JP4494041B2 - Method for forming silicon dioxide film using siloxane compound - Google Patents

Description

  The present invention relates to a method of forming a thin film on a substrate, and more particularly to a method of forming a silicon dioxide film on a substrate using an ALD (Atomic Layer Deposition) method.

  As the size of a microelectronic element becomes smaller, the characteristics of a silicon dioxide film applied to a gate oxide film, a dielectric film, and the like of a field effect transistor constituting a semiconductor element have become very important.

  In a general semiconductor device manufacturing process, a silicon dioxide film is mostly formed by a method such as thermal CVD (Chemical Vapor Deposition), LPCVD (Low Pressure CVD), or PECVD (Plasma-Enhanced CVD). Among them, the thermal CVD method provides excellent step coverage but has a disadvantage of a high temperature process. Although the PECVD method provides a high deposition rate at a low temperature, it has a disadvantage of poor step coverage. These methods have been limitedly applied to a silicon dioxide film forming process suitable for taking advantage of each advantage in a semiconductor device structure. However, as semiconductor devices are highly integrated, there is a problem that a short channel effect caused by a high process temperature during the CVD process is raised, and a low temperature of the silicon dioxide film process is required. In addition, more and more problems are highlighted due to step coverage and pattern loading effects caused as the level difference between elements constituting the semiconductor element increases. Therefore, a silicon dioxide film forming process capable of improving these problems is required.

In order to improve the above problems, a method of forming a silicon dioxide film using the ALD method has been proposed. As a typical example, Patent Document 1 discloses a method of forming a silicon dioxide film by ALD using SiCl ₄ and H ₂ O. However, according to the method of the above patent, the packing density of the SiO ₂ single layer obtained after one deposition cycle of the ALD process is low and the deposition rate is very slow, which is required in the semiconductor device manufacturing process. The throughput requirement cannot be satisfied. Further, SiCl ₄ has a structure having four Si—Cl bonds per one Si, and when performing a low temperature deposition process, the Si—Cl bond reacts with H ₂ O to form an O—H bond to form dioxide. A large amount of O—H bonds remain in the silicon film, thereby easily forming a porous silicon dioxide film.
US Pat. No. 6,090,442

  An object of the present invention is to solve the problems in the prior art as described above, and to provide excellent film characteristics by minimizing the content of impurities remaining in silicon dioxide, and at the same time, increase the deposition rate. It is an object of the present invention to provide a method for forming a silicon dioxide film that can improve throughput.

  In order to achieve the above object, in the method of forming a silicon dioxide film according to the first aspect of the present invention, a first reactant made of a siloxane compound substituted with a halogen element or -NCO group is supplied onto a substrate, and the first A chemical adsorption layer of one reactant is formed. Also, a second reactant is supplied onto the chemical adsorption layer to form a silicon dioxide film on the substrate.

The first reactant may be composed of a siloxane compound represented by Si _n O _n-1 X _{2n + 2} (wherein n is an integer of 2 to 5 and X is F, Cl, Br, I, or NCO). . Preferably, the first reactant comprises disiloxane substituted with a halogen element or -NCO. Particularly preferably, the first reactant comprises Si ₂ OCl ₆ , Si ₂ OBr ₆ or Si ₂ O (NCO) ₆ . The second reactant may consist of H ₂ O or H ₂ O ₂ .

  The method for forming a silicon dioxide film according to the first aspect of the present invention further includes a step of removing a reaction byproduct of the first reactant and a step of removing a reaction byproduct of the second reactant. A method of purging using an inert gas to remove the reaction byproduct, a method of exhausting at a pressure lower than the pressure at the time of supplying the first reactant and the second reactant, or a combination of the purge and exhaust The method of applying can be selectively used.

  The method for forming a silicon dioxide film according to the first aspect of the present invention may further include the step of annealing the silicon dioxide film having a desired thickness after it is formed. The annealing is performed by a heat treatment, a plasma treatment, or an ozone treatment method.

In order to achieve the above object, in the method of forming a silicon dioxide film according to the second aspect of the present invention, a substrate is loaded into the chamber. Si _n O _n-1 X _{2n + 2} (wherein n is an integer of 2 to 5 and X is F, Cl, Br, I, or NCO) A catalyst is supplied into the chamber together with a catalyst, and a chemical adsorption layer of the first reactant is formed on the substrate. The reaction by-product of the first reactant is removed in the chamber. A second reactant is supplied into the chamber together with a second catalyst and reacted with the chemical adsorption layer to form a silicon dioxide film on the substrate. Thereafter, reaction byproducts on the silicon dioxide film are removed.

  In order to achieve the above object, the method for forming a silicon dioxide film according to the third aspect of the present invention provides a method for forming a silicon dioxide film on a substrate surface for a semiconductor product using a catalyst-assisted ALD process. In order to accomplish this, the functionalized surface of the substrate is exposed to a first mixture of only a first reactant and a first catalyst, and then the substrate surface is subjected to a second reaction to form a silicon dioxide monolayer on the substrate surface. And a continuous step of exposing to a second mixture consisting only of the product and the second catalyst. In this method, a material in which at least one element selected from the group consisting of a halogen element or a siloxane compound substituted with a —NCO group is essentially constituted as the first reactant.

According to the present invention, when a silicon dioxide film is formed by the ALD method, a substituted siloxane compound containing two or more Si atoms is used as a Si source. The silicon dioxide film obtained by the method according to the present invention provides excellent film characteristics due to the strong bonding force of Si—O—Si present in the siloxane compound, and the amount of residual impurities in the film can be minimized. Further, since two SiO ₂ single layers are obtained for each vapor deposition cycle of the ALD process, the vapor deposition rate is increased and the throughput is improved.

In the method for forming a silicon dioxide film according to the present invention, a substituted siloxane compound containing two or more Si atoms is used as a Si source when forming a SiO ₂ film by the ALD method. The silicon dioxide film obtained by the method according to the present invention provides excellent film characteristics due to the strong bonding force of Si—O—Si present in the siloxane compound, and the amount of residual impurities in the film can be minimized. In addition, since a plurality of single SiO ₂ layers are obtained for each vapor deposition cycle of the ALD process, the vapor deposition rate is increased. As a result, the process time is greatly shortened and the throughput is improved.

  FIG. 1 is a flowchart for explaining a method of forming a silicon dioxide film according to a preferred embodiment of the present invention.

  FIG. 1 schematically shows various steps generally applied in the method of the present invention for forming a silicon dioxide film on a substrate by an ALD process using a catalyst (catalyst-assisted ALD process). .

  Referring to FIG. 1, in the method for forming a silicon dioxide film according to the present invention, first, a substrate on which a semiconductor element is to be formed is loaded into a chamber of a thin film forming apparatus (step 10). Thereafter, the substrate is preheated using a heater provided in the chamber so that the temperature of the substrate becomes a process temperature suitable for forming a silicon dioxide film, that is, a temperature of about 25 to 500 ° C. (step 20). At this time, the substrate is preheated simultaneously with the exhaust from the chamber, and the preheating step is performed, for example, for about 60 seconds.

  When the substrate is heated to a desired process temperature, a silicon dioxide film is formed on the substrate by an ALD method (step 30).

  For this purpose, first, a first reactant made of a siloxane compound substituted with a halogen element or —NCO and a first base catalyst are supplied together on the substrate, and the chemisorption layer of the first reactant on the substrate. (Step 32).

Materials suitable for use as the first reactant are Si _n O _n-1 X _{2n + 2} where n is an integer from 2 to 5, and X is F, Cl, Br, I, or NCO. Can be displayed. For example, as the first reactant, Si ₂ OCl ₆ , Si ₃ O ₂ Cl ₈ , Si ₄ O ₃ Cl ₁₀ , Si ₂ OBr ₆ , Si ₃ O ₂ Br ₈ , Si ₄ O ₃ Br ₁₀ , Si ₂ O ( NCO) ₆ or Si ₃ O ₂ (NCO) ₈ can be used.

Preferably, the first reactant comprises disiloxane substituted with a halogen element or -NCO. Particularly preferably, the first reactant comprises Si ₂ OCl ₆ , Si ₂ OBr ₆ or Si ₂ O (NCO) ₆ .

As the first base catalyst, pyridine (C ₅ H ₅ N) or amine is used. Preferably, an aliphatic tertiary amine compound having the general formula NR ₃ is used as the first base catalyst. In the formula, each R is the same or different aliphatic group having 1 to 5 carbon atoms. Particularly preferably, trimethylamine (C ₃ H ₉ N) is used as the first base catalyst.

  The process temperature in the chamber is maintained at 25 to 500 ° C., preferably 50 to 150 ° C. during the supply of the first reactant. Further, the process pressure in the chamber is maintained at 0.1 to 100 torr, preferably 0.5 to 5 torr when the first reactant is supplied. An inert gas such as argon (Ar) may be supplied into the chamber when the first reactant is supplied.

  By supplying the first reactant and the first base catalyst, H at the —OH reaction site on the substrate reacts with a substituent constituting the first reactant, that is, a halogen atom or —NCO, on the substrate. An acid is generated, and the acid thus generated generates a salt through a neutralization reaction with the first base catalyst. At the same time, one Si of the Si—O—Si bonds reacts with O at the —OH reaction site on the substrate while the first reactant retains the Si—O—Si bond. A chemical adsorption layer of the first reactant is formed thereon.

  If the first reactant chemical adsorption layer is formed on the substrate as described above, the reaction by-product of the first reactant, for example, the salt formed by the neutralization reaction of the oxidized base, the physical adsorption of the first reactant. Layers are removed (step 34).

  For this purpose, a purge process using an inert gas such as argon or an exhaust process at a pressure lower than the pressure at the time of supplying the first reactant is performed. Alternatively, in order to remove the reaction by-product, a series of processes combining the purge process and the exhaust process may be performed. For example, it is possible to first perform a purge process using an inert gas and then perform an exhaust process, and conversely to perform a purge process after performing an exhaust process.

  Next, the second reactant containing O and the second base catalyst are supplied together on the chemical adsorption layer of the first reactant, and the chemical adsorption layer of the first reactant and the second reactant are combined. Chemical reaction (step 36).

For example, H ₂ O, H ₂ O ₂ , ozone (O ₃ ), or oxygen radical can be used as the second reactant. Further, as the second base catalyst, the same substance as the first base catalyst can be used.

  The temperature and pressure conditions in the chamber during the supply of the second reactant are set to be the same as the conditions during the supply of the first reactant.

Due to the supply of the second reactant and the second base catalyst, H of the second reactant reacts with a halogen element or —NCO on the substrate to form an acid, and O of the second reactant and the second base catalyst are formed. One reactant reacts with Si in the chemical adsorption layer. The acid formed as described above generates a salt through a neutralization reaction with a base. As a result, a plurality of SiO ₂ single layers are formed on the substrate according to the number of Si—O—Si bonds in the first reactant. For example, when a substituted disiloxane compound is used as the first reactant, two SiO ₂ single layers are formed on the substrate.

  Thereafter, reaction by-products of the second reactant are removed (step 38).

  For this purpose, as in the step 34, a purge process, an exhaust process, or a series of processes combining the purge process and the exhaust process can be performed.

  Steps 32 to 38 are repeated a plurality of times until a silicon dioxide film having a desired thickness is formed on the substrate. When the silicon dioxide film is formed on the substrate to have a desired thickness, an evacuation process from the chamber is performed for a predetermined time, for example, about 90 seconds, in order to remove deposition byproducts remaining in the chamber (step 40). ). At this time, no gas is supplied into the chamber. Thereafter, the substrate is unloaded from the chamber (step 50).

The silicon dioxide film is annealed to improve resistance to the cleaning solution of the silicon dioxide film (step 60). The annealing is performed at a temperature of room temperature to 900 ° C. and a pressure of 760 torr or less, preferably 10 ^{−9 to} 760 torr for 5 minutes or less. The annealing may be performed by various methods using heat treatment, plasma treatment, ozone treatment, and the like. In the case of annealing by heat treatment, the heat treatment can be performed at a temperature of 500 to 900 ° C. in N ₂ , O ₂ , H ₂ , Ar, a combination of N ₂ and O ₂ , or an NH ₃ gas atmosphere. Preferably, the annealing by the heat treatment is performed for 5 minutes or less in a N ₂ atmosphere at a temperature of 500 to 900 ° C. and a pressure of 10 ^{−9 to} 760 torr. In the case of annealing by plasma treatment, plasma of O ₂ or H ₂ gas is used at a temperature of 200 to 700 ° C. Annealing by ozone treatment can be performed at a temperature of room temperature to 700 ° C. The annealing, plasma treatment, or ozone treatment process for annealing may be performed in situ with the ALD process for forming a silicon dioxide film described in step 30 of FIG. In this case, plasma treatment or ozone treatment is particularly desirable as the annealing method.

As described above, in the method for forming a silicon dioxide film according to the present invention, a substituted siloxane compound is used as a Si source. Therefore, during one deposition cycle of the ALD process, a plurality of single SiO ₂ layers are formed on the substrate surface due to the number of Si—O—Si bonds existing in the siloxane compound, and the deposition rate can be increased.

  FIG. 2 is a gas pulsing diagram showing a supply state of a process gas and the like applied for each deposition cycle of the ALD process in the method of forming a silicon dioxide film according to a preferred embodiment of the present invention.

  Referring to FIG. 2, in the first reactant supply stage, a first reactant comprising a substituted siloxane compound and a catalyst such as an amine are introduced into the chamber via respective supply lines. At this time, in order to purge the second reactant supply line, an inert gas, for example, argon is supplied to the chamber through the second reactant supply line.

  Further, in the purge stage after the first reactant supply, purge inert gas is supplied into the chamber from the first reactant supply line, the second reactant supply line, and the catalyst supply line, respectively.

  In the supply stage of the second reactant, the second reactant containing O and H and the base catalyst are supplied via respective supply lines. At this time, in order to purge the first reactant supply line, an inert gas, for example, argon is introduced into the chamber through the first reactant supply line.

  Then, in the purge stage after the second reactant supply, inactive for purge from the first reactant supply line, the second reactant supply line, and the catalyst supply line, respectively, as in the purge stage after the first reactant supply. Gas is supplied into the chamber.

3 to 6 are graphs illustrating pressure changes according to each process step applied to one deposition cycle of the ALD process in the method of forming a silicon dioxide film according to the preferred embodiment of the present invention. Each of the embodiments illustrated in FIGS. 3-6 uses hexachlorodisiloxane (Si ₂ OCl ₆ ) as the first reactant, H ₂ O as the second reactant, and Ar as the purge gas. Each can be applied to be more suitable when the process temperature is 105 ° C. 3 to 6 show various methods that can be applied in the step of removing reaction by-products in steps 34 and 38 of FIG. That is, in order to remove reaction by-products, when purging using an inert gas, for example, Ar, in the example of FIG. 3, in the example of FIG. When exhausting at a low pressure, the example of FIG. 5 shows the case of exhausting after Ar purging, and the example of FIG. 6 shows the case of performing Ar purging after exhausting.

  FIG. 7 shows a method for forming a silicon dioxide film according to the present invention, in which hexachlorodisiloxane is used as the first reactant and H2O is used as the second reactant. It is drawing which showed roughly the reaction process of this.

  Referring to FIG. 7, when hexachlorodisiloxane and pyridine are supplied onto the substrate in the state [I] in which the —OH reaction site is present on the substrate surface by the method described in step 32 of FIG. Of the —OH, H reacts with Cl to form HCl, O binds to Si of hexadichlorodisiloxane, and a chemisorption layer 102 of hexachlorodisiloxane is formed on the substrate surface in the same manner as [II]. Is done. Here, HCl generates a salt through a neutralization reaction with pyridine.

After purging the resultant product on which the chemical adsorption layer 102 is formed, a reaction step product is removed, and then H ₂ O and pyridine are supplied onto the substrate by the method described in step 36 of FIG. , H in H ₂ O and Cl in the chemisorption layer 102 react to form HCl, and O in H ₂ O and Si in the chemisorption layer 102 combine to form [ Two SiO ₂ single layers 104 are formed as in III]. Here, HCl generates a salt through a neutralization reaction with pyridine. These salts are removed through a purge step.

As described in the case of using hexachlorodisiloxane as the first reactant in FIG. 7, the method according to the present invention uses a siloxane compound substituted as a Si source in the ALD process for forming a silicon dioxide film. Since a Si—O—Si bond having a strong bonding force between Si and O exists in the siloxane compound, the resulting silicon dioxide film can provide excellent characteristics. In the case of using hexachlorodisiloxane as an Si source, for example, two SiO ₂ monolayers are obtained for each deposition cycle of the ALD process, so that the deposition rate can be increased. In addition, one molecule of hexachlorodisiloxane has three Si—Cl bonds per one Si. Therefore, since there are few Si-Cl bonds which may form an O-H bond compared with the prior art which uses SiCl ₄ as a Si source, the residual amount of O-H bonds in the silicon dioxide film is greatly increased. Can be reduced.

  The silicon dioxide film formed according to the embodiment of the present invention as described above can be applied in various ways in the manufacturing process of highly integrated semiconductor devices. For example, the silicon dioxide film can constitute a sidewall spacer of the gate electrode formed on the semiconductor substrate. The silicon dioxide film can also constitute a gate insulating film on the semiconductor substrate. As another example, the silicon dioxide film may constitute a silicidation blocking film. In addition, the silicon dioxide film can constitute a side wall spacer of a bit line formed on the semiconductor substrate. As another example, the silicon dioxide film can constitute an interlayer insulating film formed on the semiconductor substrate or an etching preventing film for protecting a predetermined film on the semiconductor substrate. When the silicon dioxide film is used as an etching preventing film, the silicon dioxide film may be used alone or as a composite film with a silicon nitride film. More specifically, in order to prevent a predetermined film formed on the semiconductor substrate from being damaged during the dry etching process, a silicon nitride film is mainly used as an etching preventing film during the dry etching process. At this time, the method according to the present invention is used between the predetermined film and the silicon nitride film in order to prevent a recess phenomenon that occurs due to the surface of the predetermined film underneath being etched due to overetching of the silicon nitride film. The formed silicon dioxide film can be interposed.

  The silicon dioxide film formed by the method according to the present invention can be applied in various processes required for manufacturing a highly integrated semiconductor device, and is not limited to the illustrated example.

<Evaluation Example 1>
In order to confirm the properties of the silicon dioxide film formed by the method according to the present invention, hexachlorodisiloxane (HCDSO) is used as the first reactant, H ₂ O is used as the second reactant, and pyridine is used as the base catalyst. A silicon dioxide film was formed on the substrate under the process conditions shown in Table 1.

As a control, a silicon dioxide film was formed under the same process conditions as in Table 1 except that hexachlorodisilane (Si ₂ Cl ₆ : HCD) was used as the Si source.

As a result of measuring the refractive indexes of the silicon dioxide film obtained from HCDSO and the silicon dioxide film obtained from HCD under the above conditions, the silicon dioxide film obtained from HCD is 1.5 to 1.51. On the other hand, the silicon dioxide film obtained from HCDSO according to the present invention was measured as 1.44 to 1.46, indicating a level equivalent to that of the stoichiometric SiO ₂ film.

<Evaluation Example 2>
FIG. 8 shows that after forming a silicon dioxide film obtained from HCDSO and a silicon dioxide film obtained from HCD under the same process conditions as in Table 1 except that the process temperature is 75 ° C., the respective silicon dioxides are formed. It is a FTIR (Fourier Transfer Infrared Spectrometer) spectrum acquired with respect to the film | membrane. FIG. 8 shows both FTIR spectra of a silicon dioxide film obtained from tetrachlorosilane (SiCl ₄ : TCS) according to the prior art.

  As can be seen from FIG. 8, the silicon dioxide film obtained from HCDSO shows almost no Si—OH peak and Si—H peak compared to the silicon dioxide film obtained from HCD, and the silicon dioxide film obtained from HCDSO. It can be seen that the -OH and -H contents are very low.

<Evaluation Example 3>
FIG. 9 shows a case where a silicon dioxide film is formed by ALD using HCDSO as a Si source by the method of the present invention (▲), and a silicon dioxide film is formed by ALD using TCS as a Si source according to an example of the prior art. When formed (■) and when silicon dioxide film is formed using HCD as Si source according to another example of the prior art (●) The result of comparing the deposition rate of each silicon dioxide film at various process temperatures It is the graph which showed.

From FIG. 9, it can be seen that when HCDSO is used as the Si source by the method of the present invention (▲), the deposition rate is significantly faster than when TCS or HCD is used at all applied process temperatures. I can confirm. This can be interpreted as using the HCDSO, which is a siloxane compound, as the Si source in the method according to the present invention to form _two SiO ₂ single layers for each deposition cycle of the ALD process and increase the deposition rate.

  The present invention has been described in detail with reference to the preferred embodiments. However, the present invention is not limited to the above-described embodiments, and various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. is there.

  INDUSTRIAL APPLICABILITY The present invention can be applied to the manufacture of various semiconductor devices that employ silicon dioxide films such as gate oxide films and dielectric films of field effect transistors. It can be used very effectively to manufacture a silicon dioxide film that can be used as an insulating film necessary for constituting a unit element capable of exhibiting the above.

3 is a flowchart illustrating a method for forming a silicon dioxide film according to a preferred embodiment of the present invention. 3 is a gas pulsing diagram showing a supply state of a process gas and the like applied for each deposition cycle of an ALD process in a method for forming a silicon dioxide film according to a preferred embodiment of the present invention. 3 is a graph showing pressure changes according to respective process steps applied to one deposition cycle of an ALD process in a method of forming a silicon dioxide film according to an embodiment of the present invention. 6 is a graph illustrating pressure change according to each process step applied to one deposition cycle of an ALD process in a method of forming a silicon dioxide film according to another exemplary embodiment of the present invention. 6 is a graph showing pressure changes according to respective process steps applied to one deposition cycle of an ALD process in a method of forming a silicon dioxide film according to still another preferred embodiment of the present invention. 6 is a graph showing pressure changes according to respective process steps applied to one deposition cycle of an ALD process in a method of forming a silicon dioxide film according to still another preferred embodiment of the present invention. 3 is a view illustrating a reaction process in a method for forming a silicon dioxide film according to an embodiment of the present invention. 6 is a diagram showing the FTIR spectrum of a silicon dioxide film formed by the method of the present invention compared with the case of a silicon dioxide film formed by a method according to the prior art. 3 is a graph showing an evaluation of the deposition rate of a silicon dioxide film obtained at various process temperatures according to the method of the present invention compared with the deposition rate of a silicon dioxide film by a conventional method.

Claims (45)

(A) supplying a first reactant comprising a halogen element or a siloxane compound substituted with —NCO groups onto a substrate together with a first catalyst to form a chemical adsorption layer of the first reactant;
(B) supplying a second reactant together with a second catalyst onto the chemical adsorption layer to form a silicon dioxide film on the substrate;
Only including,
The second reactant is a compound having an oxygen component;
The first catalyst and the second catalyst each comprise pyridine or amine; and
The method of forming a silicon dioxide film further comprising the step of annealing the silicon dioxide film after the step (b) . The first reactant is composed of a siloxane compound represented by Si _n O _n-1 X _{2n + 2} (where n is an integer of 2 to 5, and X is F, Cl, Br, I, or NCO). The method for forming a silicon dioxide film according to claim 1.   2. The method of forming a silicon dioxide film according to claim 1, wherein the first reactant is made of a halogen element or disiloxane substituted with -NCO. _{2. The} method of forming a silicon dioxide film according to claim 1, wherein the first reactant is selected from the group consisting of Si ₂ OCl ₆ , Si ₂ OBr ₆ and Si ₂ O (NCO) ₆ . 2. The method of forming a silicon dioxide film according to claim 1 , wherein the second reactant is selected from the group consisting of H ₂ O, H ₂ O ₂ , ozone, and oxygen radicals.   2. The method of forming a silicon dioxide film according to claim 1, wherein the steps (a) and (b) are performed at a temperature of 25 to 500 ° C., respectively.   The method of claim 1, wherein the steps (a) and (b) are each performed under a pressure of 0.1 to 100 Torr.   The inert gas is supplied to the substrate while the first reactant and the second reactant are supplied in the steps (a) and (b), respectively. Of forming a silicon dioxide film.   2. The method of forming a silicon dioxide film according to claim 1, further comprising the step of sequentially repeating the steps (a) and (b) a plurality of times until a silicon dioxide film having a desired film thickness is obtained. . 2. The method of forming a silicon dioxide film according to claim 1 , wherein the annealing is performed by a heat treatment, a plasma treatment, or an ozone treatment method. Claim 1, characterized in that a heat treatment at _{N 2,} O _2, H 2, Ar, combination of _{N 2} and _{O 2} or NH ₃ temperature 500 to 900 ° C. in a gas atmosphere, for the annealing Of forming a silicon dioxide film. _{2. The} method of forming a silicon dioxide film according to claim 1 , wherein plasma treatment is performed using O ₂ or H ₂ gas at a temperature of 200 to 700 ° C. for the annealing. Method of forming a silicon dioxide film according to claim 1, characterized in that the ozone treatment at a temperature of room temperature to 700 ° C. for the annealing. Removing a reaction byproduct of the first reactant from a region around the substrate after the step (a);
2. The method of forming a silicon dioxide film according to claim 1, further comprising a step of removing a reaction byproduct of the second reactant from a region around the substrate after the step (b). The removal step of the reaction byproduct includes the following:
(I) purge using an inert gas;
(Ii) exhaust under a pressure lower than the pressure at the time of supplying the first reactant and the second reactant,
(Iii) a combination of purge and exhaust using an inert gas;
The method of forming a silicon dioxide film according to claim 14 , wherein a process selected from among the processes is performed.   The method of forming a silicon dioxide film according to claim 1, further comprising preheating the substrate at a temperature of 25 to 500 ° C. before the step (a). (A) loading a substrate into the chamber;
(B) Si _n O _n-1 X _{2n + 2} (wherein n is an integer of 2 to 5 and X is F, Cl, Br, I, or NCO) In the chamber together with a first catalyst to form a chemisorbed layer of the first reactant on the substrate;
(C) removing the reaction byproduct of step (b) in the chamber;
(D) supplying a second reactant together with a second catalyst into the chamber and reacting with the chemisorption layer to form a silicon dioxide film on the substrate;
(E) removing the reaction byproduct of step (d);
Only including,
The second reactant is a compound having an oxygen component;
The first catalyst and the second catalyst each comprise pyridine or amine; and
The method of forming a silicon dioxide film further comprising the step of annealing the silicon dioxide film after the step (e) . 18. The method of forming a silicon dioxide film according to claim 17 , further comprising the step of sequentially repeating the steps (a) to (e) a plurality of times until a silicon dioxide film having a desired film thickness is obtained. . The method of forming a silicon dioxide film according to claim 17 , further comprising preheating the substrate at a temperature of 25 to 500 ° C. after the step (a) and before the step (b). The first reactant forming method of the silicon dioxide film according to claim 17, characterized in that it is selected from the group consisting of _{Si 2 OCl 6, Si 2 OBr} 6 and _Si 2 O _{(NCO) 6.} The method of claim 17 , wherein the second reactant is selected from the group consisting of H ₂ O, H ₂ O ₂ , ozone, and oxygen radicals. The method of claim 17 , wherein the step (b) and the step (d) are each performed at a temperature of 25 to 500C. The method of claim 17 , wherein the steps (b) and (d) are each performed under a pressure of 0.1 to 100 Torr. In the step (b) and step (d), according to claim 17, each said first reactant and a second reactant, characterized in that the inert gas between the chamber to be supplied is supplied together Of forming a silicon dioxide film. In step (c) and step (e), respectively:
(I) purge using an inert gas;
(Ii) exhaust under a pressure lower than the pressure at the time of supplying the first reactant and the second reactant,
(Iii) a combination of purge and exhaust using an inert gas;
The method of forming a silicon dioxide film according to claim 17 , wherein a process selected from among the processes is performed. The method of forming a silicon dioxide film according to claim 17 , wherein the annealing is performed by a heat treatment, a plasma treatment, or an ozone treatment method. In a method of forming a silicon dioxide film on a substrate surface for a semiconductor product using a catalyst-assisted atomic layer deposition process,
The functionalized surface of the substrate is exposed to a first mixture of only the first reactant and the first catalyst, and then the substrate surface is second and second to form a silicon dioxide monolayer on the substrate surface. Continuous exposure to a second mixture consisting only of catalyst,
The first reactant is essentially composed of at least one element selected from the group consisting of a halogen element or a siloxane compound substituted with a -NCO group ,
The second reactant is a compound having an oxygen component;
The first catalyst and the second catalyst are each selected from the group consisting of pyridine or amine; and
A method of forming a silicon dioxide film, further comprising annealing the deposited silicon dioxide film. The first reactant is essential from a siloxane compound represented by Si _n O _n-1 X _{2n + 2} (where n is an integer of 2 to 5 and X is F, Cl, Br, I, or NCO). 28. The method of forming a silicon dioxide film according to claim 27 , comprising: 29. The method of forming a silicon dioxide film according to claim 28 , wherein the first reactant is essentially composed of a halogen element or disiloxane substituted with -NCO. The first reactant forming method of the silicon dioxide film according to claim 29, characterized in that it is selected from the group consisting of _{Si 2 OCl 6, Si 2 OBr} 6 and _Si 2 O _{(NCO) 6.} The first catalyst is composed of an aliphatic tertiary amine compound having the general formula NR ₃ , wherein each R is the same or different aliphatic group having 1 to 5 carbon atoms. 28. The method for forming a silicon dioxide film according to claim 27 . 28. The method of forming a silicon dioxide film according to claim 27 , wherein the first catalyst is composed of only trimethylamine. Wherein the first reactant is configured essentially from Si ₂ OCl _6, the method of forming the silicon dioxide film according to claim 27, wherein said first catalyst is to be constructed essentially from trimethylamine. The method according to claim 27 , wherein the step is performed in a temperature range of 25 to 500C. The method according to claim 27 , wherein the step is performed in a pressure range of 0.1 to 100 Torr. 28. The method of forming a silicon dioxide film according to claim 27 , wherein the first catalyst and the second catalyst are the same as each other. 28. The method of forming a silicon dioxide film according to claim 27 , further comprising the step of removing unreacted reactants, the first catalyst, the second catalyst, and the reaction byproducts from the surface region of the substrate following each step. . 29. The method of forming a silicon dioxide film according to claim 28 , further comprising the step of removing unreacted reactants, the first catalyst, the second catalyst, and the reaction byproducts from the surface region of the substrate following each step. . 38. The method of forming a silicon dioxide film according to claim 37 , wherein the first reactant, the second reactant, the first catalyst, and the second catalyst are supplied to the substrate surface by independent supply lines. The following deposition cycle:
A first reaction period, which is a period in which the first reactant and the catalyst are supplied to the substrate surface via their respective supply lines together with an inert gas supplied via the second reactant supply line;
A first purge period in which the supply of the first reactant and the catalyst is stopped and an inert gas is supplied through the first reactant supply line, the second reactant supply line, and the catalyst supply line instead. When,
A second reaction period, which is a period during which the second reactant and the catalyst are supplied to the substrate surface via their respective supply lines together with an inert gas supplied via the first reactant supply line;
The second purge is a period in which the supply of the second reactant and the catalyst is stopped and the inert gas is supplied through the first reactant supply line, the second reactant supply line, and the catalyst supply line instead. Period,
40. The method for forming a silicon dioxide film according to claim 39 , comprising: 28. The method of forming a silicon dioxide film according to claim 27 , further comprising repeating the method a plurality of times on the same substrate to obtain a silicon dioxide film having a desired film thickness. 41. The method of forming a silicon dioxide film according to claim 40 , further comprising repeating the deposition cycle a plurality of times on the same substrate to obtain a silicon dioxide film having a desired film thickness. The annealing step is as follows:
N ₂ , O ₂ , H ₂ , Ar, a combination of N ₂ and O ₂ , or a heat treatment at a temperature of 500 to 900 ° C. in an NH ₃ gas atmosphere,
Plasma treatment using O ₂ or H ₂ gas at a temperature of 200-700 ° C.,
Ozone treatment at room temperature to 700 ° C,
28. The method of forming a silicon dioxide film according to claim 27 , wherein: The following sequence:
The first reactant and the first catalyst stage is supplied to a region including the substrate during step period t _1,
Purging the region with an inert gas for a period t ₂ immediately after the period t ₁ ;
Evacuating said region immediately after period t ₂ to at least partially drain inert gas and other gaseous substances from said region during period t ₃ ;
Immediately after the time period t _3, and supplies the second reactant during the period t ₄ and a second catalyst in said region stages,
Immediately after the time period t _4, the step of purging the space between inert gas period t _5,
Evacuating said region immediately after period t ₅ to at least partially drain inert gas and other gaseous substances from said region during period t ₆ ;
28. The method of forming a silicon dioxide film according to claim 27 , further comprising a purge evacuation process for each atomic layer deposition by the sequence of: The following sequence:
The first reactant and the first catalyst stage is supplied to a region including the substrate during step period t _1,
Evacuating said region immediately after period t ₁ to at least partially exhaust gaseous substances from said region during period t ₂ ;
Purging the region with an inert gas for a period t ₃ immediately after the period t ₂ ;
Immediately after the time period t _3, and supplies the second reactant during the period t ₄ and a second catalyst in said region stages,
Evacuating said area immediately after period t ₄ in order to at least partially discharge gaseous substances from said area during period t ₅ ;
Immediately after the period t _5, the step of purging the space between inert gas period t _6,
28. The method of forming a silicon dioxide film according to claim 27 , further comprising an exhaust purge process for each atomic layer deposition according to the sequence of:

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