Protective agent for low dielectric constant oxide film, method for forming oxide film by using same, and semiconductor substrate and semiconductor device manufactured therefrom

Abstract

The present invention relates to a protective agent for a low dielectric constant oxide film, a method for forming an oxide film by using same, and a semiconductor substrate and a semiconductor device manufactured therefrom. The present invention provides an effective high-temperature deposition oxide film formation technology by using a compound of a predetermined structure as a protective agent for a precursor compound including a structure containing a halogen group directly connected to a silane element, and thus has the effect that etching resistance, step coverage, impurity content, and the like are significantly improved while deposition rate, deposition thickness per deposition cycle, and growth rate are reduced even when an oxide film is formed at a high temperature.

Description

Low dielectric constant oxide film protective agent, method for forming an oxide film using the same, semiconductor substrate and semiconductor device manufactured therefrom

[0001] The present invention relates to a low dielectric constant oxide film protective agent, a method for forming an oxide film using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom. More specifically, the invention relates to a low dielectric constant oxide film protective agent that can significantly improve etching resistance, step coverage, and impurity content while reducing the deposition rate, deposition thickness per deposition cycle, and growth rate, even when forming an oxide film at high temperatures, by providing an effective high-temperature deposition oxide film forming technology using a compound of a predetermined structure as a protective agent for a precursor compound having a structure including a halogen group directly connected to a silane element; a method for forming a low dielectric constant oxide film including the same; and a semiconductor substrate and a semiconductor device manufactured therefrom.

[0002] Silicon-containing thin films are essential materials in semiconductor manufacturing and are utilized in various forms, including Si, SiO2, SiN, SiC, SiCN, and SiON. Recently, as the high integration and miniaturization of semiconductor devices have progressed rapidly, the need for high-performance insulating and barrier films is increasing to reduce interference between devices and improve electrical characteristics.

[0003] For example, electronic components of a SiP (System in package) or MCM (Multi Chip Module) are provided with an interposer on a package substrate (a printed substrate such as a ceramic substrate, a plastic substrate, or a glass epoxy substrate), and on the interposer, semiconductor devices (integrated circuits such as CPUs, GPUs, and FPGAs) and multiple memory devices (High Bandwidth Memory (HBM), etc.) are provided.

[0004] The above interposer may use a silicon interposer, a resin interposer, etc. The interposer has multiple wires and functions to electrically connect multiple integrated circuits with different terminal pitches. The multiple wires are provided in a single layer or a multilayer.

[0005] In addition, the interposer has the function of electrically connecting the integrated circuit provided on the interposer to the electrode provided on the package substrate.

[0006] In addition, through electrodes are provided in the interposer, and the integrated circuit and the package substrate are electrically connected using the through electrodes. Also, in the silicon interposer, a Through Silicon Via (TSV) may be used as the through electrode.

[0007] The above TSV has an insulating layer (SiO2) on a Cu electrode via a barrier layer (Ti, Ta, etc.). At this time, it is necessary to improve step coverage to reduce thin spots, and to reduce cracks, film quality improvements such as WER (etching resistance), roughness, and density are required.

[0008] Meanwhile, the above insulating layer can be implemented as a high dielectric constant or a low dielectric constant depending on the type of precursor used.

[0009] Accordingly, there is a need to develop technology that provides low dielectric constant oxide films while reducing the deposition rate during high-temperature deposition, in addition to providing crack reduction by improving film quality such as etching resistance, roughness, and density while improving step coverage when providing thin films such as SiO2.

[0010] [Prior Art Literature]

[0011] [Patent Literature]

[0012] Korean Patent Publication No. 2009-0059462

[0013] In order to solve the problems of the prior art as described above, the present invention aims to provide a low dielectric constant oxide film protective agent that can significantly improve etching resistance, step coverage, and impurity content while reducing the deposition rate, deposition thickness per deposition cycle, and growth rate, by using a compound of a predetermined structure as a protective agent for a precursor compound having a structure including a halogen group directly connected to a silane element, thereby providing an effective high-temperature deposition oxide film forming technology, and a method for forming a low dielectric constant oxide film including the same.

[0014] In addition, the present invention aims to provide an oxide film formed using the above-described low dielectric constant oxide film as a low dielectric constant oxide film, and to provide a high-performance and high-reliability semiconductor substrate and semiconductor device, etc. including the low dielectric constant oxide film.

[0015] The above and other objectives of the present invention can all be achieved by the present invention described below.

[0016] To achieve the above objective, the present invention provides a low dielectric constant oxide film protective agent characterized by comprising a carbonate-based compound as a protective agent for a precursor compound having a structure comprising a halogen group directly connected to a silane element.

[0017] The above carbonate-based compound may be selected from one or more compounds represented by the following chemical formulas 1-1 to 1-9.

[0018] [Chemical Formulas 1-1 to 1-9]

[0019]

[0020] The above precursor compound may be a chlorosilane-based compound.

[0021]

[0022] In addition, the present invention comprises the steps of: treating the surface of a substrate with a low dielectric constant oxide film protective agent; and sequentially injecting a precursor compound and an oxidizing agent into a deposition chamber to form an oxide film on the loaded substrate surface.

[0023] The present invention provides a method for forming a low dielectric constant oxide film, characterized in that each of the above steps performs a purging process using an inert gas, and the low dielectric constant oxide film protective agent comprises the aforementioned low dielectric constant oxide film protective agent.

[0024] The above precursor compound may be one or more selected from SiH2Cl2, SiH3Cl, SiCl4, Si2Cl6, Si3Cl8, SiH2I2, SiHI3, and SiI4.

[0025] The injection amount of the above low dielectric constant oxide film protective agent into the deposition chamber can be a flow rate of 1 mg / cycle for ALD and 1 mg / sec or more for CVD, based on the volume of the deposition chamber being 10 L.

[0026] The above oxidizing agent may be O3, H2O, H2O2, N2O, NO2, O2, or O2 plasma.

[0027] When the above low dielectric constant oxide film protective agent is injected, an inert gas carrier may be mixed in and provided to the chamber.

[0028] The incorporation amount (sccm) of the above inert gas carrier may be in the range of 10 to 2000 sccm based on 10 mg of the above low dielectric constant oxide film protective agent.

[0029] The above deposition temperature can be performed within the range of 300 to 800 ℃.

[0030] The above low dielectric constant oxide film protective agent and precursor compound can be transferred into the chamber by a liquid delivery system (LDS) or a vapor flow control (VFC) method.

[0031] The above oxide film can simultaneously satisfy the following five conditions.

[0032] 1) Deposition thickness per deposition cycle is 0.8 Å / cycle or less,

[0033] 2) The oxide film growth reduction rate per deposition cycle is 10 to 50%,

[0034] 3) Etching rate (room temperature, 1:500 HF etching) based on a thickness of 10 or 20 nm is < 4 nm / min, 4) Residual carbon content and residual halogen content are both 0.01% or less,

[0035] 5) Step coverage rate is 90% or higher.

[0036] The amount of purge gas introduced into the chamber at each of the above steps may be 10 to 100,000 times the volume of the introduced low dielectric constant oxide film protective agent or precursor compound.

[0037] The substrate loaded in the chamber above can be heated to 100 to 800 ℃.

[0038] The ratio of the injection amount (mg / cycle) of the low dielectric constant oxide film protective agent and the precursor compound into the chamber may be 1:1 to 1:20.

[0039]

[0040] In addition, the present invention

[0041] A step of treating the surface of a substrate with a low dielectric constant oxide film protective agent; and

[0042] The method includes the step of sequentially injecting a precursor compound and an oxidizing agent into a deposition chamber into the above-mentioned processed substrate to form an oxide film on the surface of the loaded substrate;

[0043] Each of the above steps performs a purging process using an inert gas, and

[0044] The above low dielectric constant oxide film protective agent comprises the low dielectric constant oxide film protective agent according to claim 1, and

[0045] A method for forming an oxide film is provided, characterized by injecting the above-mentioned precursor compound and an oxidizing agent to generate COCl2.

[0046]

[0047] In addition, the present invention comprises an oxide film produced by the aforementioned oxide film forming method, and

[0048] The present invention provides a semiconductor substrate characterized in that the oxide film is a low dielectric constant oxide film having a dielectric constant (Dielectric constants, k) of 4.0 or less.

[0049] The oxide film may have a multilayer structure of two or three or more layers.

[0050] The above oxide film may be used as a TSV (through silicon via) liner, a Shallow Trench Isolation (STI) separator, an insulator, a core oxide, a gate insulator, a block oxide, or a charge trap.

[0051]

[0052] In addition, the present invention provides a semiconductor device comprising the aforementioned semiconductor substrate.

[0053] The semiconductor substrate may be a logic semiconductor, low resistive metal gate interconnects, 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.

[0054] According to the present invention, there is an effect of providing an effective high-temperature deposition oxide film formation technique by using a protective agent for a precursor compound having a structure including a halogen group directly connected to a silane element, with respect to a compound having a predetermined structure.

[0055] In addition, even when forming an oxide film at high temperatures, there is an effect of significantly improving etching resistance, step coverage, and impurity content while reducing the deposition rate, deposition thickness per deposition cycle, and growth rate.

[0056] In addition, process by-products are more effectively reduced during oxide film formation, which prevents corrosion or deterioration and improves the electrical properties of the oxide film by modifying the film quality and enhancing its crystallinity.

[0057] In addition, process by-products are reduced during oxide film formation, and step coverage and oxide film density can be improved. Furthermore, there is an effect of providing an oxide film formation method using this and a semiconductor substrate manufactured therefrom.

[0058] FIG. 1 is a diagram comparing the high-temperature deposition rate of an oxide film according to whether a low dielectric constant oxide film protective agent is used in Examples 1 to 3 and Comparative Examples 1 to 3 according to the present invention.

[0059] Figure 2 is a diagram comparing carbon impurities in the oxide film according to whether a low dielectric constant oxide film protective agent is used in Example 1 and Comparative Example 1 according to the present invention.

[0060] FIG. 3 is a diagram comparing the etching resistance of an oxide film according to whether a low dielectric constant oxide film protective agent is used in Example 1 and Comparative Example 1 according to the present invention.

[0061] Figure 4 is a diagram showing the results of confirming the Cl impurity content in the oxide film according to whether a low dielectric constant oxide film protective agent was used in Example 1 and Comparative Example 1 according to the present invention using SIMS analysis.

[0062] FIG. 5 is a schematic diagram of the process used in the oxide film formation method of Example 1 according to the present invention.

[0063] Figure 6 is a diagram showing the results of analyzing the gas components emitted when materials such as protective agents, precursors, and reactants are injected into the deposition chamber by installing an RGA (reaction gas analyzer) consisting of a quadrupole mass spectrometer (detectable molecular weight range 1 to 200 amu) in-line in the vacuum exhaust line of an atomic layer deposition equipment.

[0064] The low dielectric constant oxide film protective agent of the present invention, a method for forming an oxide film using the same, and a semiconductor substrate manufactured therefrom are described in detail below.

[0065] In this description, the term “low dielectric constant oxide film protective agent” means a material that effectively provides a low dielectric constant oxide film while reducing the deposition rate when an oxide film is formed using an atomic layer equipment in a high-temperature deposition process of 400°C or higher, unless otherwise specified.

[0066] The above deposition rate can be confirmed by the reduction rate of the oxide film growth rate.

[0067] Unless otherwise specified, the above oxide film growth rate reduction rate can be calculated using the following mathematical formula 1.

[0068] [Mathematical Formula 1]

[0069] Oxide film growth reduction rate = [{(DR i )-(DR f )} / (DR i )]×100

[0070] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which the oxide film is deposited. In the deposition of an oxide film formed by a precursor and an oxidizing agent, DR i (Initial deposition rate) is the deposition rate of the oxide film formed without the addition of a low-dielectric constant oxide film protective agent. DR fThe final deposition rate is the deposition rate of the oxide film formed by adding a low-dielectric constant oxide film protective agent during the above-mentioned process. Here, the deposition rate (DR) is a value measured using an ellipsometer for an oxide film with a thickness of 3 to 30 nm under room temperature and atmospheric pressure conditions, and is expressed in units of Å / cycle.

[0071] While researching a technology that reduces deposition rate and carbon impurities and improves etching resistance and step coverage even when used in a high-temperature deposition process for a predetermined precursor compound capable of providing a low dielectric constant oxide film, the inventors identified a protective agent capable of protecting the low dielectric constant oxide film and, based on this, devoted themselves to related research to complete the present invention.

[0072]

[0073] The low dielectric constant oxide film protective agent of the present invention is a protective agent for precursor compounds having a structure including a halogen group directly connected to a silane element, and even when used in a high-temperature deposition process including a carbonate-based compound, the deposition rate and carbon impurities are reduced, and the etching resistance and step coverage are improved.

[0074] The above low dielectric constant oxide film protective agent is preferably a liquid at room temperature (22℃) and has a density of 0.8 to 2.5 g / cm³ 3 or 0.8 to 1.5 g / cm³ 3 The vapor pressure (20°C) may be 0.1 to 300 mmHg or 1 to 300 mmHg, and within this range, effective protection of the low dielectric constant oxide film is achieved, and even when used in a high-temperature deposition process, the deposition rate and carbon impurities are reduced, and the etching resistance and step coverage are improved.

[0075] More preferably, the low dielectric constant oxide film protective agent has a density of 0.75 to 2.0 g / cm³ 3 or 0.8 to 1.3 g / cm³ 3The vapor pressure (20°C) can be 1 to 260 mmHg, and in this range, low dielectric constant oxide film protection is effectively achieved. Even when used in a high-temperature deposition process, the deposition rate and carbon impurities are reduced, and the etching resistance and step coverage are improved.

[0076] As the above low dielectric constant oxide film protective agent, a carbonate-based compound with a predetermined structure may be used.

[0077] The above carbonate-based compound may include, for example, one or more compounds selected from the compounds represented by the following chemical formulas 1-1 to 1-9. In this case, when forming an oxide film at a high temperature, the oxide film thickness and growth rate are significantly controlled, and even when forming a multilayer oxide film, the effect of improving step coverage and etching resistance is excellent.

[0078] [Chemical Formulas 1-1 to 1-9]

[0079]

[0080] The above precursor compound may be a chlorosilane-based compound. For reference, when using an aminosilane-based compound, as can be seen in the comparative example described later, there is an advantage that chlorine impurities do not remain in the oxide film; however, to perform high-temperature deposition, a CVD process must be carried out, making it difficult to perform a high-temperature ALD process. Furthermore, it is confirmed that the step coverage and etching resistance are all inferior compared to the example using a chlorosilane-based compound.

[0081]

[0082] The above low dielectric constant oxide film protective agent is used, for example, in an atomic layer deposition (ALD) process, preferably in a high-temperature ALD process, and in this case, it effectively implements low dielectric constant oxide film protection. Even when used in a high-temperature deposition process, it has the advantage of reducing the deposition rate and carbon impurities, and improving etching resistance and step coverage.

[0083]

[0084] The method for forming an oxide film according to the present invention is characterized by comprising: a step of treating the surface of a substrate with the aforementioned low dielectric constant oxide film protective agent; and a step of sequentially injecting a precursor compound and a reaction gas into a deposition chamber to form an oxide film on the loaded substrate surface. In this case, the deposition rate of the oxide film on the substrate is reduced and the oxide film growth rate is appropriately lowered, so that even when forming an oxide film at high temperatures, step coverage and etching resistance are greatly improved, and carbon impurities are also reduced.

[0085] Each of the above steps can perform a purging process using an inert gas.

[0086] The step of treating the surface of a substrate with the above-mentioned low dielectric constant oxide film protective agent has a feeding time (sec) of the low dielectric constant oxide film protective agent on the substrate surface that is preferably 0.1 seconds or more per cycle, more preferably 1 to 15 seconds, and even more preferably 2 to 10 seconds, and within this range, there is an advantage of low oxide film growth rate and excellent step coverage and economic efficiency.

[0087]

[0088] The above precursor compound may be, for example, a chlorosilane-based compound.

[0089] Specifically, the ligands of the above precursor compound may include 1 to 6 or 2 to 8 within the Cl molecule, and the Si in the above precursor compound may be 1 to 3. In this case, when forming the oxide film at high temperature, the oxide film thickness and growth rate are significantly controlled, and even when forming a multilayer oxide film, there is an excellent effect of improving step coverage and etching resistance.

[0090] As a specific example, the above precursor compound may be one or more selected from SiH2Cl2, SiH3Cl, SiCl4, Si2Cl6, Si3Cl8, SiH2I2, SiHI3, and SiI4.

[0091] In this description, the feeding time of the precursor compound is based on a flow rate of 0.1 to 500 mg / cycle with a chamber volume of 15 to 20 L, and more specifically, based on a flow rate of 0.8 to 200 mg / cycle with a chamber volume of 18 L.

[0092] In particular, when the above precursor compound has a vapor pressure of 0.01 Torr to 100 Torr at 25 ℃, it can maximize the aforementioned low dielectric constant oxide film protection effect despite natural oxidation.

[0093] The amount of the low dielectric constant oxide film protective agent injected into the deposition chamber can be, for example, 1 mg / cycle in the case of ALD and 1 mg / sec or more in the case of CVD, based on the volume of the deposition chamber being 10 L, specifically in the range of 10 to 150 mg / s or mg / cycle, preferably 10 to 100 mg / s or mg / cycle. In this case, when forming the oxide film at high temperature, the oxide film thickness and growth rate are significantly controlled, and even when forming a multilayer oxide film, there is an excellent effect of improving step coverage and etching resistance.

[0094]

[0095] When the above low dielectric constant oxide film protective agent is injected, an inert gas carrier may be mixed in and provided to the chamber.

[0096] The mixing amount (sccm) of the above inert gas carrier may be, for example, 3000 sccm / mg or less based on the total injection amount (mg) of the low dielectric constant oxide film protective agent into the deposition chamber, specifically 30 to 3000 sccm / mg, preferably 50 to 2000 sccm / mg, more preferably 70 to 1000 sccm / mg, and even more preferably 100 to 500 sccm / mg. In this case, when forming the oxide film at high temperature, the oxide film thickness and growth rate are significantly controlled, and even when forming a multilayer oxide film, there is an excellent effect of improving step coverage and etching resistance.

[0097] Here, sccm refers to Standard Cubic Centimeter per Minute.

[0098] The incorporation amount (sccm) of the above inert gas carrier may be in the range of 10 to 2000 sccm based on 10 mg of the above low dielectric constant oxide film protective agent.

[0099]

[0100] The ratio of the above precursor compound and the low dielectric constant oxide film protective agent introduced into the chamber (mg / cycle) can preferably be 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 effect of improving step coverage and the effect of reducing process by-products are significant.

[0101] The above low dielectric constant oxide film protective agent and precursor compound can preferably be transferred into an ALD chamber by a liquid delivery system (LDS) or a vapor flow control (VFC).

[0102]

[0103] The above oxidizing agent may be O3, H2O, H2O2, N2O, NO2, O2, or O2 plasma.

[0104] For example, in the above method for forming an oxide film, when the low dielectric constant oxide film protective agent is deposited before the 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 oxide film thickness can be obtained while sufficiently achieving the effect intended to be achieved in the present invention.

[0105] The substrate loaded in the chamber may be heated, for example, to 100 to 650°C, specifically to 150 to 550°C, and the low dielectric constant oxide film protective agent or precursor compound may be injected onto the substrate without heating or in a heated state, and depending on the deposition efficiency, it may be injected without heating and then the heating conditions may be adjusted during the deposition process. For example, it may be injected onto the substrate for 1 to 20 seconds at 100 to 650°C.

[0106] The above oxide film formation method can be performed, for example, at 400°C or higher, specifically at 400 to 800°C, preferably at 500 to 900°C, and more preferably at 600 to 700°C, and within this range, the improvement effect of the oxide film growth reduction rate and deposition thickness per deposition cycle is significant.

[0107]

[0108] In a preferred embodiment, the above oxide film forming method may include: i) a step of vaporizing the low dielectric constant oxide film protective agent and treating the surface of a substrate loaded in an atomic layer deposition (deposition) chamber; ii) a step of first purging the inside of the chamber with a purge gas; iii) a step of vaporizing a precursor compound and adsorbing it onto the surface of a substrate loaded in the chamber; iv) a step of secondarily purging the inside of the chamber with a purge gas; v) a step of supplying an oxidizing agent into the chamber; and vi) a step of thirdly purging the inside of the chamber with a purge gas.

[0109] At this time, steps i) to vi) above can be performed as a unit cycle, and the cycle can be repeated until an oxide film of the desired thickness is obtained. In this way, when the low dielectric constant oxide film protective agent of the present invention is introduced before the precursor compound and adsorbed onto the substrate within one cycle, the oxide film growth rate can be appropriately lowered even when deposited at high temperatures, and the generated process by-products are effectively removed and reduced, and the step coverage and etching resistance are greatly improved.

[0110] In a preferred embodiment, the low dielectric constant oxide film protective agent can be manufactured by applying it to a substrate loaded in a chamber at a temperature of 20 to 800 ℃.

[0111] The oxide film formation method of the present invention can be provided at a low temperature using, for example, atomic layer deposition equipment. In this case, even if the oxide film is deposited at a low temperature, the oxide film growth rate is appropriately reduced, thereby significantly reducing process by-products and greatly improving step coverage and etching resistance. Furthermore, even when applied to semiconductor devices with a large aspect ratio, the thickness uniformity of the oxide film is greatly improved, which has the advantage of ensuring the reliability of the semiconductor device.

[0112] For example, in the above method for forming an oxide film, when the precursor compound is deposited before or after the 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 oxide film thickness can be obtained while sufficiently achieving the effect intended to be achieved in the present invention.

[0113] In the present invention, the chamber may be, for example, an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0114] In the present invention, the low dielectric constant oxide film protective agent or precursor compound may include a step of vaporizing and injecting, followed by plasma post-treatment, and in this case, the growth rate of the oxide film can be improved while reducing process by-products.

[0115]

[0116] In the case where the low dielectric constant oxide film protective agent is first adsorbed on the substrate, followed by the adsorption of the precursor compound and then the adsorption of the precursor compound, the amount of purge gas introduced into the chamber during the step of purging the unadsorbed low dielectric constant oxide film protective agent is not particularly limited as long as it is sufficient to remove the unadsorbed low dielectric constant oxide film protective agent, but for example, it may be 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, and within this range, the unadsorbed low dielectric constant oxide film protective agent can be sufficiently removed so that the oxide film is formed evenly and the deterioration of the film quality can be prevented. Here, the amount of purge gas and the amount of low dielectric constant oxide film protective agent introduced are each based on one cycle, and the volume of the low dielectric constant oxide film protective agent refers to the volume of the removed low dielectric constant oxide film protective agent vapor.

[0117] As a specific example, when the injection amount of the low dielectric constant oxide film protective agent is 200 sccm and the purge gas flow rate is 5000 sccm in the step of purging the unadsorbed low dielectric constant oxide film protective agent, the injection amount of the purge gas is about 25 times the injection amount of the low dielectric constant oxide film protective agent.

[0118]

[0119] In addition, the amount of purge gas introduced into the chamber during the step of purging the unadsorbed precursor compound is not particularly limited as long as it is sufficient to remove the unadsorbed precursor compound, but for example, it may be 10 to 10,000 times the volume of the precursor compound introduced into the chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the unadsorbed precursor compound can be sufficiently removed to form an oxide film evenly and prevent deterioration of the film quality. Here, the amounts of the purge gas and the precursor compound introduced are each based on one cycle, and the volume of the precursor compound refers to the volume of the removed precursor compound vapor.

[0120]

[0121] In addition, the amount of purge gas introduced into the chamber during the purging step performed immediately after the reaction gas supply step may, for example, be 10 to 10,000 times the volume of the reaction gas introduced 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 amounts of the purge gas and the reaction gas introduced are each based on one cycle.

[0122]

[0123] The above low dielectric constant oxide film protective agent and precursor compound can preferably be transferred into an ALD chamber by a liquid delivery system (LDS) or a vapor flow control (VFC).

[0124] The substrate loaded in the chamber may be heated, for example, to 100 to 650°C, specifically to 150 to 550°C, and the low dielectric constant oxide film protective agent or precursor compound may be injected onto the substrate without heating or in a heated state, and depending on the deposition efficiency, it may be injected without heating and then the heating conditions may be adjusted during the deposition process. For example, it may be injected onto the substrate for 1 to 20 seconds at 100 to 650°C.

[0125]

[0126] The ratio of the above precursor compound and the low dielectric constant oxide film protective agent introduced into the chamber (mg / cycle) can preferably be 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 effect of improving step coverage and the effect of reducing process by-products are significant.

[0127] The above oxide film formation method can be performed, for example, at 400°C or higher, and within this range, the reduction rate of oxide film growth and the improvement effect of deposition thickness per deposition cycle of the oxide film are significant.

[0128]

[0129] When using the above low dielectric constant oxide film protective agent and the above precursor compound, the oxide film growth reduction rate (%) per deposition cycle of the oxide film may preferably be 10 to 50%, more preferably 15 to 45%, and even more preferably 20 to 40%, and within this range, the oxide film growth rate per cycle is appropriately controlled and deposition is performed as an atomic mono-layer or close to it, which has an advantageous effect in terms of film quality.

[0130] The growth reduction rate (%) per deposition cycle mentioned above refers to the ratio of the growth rate before the addition of the low-dielectric oxide protective agent and the deposition rate after the addition of the low-dielectric oxide protective agent, and was calculated as a percentage using the respective measured A / cycle values.

[0131] Specifically, the oxide film growth rate reduction rate was calculated by dividing the oxide film thickness measured by an ellipsometer—a device capable of measuring optical properties such as the thickness or refractive index of an oxide film using the polarization characteristics of light—by the number of cycles to calculate the oxide film thickness deposited per cycle. Specifically, it was calculated using the following Equation 1.

[0132] [Mathematical Formula 1]

[0133] Oxide film growth reduction rate = [{(DR i )-(DR f )} / (DR i )]×100

[0134] (In the above Equation 1, DR (Deposition rate, Å / cycle) is the rate at which the oxide film is deposited. In the deposition of an oxide film formed by a precursor and an oxidizing agent, DR i (Initial deposition rate) is the deposition rate of the oxide film formed without the addition of a low-dielectric constant oxide film protective agent. DR fThe final deposition rate is the deposition rate of the oxide film formed by adding a low-dielectric constant oxide film protective agent during the above-mentioned process. Here, the deposition rate (DR) is a value measured using an ellipsometer for an oxide film with a thickness of 3 to 30 nm under room temperature and atmospheric pressure conditions, and is expressed in units of Å / cycle.

[0135]

[0136] When using the above low dielectric constant oxide film protective agent and the above precursor compound, the uniformity (% in wafer) calculated by the following mathematical formula 2 may be 0.5 to 5.5%, specifically 1.0 to 5.0%, preferably 1.5 to 4.5%, and in this case, even when forming an oxide film at high temperature, step coverage, deposition thickness and growth rate per deposition cycle of the oxide film, and non-uniformity can be improved.

[0137] [Mathematical Formula 2]

[0138] [{(maximum thickness - minimum thickness) / 2} / average thickness] × 100

[0139] (In the above mathematical formula 2, the maximum and minimum thicknesses are selected from the oxide film thicknesses measured by an ellipsometer, respectively. As shown in FIG. 2, the oxide film thickness is measured by dividing a 300mm wafer into 13 areas of 6x6 cm² in a grid pattern and measuring the thickness at the center of each corresponding area. The average thickness (nm) is calculated by averaging the thicknesses measured in the 13 areas.)

[0140]

[0141] The above method for forming an oxide film may have a deposition thickness (Å / cycle) of the oxide film per deposition cycle that is preferably 0.8 Å / cycle or less, more preferably 0.3 to 0.8 Å / cycle, and even more preferably 0.4 to 0.8 Å / cycle, within this range, the oxide film growth rate per cycle is appropriately controlled, and deposition is performed as an atomic mono-layer or close to it, which has an advantageous effect in terms of film quality.

[0142] The deposition thickness (Å / cycle) per deposition cycle and the deposition rate (DR) may be measured using an ellipsometer to measure an oxide film with a thickness of 3 to 30 nm under conditions of room temperature and atmospheric pressure.

[0143]

[0144] The above ALD (Atomic Layer Deposition) process is highly advantageous for fabricating integrated circuits (ICs) that require a high aspect ratio, and in particular, due to the self-limiting oxide film growth mechanism, it offers advantages such as excellent conformality, uniformity, and precise thickness control.

[0145] The above oxide film formation method can be carried out, for example, at a high deposition temperature of 400°C or higher, and within this range, it has the effect of growing an oxide film of excellent quality while realizing ALD process characteristics.

[0146] The above method for forming an oxide film can be carried out, for example, at a deposition pressure in the range of 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and most preferably at a deposition pressure in the range of 0.3 to 7 Torr, and has the effect of obtaining an oxide film of uniform thickness within this range.

[0147] In this description, the deposition temperature and deposition pressure may 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.

[0148] The above oxide film forming method may preferably include the step of raising the temperature inside the chamber to a deposition temperature before introducing the precursor compound into the chamber; and / or the step of purging by injecting an inert gas into the chamber before introducing the precursor compound into the chamber.

[0149] In addition, the present invention allows for the selection and use of a general type atomic layer deposition (ALD) equipment, a batch type (furnace type) ALD equipment, etc., as an oxide film manufacturing apparatus capable of implementing the above-mentioned oxide film manufacturing method, depending on the usage conditions. For example, a batch type (furnace type) ALD equipment can be selected when the material is injected into the chamber for a long time.

[0150] The above general type atomic layer deposition equipment may include a space-division type single chamber, a time-division type single chamber, etc., but is not limited thereto.

[0151] The above-described atomic layer deposition equipment may include, for example, an ALD chamber, a first vaporizer for vaporizing a precursor compound, a first transfer means for transferring the vaporized precursor compound into the ALD chamber, a second vaporizer for vaporizing an oxide film precursor, and a second transfer means for transferring the vaporized oxide film precursor 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.

[0152]

[0153] As a specific example, to explain the above method for forming an oxide film, first, a substrate on which an oxide film is to be formed is placed inside a deposition chamber capable of atomic layer deposition.

[0154] The above substrate may include a semiconductor substrate such as a silicon substrate or silicon oxide.

[0155] The above substrate may further have a conductive layer or an insulating layer formed on its upper surface.

[0156] In order to deposit an oxide film on a substrate placed in the deposition chamber, the aforementioned low dielectric constant oxide film protective agent and a precursor compound are prepared, and if necessary, an inert gas is additionally prepared as a carrier gas.

[0157] Subsequently, the prepared low-dielectric oxide protective agent is injected into a vaporizer, converted into a vapor phase, and transferred to a deposition chamber to be adsorbed onto the substrate, and the unadsorbed low-dielectric oxide protective agent is removed by purging.

[0158] Next, the prepared precursor compound is injected into a vaporizer, converted into a vapor phase, and transferred to a deposition chamber to be adsorbed onto a substrate, and any unadsorbed precursor compound is purged.

[0159] In the present invention, the process of removing an unadsorbed low dielectric constant oxide film protective agent by adsorbing the precursor compound onto a substrate and then purging; and the process of removing an unadsorbed precursor compound by adsorbing the precursor compound onto a substrate and purging may be carried out in a different order as necessary.

[0160] In this description, the method of delivering the low dielectric constant oxide film protective agent and the metal precursor compound to the deposition chamber may, for example, use a liquid delivery system (LDS) or a vapor flow control (VFC) method.

[0161] At this time, as a carrier gas or diluent gas for transporting a low dielectric constant oxide film protective agent, a metal precursor compound, etc. onto a substrate, one or more mixed gases selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He) may be used, but are not limited thereto.

[0162] In the present invention, an inert gas may be used as the purge gas, for example, and preferably, the carrier gas or diluent gas may be used.

[0163]

[0164] Next, an oxidizing agent is supplied. The oxidizing agent is not particularly limited as long as it is a reaction gas commonly used in the technical field to which the present invention belongs, and the oxidizing agent reacts with the precursor compound adsorbed on the substrate to form an oxide film.

[0165] Preferably, the oxidizing agent is O2, O3, N2O, NO2, H2O, or O2 plasma.

[0166] Next, unreacted residual oxidizing agent is purged using an inert gas. Accordingly, not only the excess reaction gas but also the generated by-products can be removed.

[0167] As described above, the oxide film formation method comprises, for example, the steps of treating a low dielectric constant oxide film protective agent on a substrate, shielding a precursor compound on the substrate, purging the unadsorbed low dielectric constant oxide film protective agent, adsorbing a precursor compound on the substrate, purging the unadsorbed precursor compound, supplying an oxidizing agent, and purging the residual oxidizing agent as a unit cycle, and the unit cycle may be repeated to form an oxide film of a desired thickness.

[0168] 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, the desired oxide film characteristics are well expressed.

[0169]

[0170] In addition, the method for forming an oxide film according to the present invention comprises the steps of: treating the surface of a substrate with a low dielectric constant oxide film protective agent; and sequentially injecting a precursor compound and an oxidizing agent into a deposition chamber to form an oxide film on the loaded substrate surface; wherein each step performs a purging process using an inert gas, and the low dielectric constant oxide film protective agent includes the low dielectric constant oxide film protective agent according to claim 1, and COCl2 can be generated by injecting the precursor compound and the oxidizing agent.

[0171] A schematic diagram of the process used in the above oxide film formation method is shown in Fig. 5 below.

[0172] As shown in Fig. 5 below, a reaction gas analyzer (RGA) consisting of a quadrupole mass spectrometer (detectable molecular weight range 1 to 200 amu) is installed in-line in the vacuum exhaust line of the atomic layer deposition equipment to analyze the gas components emitted when materials such as protective agents, precursors, and reactants are injected into the deposition chamber.

[0173] As shown in Figure 6 below, which illustrates the analysis results, the principle by which Cl impurities are reduced by more than 75% when using the chlorosilane-based precursor according to the present invention is that the carbon monoxide (CO) component originating from the protective agent reacts with the chlorine component to convert into COCl2, which is highly advantageous for desorption, thereby removing HCl, a byproduct generated during precursor injection, from being re-adsorbed onto the substrate. As shown in Test Example 2 described later, the vapor pressure of the generated COCl2 is measured to be approximately 1216 Torr at 20 °C.

[0174]

[0175] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the oxide film formation method of the present invention, and in this case, the step coverage, etching resistance, and thickness uniformity of the oxide film are significantly excellent, and the density and dielectric properties of the oxide film are excellent.

[0176] The oxide 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 oxide film properties are excellent.

[0177] The oxide 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 oxide film properties are excellent while the oxide film growth rate is reduced.

[0178] The oxide film manufactured above preferably has a thickness of 20 nm or less, a dielectric constant of 1 to 5 based on an oxide film thickness of 10 nm, a carbon, nitrogen, and halogen content of 5,000 counts / sec or less, and a step coverage rate of 90% or more, and within this range, it has excellent performance as a dielectric film or blocking film, but is not limited thereto.

[0179] The oxide film may preferably have a roughness of 4.0 or higher, preferably 4.0 to 5.0, and more preferably 4.0 to 4.5, and within this range, the oxide film properties are excellent while the oxide film growth rate is reduced.

[0180]

[0181] The oxide film manufactured above preferably satisfies an etching rate (room temperature, 1:500 HF etching) based on a thin film thickness of 10 or 20 nm of less than 4 nm / min, and both residual carbon content and residual halogen content are 0.01% or less, and has a step coverage rate of 90% or more, and performs excellently as a film within this range, but is not limited thereto.

[0182] The above oxide film can be used for TSV (through silicon via) liners, Shallow Trench Isolation (STI) isolation films, insulators, core oxides, gate insulating films, block oxides, or charge traps.

[0183] The oxide film may, for example, have a multilayer structure of two or three or more layers as needed, preferably a multilayer structure of two or three layers. The multilayer film of the two-layer structure may, as a specific example, be a lower layer-middle layer structure, and the multilayer film of the three-layer structure may, as a specific example, be a lower layer-middle layer-upper layer structure.

[0184] The above lower layer may comprise, for example, 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.

[0185] The above-mentioned layer is, for example, Ti x N y , preferably, it can be made including TN.

[0186] The above upper layer may comprise, for example, one or more types selected from the group consisting of W and Mo.

[0187] 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.

[0188]

[0189] Hereinafter, preferred embodiments and drawings are presented to aid in understanding the present invention; however, the following embodiments and drawings are merely 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 spirit of the present invention, and that such variations and modifications fall within the scope of the appended claims.

[0190]

[0191] [Example]

[0192] Example 1

[0193] An ALD deposition process was performed using the components and process conditions shown in Table 1 below.

[0194] Argon was introduced into the chamber of the atomic layer deposition equipment at a rate of 5000 ml / min, and a vacuum pump was used to increase the pressure inside the chamber to 1.5 Torr to create a dilute inert atmosphere.

[0195] The low dielectric constant protective agent shown in Table 1 below was placed in a canister, and the partial pressure and temperature were adjusted to achieve an injection amount (mg / cycle) via a liquid delivery system (LDS) or vapor flow control (VFC) method. The agent was then introduced into a deposition chamber loaded with a substrate for 3 seconds to apply to the substrate, while argon was mixed in at the concentration shown in Table 1 below, and the chamber was purged for 10 seconds.

[0196] Next, HCDS (hexachlorodisilane) was placed in a canister as a precursor compound and introduced into the deposition chamber via a VFC (vapor flow controller) as shown in Table 1 below, and the chamber was purged for 10 seconds.

[0197] Next, the concentration of O3 as a reactive gas is 200 g / m³ 3The substrate was prepared to this condition, introduced into the deposition chamber, and the chamber was purged for 10 seconds. At this time, the substrate on which the oxide film is to be formed was heated to the temperature conditions shown in Table 1 below.

[0198] A self-limiting atomic layer oxide film was formed by repeating this process 100 to 400 times at a temperature of 550 ℃, as shown in Table 1 below.

[0199]

[0200] Example 2

[0201] The same process was repeated except that the deposition temperature in Example 1 above was replaced with 510 ℃.

[0202]

[0203] Example 3

[0204] The same process was repeated except that the deposition temperature in Example 1 above was replaced with 600 ℃.

[0205]

[0206] Comparative Examples 1 to 3

[0207] The same process was repeated in Examples 1 to 3 above, except that a low dielectric constant oxide film protective agent was not used.

[0208]

[0209] Comparative Example 4

[0210] The same process was repeated except that DIPAS (diisopropylaminosilane) was used as the precursor compound in Comparative Example 1 above.

[0211]

[0212] Comparative Example 5

[0213] The same process was repeated except that DIPAS (diisopropylaminosilane) was used as the precursor compound in Example 1 above.

[0214]

[0215] [Test Example 1]

[0216] For the oxide films of Examples 1 to 3 and Comparative Examples 1 to 5 obtained, the deposition thickness per deposition cycle, average deposition thickness, growth reduction rate per deposition cycle, and non-uniformity were measured in the following manner and are shown in Table 1 below.

[0217] * Deposition rate per cycle (Å / cycle): The deposition rate (DR) was measured using an ellipsometer on oxide films with a thickness of 3 to 30 nm under room temperature and atmospheric pressure conditions and is shown in Table 1 and Figure 1 below.

[0218] * Average deposition thickness (nm): The thickness was measured three times and the average value was calculated.

[0219] * Growth reduction rate per deposition cycle (%): This refers to the ratio of the growth rate before the addition of the low-dielectric oxide protective agent to the reduction in deposition rate after the addition of the low-dielectric oxide protective agent. It was calculated as a percentage using the respective measured A / cycle values.

[0220] Specifically, the oxide film growth rate reduction rate was calculated by dividing the oxide film thickness measured by an ellipsometer—a device capable of measuring optical properties such as the thickness or refractive index of an oxide film using the polarization characteristics of light—by the number of cycles to calculate the oxide film thickness deposited per cycle. Specifically, the calculation was performed using the following Equation 1, and the results are shown in Table 1 and Figure 1 below.

[0221] [Mathematical Formula 1]

[0222] Oxide film growth reduction rate = [{(DR i )-(DR f )} / (DR i )]×100

[0223] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which the oxide film is deposited. In the deposition of an oxide film formed by a precursor and an oxidizing agent, DR i(Initial deposition rate) is the deposition rate of the oxide film formed without the addition of a low-dielectric constant oxide film protective agent. DR f The final deposition rate is the deposition rate of the oxide film formed by adding a low-dielectric constant oxide film protective agent during the above-mentioned process. Here, the deposition rate (DR) is a value measured using an ellipsometer for an oxide film with a thickness of 3 to 30 nm under room temperature and atmospheric pressure conditions, and is expressed in units of Å / cycle.

[0224] The deposition thickness uniformity (%) is determined by selecting the highest and lowest thicknesses among the oxide film thicknesses measured by the above ellipsometer equipment. The oxide film thickness was determined by dividing a 300mm wafer into 6x6cm² areas in a grid pattern, measuring the thickness of the central part of each area, and is shown in Table 1 below.

[0225] [Mathematical Formula 2]

[0226] [{(maximum thickness - minimum thickness) / 2} / average thickness] × 100

[0227] (In the above mathematical formula 2, the maximum and minimum thicknesses are selected from the oxide film thicknesses measured by an ellipsometer, respectively. As shown in FIG. 2, the oxide film thickness is measured by dividing a 300mm wafer into 13 areas of 6x6 cm² in a grid pattern and measuring the thickness at the center of each corresponding area. The average thickness (nm) is calculated by averaging the thicknesses measured in the 13 areas.)

[0228] *Impurities: SIMS analysis was performed to verify whether carbon was detected at ppb levels, and the results obtained are shown in Figure 2 below, and the Cl analysis results are shown in Figure 5 below.

[0229] *WER (Etching Resistance): To verify the etching rate, a deposited thin film was immersed in a 1:500 HF etching solution at room temperature for 60 seconds, and the reduced thickness was measured as the optical thickness to calculate the etching rate. The calculation results are shown in Table 1 and Figure 3 below.

[0230] *Step coverage: A thin film was deposited on an aspect ratio 22:1 pattern with a hole diameter of 10 nm and a depth of 2200 nm. The thickness deposited on the inner wall of the pattern was measured through analysis by observing the microstructure by cutting and processing the specimen horizontally at the position of the mark in the top region of the vertical hole and the mark in the bottom region, respectively. The result of calculating the step coverage (%) as the ratio of the thickness deposited in the bottom region to the thickness deposited in the top region is shown in Table 1 below.

[0231] Classification Example 1 Comparative Example 1 Comparative Example 4 Comparative Example 5 Precursor Compound HCDS HCDS DIPAS Reactant O3 / O2 O3 / O2 O3 / O2 O3 / O2 Deposition Temperature (°C) 550 550 600 600 Low Dielectric Constant Oxide Film Protectant Injection Amount (mg) 36 -- 36 Low Dielectric Constant Oxide Film Protectant Injection Time (s) 3 -- 3 Inert Gas Carrier (sccm) 500 500 500 500 Precursor Compound Injection Amount (mg / s) 36 36 36 36 Precursor Compound Injection Time (s) 33 33 Inert Gas Carrier (sccm) 500 500 500 500 Deposition Rate per Cycle (Å / cycle) 0.20 50.26 91.00 80.99 Growth Reduction Rate per Deposition Cycle (%) 24 -- 1.2 Deposition Thickness Uniformity (%) 1.35 4.02 0.92 1.00 WER(nm / min) 3.05 4.34.1 - Step Coverage(%) 98.88 0.9--

[0232] As shown in Table 1 above and Figures 1 to 5 below, it was confirmed that Example 1, using a low dielectric constant oxide film protective agent and a precursor compound according to the present invention, provided effects of improved deposition rate at high temperatures, reduction of carbon impurities, reduction of chlorine impurities, roughness, etching resistance, and step coverage compared to Comparative Examples 1 to 5, which did not use a low dielectric constant oxide film protective agent. In particular, it was confirmed that Example 1, using a low dielectric constant oxide film protective agent according to the present invention, not only significantly improved the reduction rate of the deposition rate compared to Comparative Examples 4 to 5, which included a monoaminosilane precursor rather than the chlorosilane-based precursor used in the present invention, but also had a uniform thickness of the thin film grown on the substrate, as well as excellent impurity reduction characteristics and step coverage.

[0233]

[0234] [Test Example 2]

[0235] A schematic diagram of the process used in the above oxide film formation method is shown in Fig. 5 below, and the analysis results are shown in Fig. 6 below.

[0236] First, according to the process schematic of Fig. 5 below, an RGA (reaction gas analyzer) consisting of a quadrupole mass spectrometer (detectable molecular weight range 1~200 amu) was installed in-line in the vacuum exhaust line of the atomic layer deposition equipment to analyze the gas components emitted when materials such as protective agents, precursors, and reactants were injected into the deposition chamber.

[0237] As shown in Fig. 6 below, it was confirmed that Cl impurities are reduced by more than about 75% when the chlorosilane precursor according to the present invention is used. For reference, the vapor pressure of the generated COCl2 was measured to be about 1216 Torr at 20 °C.

[0238] The principle by which Cl impurities are reduced by more than 75% when using a chlorosilane-based precursor is inferred to be that the carbon monoxide (CO) component originating from the protective agent reacts with the chlorine component to be converted into COCl2, which is highly advantageous for desorption, so that HCl, a byproduct generated during precursor injection, is not re-adsorbed onto the substrate.

[0239] Specifically, regarding Figure 6 below, which shows data measured by the RGA device of Figure 5 below, the details are as follows.

[0240] In Figure 6 above, the X-axis represents a function of time, and the Y1 and Y2 axes represent signal sensitivity. The Y1 axis represents the signal sensitivity of the solid line, and the Y2 axis represents the signal sensitivity of the dotted line. As a result of real-time monitoring of the reaction gases generated during the injection of the low dielectric constant oxide film protective agent, the injection of the precursor, and the injection of the reactant during one cycle of the deposition process, it was clearly observed that COCl2 (vapor pressure 1216 Torr @ 20 °C) is generated during the injection of the precursor.

[0241] It was confirmed that this effectively discharges Cl and HCl components adsorbed or re-adsorbed on the thin film, significantly reducing the content of residual Cl impurities. Furthermore, the large amounts of methane and water observed during the reactant injection step indicate that the low-dielectric oxide protective agent is effectively decomposed and removed; this can be considered as evidence that C impurities in the thin film do not increase or may even decrease slightly compared to the comparative example process.

[0242]

[0243] As a result, when the low dielectric constant oxide film protective agent according to the present invention is applied to a predetermined precursor compound, carbon and chlorine impurities are sufficiently reduced while reducing the high-temperature deposition rate to provide a low dielectric constant oxide film, and at the same time, roughness, etching resistance, and step coverage are improved to provide an oxide film suitable for application to next-generation semiconductor devices, etc.

Claims

1. A low dielectric constant oxide film protective agent characterized by comprising a carbonate-based compound as a protective agent for a precursor compound having a structure containing a halogen group directly connected to a Si element.

2. In Paragraph 1, A low-temperature, low-dielectric constant oxide film protective agent characterized in that the above carbonate-based compound is selected from one or more compounds represented by the following chemical formulas 1-1 to 1-9. [Chemical Formulas 1-1 to 1-9] 3. In Paragraph 1, A low dielectric constant oxide film protective agent characterized in that the above-mentioned precursor compound is a chlorosilane-based compound.

4. A step of treating the surface of the substrate with a low dielectric constant oxide film protective agent; and The method includes the step of sequentially injecting a precursor compound and an oxidizing agent into a deposition chamber into the above-mentioned processed substrate to form an oxide film on the surface of the loaded substrate; Each of the above steps performs a purging process using an inert gas, and A method for forming an oxide film characterized by comprising the low dielectric constant oxide film protective agent according to claim 1.

5. In Paragraph 4, A method for forming an oxide film characterized in that the above precursor compound is one or more selected from SiH2Cl2, SiH3Cl, SiCl4, Si2Cl6, Si3Cl8, SiH2I2, SiHI3, and SiI4.

6. In Paragraph 4, A method for forming an oxide film, characterized in that the injection amount of the low dielectric constant oxide film protective agent into the deposition chamber is a flow rate of 1 mg / s or more or mg / cycle or more, based on the volume of the deposition chamber being 10 L.

7. In Paragraph 4, A method for forming an oxide film characterized by using O3, H2O, H2O2, N2O, NO2, O2, or O2 plasma as the oxidizing agent.

8. In Paragraph 1, A method for forming an oxide film characterized by incorporating an inert gas carrier and providing it to the chamber when the above-mentioned low dielectric constant oxide film protective agent is injected.

9. In Paragraph 8, A method for forming an oxide film characterized in that the amount of the inert gas carrier incorporated (sccm) is within the range of 10 to 2000 sccm based on 10 mg of the low dielectric constant oxide film protective agent.

10. In Paragraph 4, A method for forming an oxide film characterized by performing the deposition temperature within the range of 400 to 800 ℃.

11. In Paragraph 4, A method for forming an oxide film characterized by the above-mentioned low dielectric constant oxide film protective agent and precursor compound being transferred into a chamber by a liquid delivery system (LDS) or a vapor flow control (VFC) method.

12. In Paragraph 7, A method for forming an oxide film characterized by the above oxide film satisfying the following five conditions. 1) Deposition thickness per deposition cycle is 0.8 Å / cycle or less, 2) The oxide film growth reduction rate per deposition cycle is 10 to 50%, 3) Etching rate (room temperature, 1:500 HF etching) based on a thickness of 10 or 20 nm is < 4 nm / min, 4) Residual carbon content and residual halogen content are both 0.01% or less, 5) Step coverage rate is 90% or higher.

13. A step of treating the surface of a substrate with a low dielectric constant oxide film protective agent; and The method includes the step of sequentially injecting a precursor compound and an oxidizing agent into a deposition chamber into the above-mentioned processed substrate to form an oxide film on the surface of the loaded substrate; Each of the above steps performs a purging process using an inert gas, and The above low dielectric constant oxide film protective agent comprises the low dielectric constant oxide film protective agent according to claim 1, and A method for forming an oxide film characterized by injecting the above-mentioned precursor compound and an oxidizing agent to generate COCl2.

14. Includes an oxide film manufactured by the oxide film formation method according to paragraph 4, A semiconductor substrate characterized in that the oxide film is a low dielectric constant oxide film having a dielectric constant of 4.0 or less.

15. In Paragraph 14, A semiconductor substrate characterized in that the oxide film has a multilayer structure of two or three or more layers.

16. A semiconductor device comprising the semiconductor substrate of claim 14.

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