.

[0119] The above brittle resistivity improver is preferably liquid at room temperature (22°C) and has a density of 0.8 to 2.5 g / cm. 3 or 0.8 to 1.5 g / cm 3 , and the vapor pressure (20°C) may be 0.1 to 1 Torr, 0.1 to 300 mmHg, or 1 to 300 mmHg, and within this range, the ligand of the precursor compound is effectively exchanged, and there is an excellent effect of improving the step rate, thickness uniformity of the heterofilm, growth rate, and film quality.

[0120] More preferably, the brittle resistivity improving agent has a density of 0.75 to 2.0 g / cm 3 or 0.8 to 1.3 g / cm 3 , and the vapor pressure (20 ℃) ​​can be 1 to 260 mmHg, and within this range, the ligand of the precursor compound is effectively exchanged, and there is an effect of improving film properties such as brittleness, resistivity, and density.

[0121] The above heterofilm is characterized by having a low resistance of 10,000 μΩ·cm or less. Here, the resistivity can be calculated using the cross-sectional area and material resistance that are commonly used, or measured using a resistivity meter. Since there is no difference between the calculated value and the measured value, either method can be used.

[0122] The crystallinity of the above heterofilm, as measured by XRD, is characterized by improvement due to the effect of reducing impurities inside the film through a stronger redox reaction of the metal precursor.

[0123]

[0124] The heterolayer of the present invention is characterized in that it is formed by including a step of pre-depositing one or more precursor compounds selected from Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga having one or more halogens (F, Cl, Br) as ligands on a substrate loaded inside a chamber; and a step of post-depositing one or more precursor compounds selected from Si, Y, Nb, La, Ce having one or more halogens (F, Cl, Br) as ligands; In this case, the ligands of the substrate-adsorbed precursor species of the bilayer are chemically smoothly removed, thereby realizing an ideal atomic layer deposition process, while improving the crystallinity of the bilayer, thereby improving the density of the bilayer, and at the same time forming a high-purity bilayer with reduced impurity content in the bilayer, and at the same time improving the brittleness and resistivity of the bilayer.

[0125] The method for manufacturing the above heterofilm may further include one or more steps selected from a pretreatment step of purging the inside of a chamber where pre-deposition and post-deposition are performed with a purge gas; a ligand exchange reaction step of exchanging a ligand of a central metal deposited on a substrate after the pre-deposition; a post-treatment step of purging the inside of the chamber with a purge gas after the pre-deposition; a ligand exchange reaction step of exchanging a ligand of a central metal deposited on a substrate after the post-deposition; a post-treatment step of purging the inside of the chamber with a purge gas after the post-deposition; a step of forming a deposition film through a reduction reaction; and a post-treatment step of purging the inside of the chamber with a purge gas after forming the deposition film.

[0126] For example, the method for forming a heterofilm of the present invention may include a pretreatment step of purging the inside of a chamber where pre-deposition and post-deposition are performed with a purge gas in advance; a step of pre-depositing at least one selected from among Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga precursors having at least one halogen (F, Cl, Br) as a ligand on a substrate loaded inside the chamber; and a step of post-depositing at least one selected from among Si, Y, Nb, La, and Ce.

[0127] As another example, the method for forming a heterofilm of the present invention may include a pretreatment step of purging the inside of a chamber where pre-deposition and post-deposition are performed with a purge gas in advance; a pre-depositing step of at least one selected from among Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga precursors having at least one halogen (F, Cl, Br) as a ligand on a substrate loaded inside the chamber; a post-treatment step of purging the inside of the chamber with a purge gas after the pre-deposition; a post-depositing step of at least one selected from among Si, Y, Nb, La, and Ce having at least one halogen (F, Cl, Br) as a ligand; a post-treatment step of purging the inside of the chamber with a purge gas after the post-deposition; and a step of forming a deposition film through a reduction reaction.

[0128] As another example, the method for forming a heterofilm of the present invention may include a pretreatment step of purging the inside of a chamber where pre-deposition and post-deposition are performed with a purge gas in advance; the pre-deposition step described above on a substrate loaded inside the chamber; a ligand exchange reaction step of exchanging a ligand of a central metal deposited on the substrate after the pre-deposition; a post-treatment step of purging the inside of the chamber with a purge gas after the pre-deposition; the post-deposition step described above; a post-treatment step of purging the inside of the chamber with a purge gas after the post-deposition; and a step of forming a deposition film through a reduction reaction.

[0129] As another example, the method for forming a heterofilm of the present invention may include a pretreatment step of purging the inside of a chamber where pre-deposition and post-deposition are performed with a purge gas in advance; a pre-deposition step described above on a substrate loaded inside the chamber; a ligand exchange reaction step of exchanging a ligand of a central metal deposited on the substrate after the pre-deposition; a post-treatment step of purging the inside of the chamber with a purge gas after the pre-deposition; the post-deposition step described above; a ligand exchange reaction step of exchanging a ligand of a central metal deposited on the substrate after the post-deposition; a post-treatment step of purging the inside of the chamber with a purge gas after the post-deposition; and a step of forming a deposition film through a reduction reaction.

[0130] The brittle resistivity improving agent described above can be added to the above ligand exchange reaction step.

[0131] The feeding time (feeding time, sec) of the above brittle resistivity improving agent is preferably 0.01 to 10 seconds per cycle, more preferably 0.02 to 8 seconds, still more preferably 0.04 to 6 seconds, and still more preferably 0.05 to 5 seconds, and within this range, there is an advantage of low heterogeneous film growth rate and excellent economic efficiency.

[0132] In this description, the feeding time of the precursor compound is based on a flow rate of 0.1 to 500 mg / cycle at a chamber volume of 15 to 20 L, and more specifically, based on a flow rate of 0.8 to 200 mg / cycle at a chamber volume of 18 L.

[0133] A single treatment including a purging step in the aforementioned steps can be performed as a unit cycle, and the above cycle can be repeated until a heterogeneous film of a desired thickness is obtained. In this way, when the brittle resistivity improving agent of the present invention and the precursor compound are introduced and adsorbed onto a substrate within one cycle, the heterogeneous film growth rate can be appropriately reduced, and the process byproducts generated are effectively removed, so that the resistivity of the heterogeneous film is reduced and the step rate is greatly improved, which has the advantage of being able to.

[0134] The amount of purge gas injected into the chamber in the purging step is not particularly limited as long as it is an amount sufficient to remove the non-adsorbed brittle resistivity improving agent, but may be, for example, 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, and within this range, non-adsorbed substances and / or process by-products, etc. can be sufficiently removed to form a heterogeneous film evenly and prevent deterioration of the film quality. Here, each injection amount of the purge gas is based on one cycle.

[0135] For example, the volume of the brittle resistivity improver removed by the purge gas refers to the volume of the vapor of the brittle resistivity improver that has been exposed. As a specific example, when the injection amount of the brittle resistivity improver is 200 sccm and the purge gas is used at a flow rate of 5000 sccm in the step of purging the unabsorbed brittle resistivity improver, the injection amount of the purge gas is 25 times the injection amount of the brittle resistivity improver.

[0136]

[0137] In the step of purging the non-absorbed precursor compound, the amount of purge gas injected into the chamber is not particularly limited as long as it is an amount sufficient to remove the non-absorbed precursor compound. However, for example, it may be 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, based on the volume of the precursor compound injected into the chamber. Within this range, the non-absorbed precursor compound is sufficiently removed so that the heterogeneous film is formed evenly and deterioration of the film quality can be prevented. Here, the amounts of the purge gas and the precursor compound injected are each based on one cycle, and the volume of the precursor compound means the volume of the vapor of the precursor compound injected.

[0138]

[0139] A reaction gas can be supplied to the above reduction reaction.

[0140] The above reaction gas may be O2, O3, N2O, NO2, NH3, N2O, H2O, H2O2, CO or CO2.

[0141] In the purging step performed immediately after the reaction gas supply step, the amount of purge gas injected into the chamber may be, for example, 10 to 10,000 times the volume of the reaction gas injected into the chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, and the desired effect can be sufficiently obtained within this range. Here, the injection amounts of the purge gas and the reaction gas are each based on one cycle.

[0142] In the method for forming the heterogeneous film, for example, when the brittle resistivity improving agent is injected after the pre-deposition and post-deposition of the precursor compound, the unit cycle can be repeated 1 to 99,999 times as needed, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, and within this range, the desired thickness of the heterogeneous film can be obtained while sufficiently obtaining the effect to be achieved in the present invention.

[0143]

[0144] The above precursor compound may be a compound having at least one selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce and Nd as a central metal atom (M) and at least one ligand composed of C, N, O, H, X (halogen), Cp (cyclopentadiene), and a compound having at least one ligand composed of C, N, O, H, X (halogen), Cp (cyclopentadiene) centered on silicon (S), and in the case of precursors having a vapor pressure of 1 mTorr to 100 Torr at 25°C, the effect of forming a ligand exchange region by the aforementioned brittle resistivity improving agent can be maximized despite natural oxidation.

[0145] In the present invention, the chamber may be, for example, an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0146] In the present invention, the precursor compound or precursor compound may include a step of vaporizing and then injecting and then performing a plasma post-treatment, in which case the growth rate of the heterofilm can be improved while reducing process byproducts.

[0147] The above precursor compound and precursor compound can be preferably transferred into the ALD chamber by the VFC method, the DLI method or the LDS method, and more preferably transferred into the chamber by the LDS method.

[0148] The substrate loaded in the chamber can be heated, for example, to 100 to 700°C, specifically, to 300 to 700°C, and the brittle resistivity improving agent or precursor compound can be injected onto the substrate in an unheated or heated state, and depending on the deposition efficiency, it is possible to first inject the agent in an unheated state and then adjust the heating conditions during the deposition process. For example, it can be injected onto the substrate at 300 to 700°C for 1 to 20 seconds.

[0149] The ratio of the amount (mg / cycle) of the precursor compound and the brittle resistivity improving agent injected into the chamber may be preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, even more preferably 1:2 to 1:12, and even more preferably 1:2.5 to 1:10, and within this range, the brittleness and resistivity improving effects and the reduction of process by-products are significant.

[0150] The method for forming the heterofilm above can be such that the residual halogen intensity (c / s) within the heterofilm measured by SIMS based on a thickness of 100 Å is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less, and in a preferred embodiment, 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800, and within this range, the effect of preventing corrosion and deterioration is excellent.

[0151] Here, the residual halogen content may include chlorine (Cl), iodine (I), etc.

[0152] In the present invention, purging 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 heterogeneous film growth rate per cycle is appropriately controlled, and deposition is performed as or close to a single atomic monolayer, which is advantageous in terms of film quality.

[0153]

[0154] The above ALD (atomic layer deposition process) is very advantageous in the production of integrated circuits (ICs) that require a high aspect ratio, and in particular, has advantages such as excellent conformality, uniformity, and precise thickness control due to a self-limiting heterogeneous film growth mechanism.

[0155] The above method for forming a heterogeneous film can be carried out at a deposition temperature in the range of, for example, 300 to 700°C, preferably at a deposition temperature in the range of 350 to 700°C, more preferably at a deposition temperature in the range of 400 to 600°C, and even more preferably at a deposition temperature in the range of 450 to 600°C, and has the effect of growing a heterogeneous film of excellent film quality while implementing ALD process characteristics within this range.

[0156] The above method for forming a heterogeneous film can be performed at a deposition pressure ranging from 0.01 to 20 Torr, for example, and is preferably performed at a deposition pressure ranging from 0.1 to 20 Torr, more preferably at a deposition pressure ranging from 0.1 to 10 Torr, and most preferably at a deposition pressure ranging from 0.3 to 7 Torr, and within this range, there is an effect of obtaining a heterogeneous film of uniform thickness.

[0157] In this description, the deposition temperature and deposition pressure can be measured as the temperature and pressure formed within the deposition chamber, or as the temperature and pressure applied to the substrate within the deposition chamber.

[0158] In addition, the present invention may include a heterogeneous film manufacturing device capable of implementing the heterogeneous film forming method, which includes an ALD chamber, a first vaporizer for vaporizing a metal precursor compound, a first transfer means for transferring the vaporized precursor compound into the ALD chamber, a second vaporizer for vaporizing a silicon precursor compound, a second transfer means for transferring the vaporized silicon precursor into the ALD chamber, a third vaporizer (if necessary) for vaporizing a brittle resistivity improving agent, a third transfer means for transferring the vaporized brittle resistivity improving agent into the ALD chamber, and a fourth transfer means for transferring a reaction gas into the ALD chamber. Here, the vaporizer and the transfer means are not particularly limited as long as they are vaporizers and transfer means commonly used in the technical field to which the present invention belongs.

[0159]

[0160] As a specific example, to explain the method for forming the heterogeneous film, first, a substrate on which a heterogeneous film is to be formed is placed in a deposition chamber capable of atomic layer deposition.

[0161] The above substrate may include a semiconductor substrate such as a silicon substrate or silicon oxide.

[0162] The above substrate may further have a conductive layer or an insulating layer formed on top thereof.

[0163] In order to deposit a heterogeneous film on a substrate positioned in the above deposition chamber, the above-described brittle resistivity improving agent and a precursor compound or a mixture thereof with a non-polar solvent are each prepared.

[0164] Afterwards, at least one selected from the prepared metal precursor compound or a mixture thereof and a non-polar solvent is injected into the vaporizer, changed into a vapor phase, transferred to the deposition chamber, and adsorbed onto the substrate, and purging is performed to remove unadsorbed metal precursor compounds and process byproducts.

[0165] Next, the prepared brittle resistivity improver is changed into a vapor phase and transferred to a deposition chamber to exchange the ligand of the metal precursor compound, and purging is performed to remove unadsorbed brittle resistivity improver and process byproducts.

[0166] Next, at least one selected from the prepared silicon precursor compound or a mixture thereof and a non-polar solvent is injected into a vaporizer, changed into a vapor phase, transferred to a deposition chamber, and adsorbed onto a substrate, and purging is performed to remove unadsorbed silicon precursor compounds and process byproducts.

[0167] Next, the prepared brittle resistivity improver is changed into a vapor phase and delivered to a deposition chamber to exchange the ligand of the silicon precursor compound, and purging is performed to remove unadsorbed brittle resistivity improver and process byproducts.

[0168] In the present invention, the process of adsorbing the metal precursor compound onto a substrate and then purging it; and the process of adsorbing the silicon precursor compound onto a substrate and then purging it can be performed in different orders as needed.

[0169] In the present invention, the method for delivering the brittle resistivity improver, metal precursor compound, silicon precursor compound, etc. to the deposition chamber may be, for example, a method for delivering volatilized gas using a mass flow controller (MFC) method (Vapor Flow Control; VFC) or a method for delivering liquid using a liquid mass flow controller (LMFC) method (Liquid Delivery System; LDS), and preferably, the LDS method is used.

[0170] At this time, as a transport gas or dilution gas for moving the brittle resistivity improver, metal precursor compound, and silicon precursor compound onto the substrate, one or more mixed gases selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He) may be used, but is not limited thereto.

[0171] In the present invention, an inert gas may be used as the purge gas, for example, and preferably, the carrier gas or dilution gas may be used.

[0172]

[0173] Next, a reaction gas is supplied. The reaction gas is not particularly limited as long as it is a reaction gas commonly used in the technical field to which the present invention pertains, and may preferably include a nitriding agent. The nitriding agent reacts with the precursor compound adsorbed on the substrate to form a heterogeneous film.

[0174] Preferably, the reaction gas may be O2, O3, N2O, NO2, NH3, N2O, H2O, H2O2, CO or CO2.

[0175] Next, the unreacted residual reaction gas is purged using an inert gas. This removes not only the excess reaction gas but also any generated byproducts.

[0176] As described above, the method for forming a heterogeneous film comprises, for example, sequentially injecting a brittle resistivity improving agent, a precursor compound for a heterogeneous film, and a reaction gas onto a substrate to form a heterogeneous film on the surface of a substrate loaded in a chamber, and a step of purging unabsorbed substances and reaction byproducts after each step is performed as a unit cycle, and the unit cycle can be repeated to form a heterogeneous film of a desired thickness.

[0177] The above unit cycle can be repeated, for example, 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, and within this range, there is an effect of well expressing the desired heterogeneous film characteristics.

[0178]

[0179] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the method for forming a heterogeneous film of the present invention, in which case the step ratio of the heterogeneous film and the uniformity of the thickness of the heterogeneous film are greatly improved, and the density and electrical characteristics of the heterogeneous film are excellent.

[0180] The above heterogeneous film may have a thickness of, for example, 0.1 to 20 nm, preferably 0.5 to 20 nm, more preferably 1.5 to 15 nm, and even more preferably 2 to 10 nm, and within this range, the heterogeneous film has excellent properties.

[0181] The above heterogeneous film may preferably have a hydrogen content of 5,000 counts / sec or less, or 1 to 3,000 counts / sec, more preferably 10 to 1,500 counts / sec, and even more preferably 50 to 1500 counts / sec, and within this range, the heterogeneous film has excellent characteristics while the heterogeneous film growth rate is reduced and controllable.

[0182] The above heterofilm may preferably have a halogen content including chlorine and iodine of 5,000 counts / sec or less, or 1 to 3,000 counts / sec, more preferably 10 to 1,000 counts / sec, and even more preferably 50 to 500 counts / sec, and within this range, the heterofilm has excellent properties while the heterofilm growth rate is reduced and controllable.

[0183] The above heterogeneous film may preferably have a carbon impurity content of 5,000 counts / sec or less, or 1 to 3,000 counts / sec, more preferably 10 to 1,000 counts / sec, and even more preferably 50 to 500 counts / sec, and within this range, the heterogeneous film has excellent characteristics while the heterogeneous film growth rate is reduced and the step rate is improved, and at the same time, there is a controllable effect.

[0184] The above heterogeneous film has, for example, a step ratio of 90% or more, preferably 92% or more, and more preferably 95% or more, and within this range, even a heterogeneous film with a complex structure can be easily deposited on a substrate, so it has the advantage of being applicable to next-generation semiconductor devices.

[0185] The heterofilm manufactured above preferably has a thickness of 20 nm or less, a resistivity of 10,000 uΩ.cm or less based on a thickness of 10 nm, and a hydrogen, carbon, and halogen content of 5,000 counts / sec or less, and has excellent performance as an electrode or barrier film within this range, but is not limited thereto.

[0186]

[0187] The above heterogeneous film may be, for example, a multilayer structure of two or three or more layers, preferably a multilayer structure of two or three layers, as needed. The multilayer film having a two-layer structure may be, for example, a lower layer film-middle layer film structure, and the multilayer film having a three-layer structure may be, for example, a lower layer film-middle layer film-upper layer film structure.

[0188] The above-mentioned lower layer may be formed by including at least one selected from the group consisting of, for example, Si, -SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, and TiO2.

[0189] The above-mentioned multilayer film is, for example, Ti x N y , preferably including TN.

[0190] The above upper layer may be formed by including at least one selected from the group consisting of, for example, W and Mo.

[0191] The semiconductor substrate may be a low resistive metal gate interconnect, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a 3D Gate-All-Around (GAA), or a 3D NAND flash memory.

[0192]

[0193] Hereinafter, preferred examples and drawings are presented to help understand the present invention, but the following examples and drawings are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0194]

[0195] [Example]

[0196] Examples 1 to 4, Comparative Examples 1 to 4

[0197] An ALD deposition process was performed using the components and process conditions shown in Tables 1 and 2 below.

[0198] First, HI was prepared as a brittle resistivity improver.

[0199] Additionally, Si2Cl6 and TiCl4 were prepared as precursor compounds, respectively.

[0200] Specifically, the working pressure of the chamber containing a silicon wafer preheated to 300 to 600°C was set to 0.5 to 1.5 Torr by injecting a flow rate of nitrogen gas of 500 to 5000 sccm into the chamber using a vacuum pump to form a thin inert atmosphere.

[0201] The above brittle resistivity improving agent was injected as a gaseous substance at 50 to 1000 sccm, and the liquid Ti precursor and Si precursor compounds were each cooled or heated to generate a vapor pressure of 0.01 to 10 Torr.

[0202] Each vapor was injected into the chamber while injecting nitrogen as a carrier gas at 100 to 500 sccm. At this time, TiCl4 was injected first, followed by the brittle resistivity improving agent, and then Si2Cl6 was injected, followed by the brittle resistivity improving agent.

[0203] The injection time of the brittle resistivity improver and each precursor was 2 seconds.

[0204] Nitrogen was used as the reaction gas, and 100 to 1000 sccm was injected into the deposition chamber for 3 seconds to purge the chamber. At this time, the substrate on which the heterogeneous film was to be formed was heated to a temperature of 300 to 700°C.

[0205] Evaluation was performed in an atomic layer deposition process that included a step of purging with nitrogen equivalent to three times the amount of all materials injected.

[0206] This process was repeated 100 to 400 times to form a self-limiting atomic layer heterolayer with a thickness of 10 nm.

[0207] The results of measurements or calculations of deposition rate, resistivity, SIMS analysis, brittleness increase rate, etc. for each of the obtained heterogeneous films of Examples 1 to 4 and Comparative Examples 1 to 4 are shown together in Table 2 and Figures 1 to 8 below.

[0208] * SIMS (Secondary-ion mass spectrometry): The H, Cl, I, and C values ​​were confirmed in the SIMS graph by considering the H, Cl, I, and C contents (counts) when the sputter time was 50 seconds, which is low in contamination on the substrate surface layer, while axially digging into the heterogeneous film using ion sputtering.

[0209] *Ti+Si / N calculation: The contents of Ti, Si, and N elements were confirmed through XPS analysis of the heterogeneous films of Examples 1 to 4 and Comparative Examples 1 to 4, and the composition ratio was determined by dividing the contents of Ti and Si by the diffused contents.

[0210] *Brittleness increase rate (%): Calculated according to the following mathematical formula 1 derived by referring to the literature Surface & Coatings Technology, 204 (2010) 2123.

[0211] [Mathematical Formula 1]

[0212] Brittleness Increase Rate (%) = 1.6615x + 36.2 (R2 = 0.9969)

[0213] (where x represents the Si content (wt%))

[0214] ClassificationInjection methodPrecursor compoundPurgeBrittle resistivityimprovementPurgeReaction gasPurgeComparative exampleStep 1TiCl4N2-N2NH3N2Step 2Si2Cl6N2-N2NH3N2ExampleStep 1TiCl4N2HIN2NH3N2Step 2Si2Cl6N2HIN2NH3N2

[0215] Separate deposition process properties Step 1 (TiN process) Step 2 (SiN process) TiN / heterofilm ratio (%) Resistivity (uΩ·cm) Ti+Si / N ratio Brittleness increase rate (%) Comparative example 11-50 25 43 70.96 8100 Comparative example 2 4 16 7 34 0 10.94 6116 Comparative example 3 2 18 0 9 0 40.99 4132 Comparative example 4 1 1 0 0 10 10.99 7147 Example 11-50 89 181.02 0100 Example 2 4 16 7 15 6 6 1.01 9116 Example 3 2 18 0 49 0 1.04 2132 Example 4 1 1 0 0 54 1.03 0147

[0216] As shown in Tables 1 to 2 above, it was confirmed that Examples 1 to 4 of the heterogeneous film manufactured using the brittle resistivity improving agent and precursor compound according to the present invention showed improved resistivity at the same brittleness increase rate compared to Comparative Examples 1 to 4 that did not use the brittle resistivity improving agent.

[0217] The resistivity, etc. of Example 1 and Comparative Example 1 were compared in FIGS. 1 to 8 below. Specifically, FIG. 1 below is a diagram comparing the resistivity measured for the heterogeneous films of Examples 1 to 4 with the heterogeneous films of Comparative Examples 1 to 4. FIG. 2 below is a diagram comparing the composition ratio obtained by dividing the content of Ti, Si, and N elements by the diffused content of Ti and Si. FIGS. 3 to 4 below are diagrams comparing the H element content between the heterogeneous films of Examples 1 to 4 with the heterogeneous films of Comparative Examples 1 to 4. FIGS. 5 to 6 below are diagrams comparing the Cl element content between the heterogeneous films of Examples 1 to 4 with the heterogeneous films of Comparative Examples 1 to 4. FIGS. 7 to 8 below are diagrams comparing the iodine doping content between the heterogeneous films of Examples 1 to 4 with the heterogeneous films of Comparative Examples 1 to 4.

[0218] First, the following Figure 1 is a resistivity graph, and it was confirmed that the resistivity was reduced by approximately 1 / 2 to 1 / 3 in Examples 1 to 4 using a brittle resistivity improving agent compared to Comparative Examples 1 to 4 that did not use a brittle resistivity improving agent.

[0219] In particular, among Examples 1 to 4, it was confirmed that the resistivity reduction effect was improved as the Si content increased, and from this, it can be seen that the resistivity, which was in a trade-off relationship with brittleness in the past, was effectively improved.

[0220] In addition, Fig. 2 below is a graph comparing the Ti+Si / N ratio, and it can be seen that in Examples 1 to 4 using a brittle resistivity improver, a thin film having a ratio exceeding 1 was obtained compared to Comparative Examples 1 to 4 in which a brittle resistivity improver was not used, and when linked to Fig. 1 described above, it was found that this value affected the resistivity.

[0221] In addition, the graphs of Figures 3 and 4 below are H impurity content graphs, and it was confirmed that an increase in the Si fraction significantly affects an increase in the H impurity content, and from this, it was confirmed that the H impurity content is the factor that can have the greatest effect on an increase in resistivity. Meanwhile, even in the case of a silicon precursor compound that does not contain H, the H component may remain in the thin film due to H included in the reaction gas in the SiN process.

[0222] That is, it was confirmed that the H content was greatly reduced in Examples 1 to 4 using the brittle resistivity improver compared to Comparative Examples 1 to 4 in which the brittle resistivity improver was not used, and from this, it was confirmed that the resistivity was greatly reduced as the H content was reduced.

[0223] In addition, the following Figures 5 and 6 are graphs of Cl impurity content, and it was confirmed that an increase in the Si fraction slightly affected an increase in the Cl impurity content, and from this, the Cl impurity content was confirmed as a factor that can affect an increase in resistivity next to H impurity. Meanwhile, when a silicon precursor compound containing Cl is used, it may react with reaction gas components, etc. in the SiN process and remain in the thin film in the form of NH4Cl, etc.

[0224] That is, it was confirmed that the Cl content was significantly reduced in Examples 1 to 4 using the brittle resistivity improver compared to Comparative Examples 1 to 4 in which the brittle resistivity improver was not used, and from this, it was confirmed that the resistivity was significantly reduced as the Cl content was reduced. In particular, when the aforementioned NH4Cl is dissolved in the etchant, a problem of reduced corrosion resistance may occur in which pinholes are formed.

[0225] In addition, FIGS. 7 to 8 below are SIMS graphs, and based on a deposition time of 25 sec, the P sensitivity was 100 counts / s or less for Comparative Examples 1 to 4, 150 counts / s for Example 1 including a heterogeneous film modifier, 200 counts / s for Example 2, 250 counts / s for Example 3, and 300 counts / s for Example 4, where iodine could be doped. From this, it can be inferred that the resistivity is reduced by affecting the thin film crystal orientation, etc. When filling the inside of the cylindrical channel oxide of NAND flash memory with a core oxide, it is expected to induce uniform channel characteristics when introduced to the core oxide process.

[0226]

[0227] From this, it was confirmed that the present invention is suitable for providing a brittle resistivity improving agent capable of improving both brittleness and resistivity, which are in a trade-off relationship, when forming a heterofilm including a compound containing an element having a predetermined electronegativity, as well as improving the roughness and continuity of the thin film, a method for forming a heterofilm including the same, and a semiconductor substrate and semiconductor device including the same.

Claims

1. As a brittle resistivity improver for heterogeneous films, The above heterofilm comprises at least one selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga and at least one selected from the group consisting of Si, Y, Nb, La, and Ce. A brittle resistivity improver characterized in that the above brittle resistivity improver is a compound containing an element having an electronegativity within the range of 2.2 to 2.

8.

2. In paragraph 1, A brittle resistivity improving agent characterized in that the element having the electronegativity within the range of 2.2 to 2.8 is iodine.

3. In paragraph 1, A brittle resistivity improving agent characterized in that the compound containing an element having an electronegativity within the range of 2.2 to 2.8 is a compound having an iodine ligand.

4. In paragraph 1, A brittle resistivity improving agent characterized in that the compound containing an element having an electronegativity within the range of 2.2 to 2.8 is at least one selected from among a compound having a direct bond between hydrogen (H) and iodine, a compound having a direct bond between carbon (C) and iodine, and a compound having a direct bond between a halogen element (F, Cl, Br) and iodine.

5. In paragraph 1, A brittle resistivity improving agent characterized in that the compound containing an element having an electronegativity within the range of 2.2 to 2.8 is at least one selected from compounds represented by the following chemical formulas 1-1 to 1-8. [Chemical Formulas 1-1 to 1-8] 6. In paragraph 1, A brittle resistivity improving agent characterized in that the above heterogeneous film is provided from an iodine-free precursor compound.

7. In paragraph 6, A brittle resistivity improving agent characterized in that the above iodine-free precursor compound comprises a compound having at least one selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga as a central metal atom (M) and at least one halogen (F, Cl, Br) as a ligand, and a compound having at least one selected from the group consisting of Si, Y, Nb, La, and Ce as a central metal atom (M) and at least one halogen (F, Cl, Br) as a ligand.

8. In paragraph 1, A brittle resistivity improving agent characterized in that the above heterofilm is represented by TixSiyNz (wherein x is an integer from 0.2 to 0.8, y is an integer from 0.001 to 0.3, and z is an integer from 0.3 to 0.7) and has a resistivity of 10,000 μΩ·cm or less.

9. A method for forming a heterolayer, characterized by comprising: a step of pre-depositing at least one precursor compound selected from among Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga, each having at least one halogen (F, Cl, Br) as a ligand, onto a substrate loaded inside a chamber; and a step of post-depositing at least one precursor compound selected from among Si, Y, Nb, La, and Ce, each having at least one halogen (F, Cl, Br) as a ligand.

10. In paragraph 9, The above heterogeneous film forming method is, A pretreatment step of purging the interior of the chamber where pre-deposition and post-deposition are performed with purge gas; A ligand exchange reaction step for exchanging the ligand of the central metal deposited on the substrate after the above-mentioned pre-deposition; A post-processing step of purging the inside of the chamber with a purge gas after the above-mentioned pre-deposition; A ligand exchange reaction step of exchanging the ligand of the central metal deposited on the substrate after the above-mentioned post-deposition; A post-treatment step of purging the inside of the chamber with purge gas after the above deposition; a step of forming a deposition film through a reduction reaction; and A method for forming a heterogeneous film, characterized in that it further comprises at least one step selected from among a post-treatment step of purging the inside of the chamber with a purge gas after forming the above deposition film.

11. In paragraph 10, A method for forming a heterogeneous film, characterized in that the brittle resistivity improving agent of claim 1 is added to the ligand exchange reaction step.

12. In paragraph 9, A method for forming a heterogeneous film, characterized in that the chamber is an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

13. In paragraph 10, A method for forming a heterogeneous film, characterized in that the substrate is heated to 300 to 700°C.

14. In paragraph 10, A method for forming a heterogeneous film, characterized in that the process temperature of the above-mentioned pre-deposition step and the air temperature of the post-deposition step are independently within the range of 300 to 700°C.

15. In paragraph 10, A method for forming a heterofilm, characterized in that the ligand exchange reaction temperature is in the range of 300 to 700°C.

16. In paragraph 10, A method for forming a heterogeneous film, characterized in that the ratio of the amount (mg / cycle) of the brittle resistivity improving agent and the precursor compound injected into the chamber is 1:1 to 1:

20.

17. A semiconductor substrate characterized by including a heterogeneous film manufactured by the heterogeneous film forming method of Article 9.

18. A semiconductor device characterized by including a semiconductor substrate according to claim 17.

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