KR100560963B1 - Method of forming material using atomic layer deposition process, method of forming thin film, and method of forming capacitor using the same - Google Patents

Abstract

Disclosed are a method of forming a material having improved leakage current control characteristics and excellent insulating properties using an atomic layer deposition process, a method of forming a thin film, and a method of manufacturing a capacitor using the same. Chemically adsorbing the first reactant containing the first element on the substrate, and chemically reacting the first reactant and the second reactant including the second element chemically adsorbed on the substrate to the chemical reaction of the first element and the second element on the substrate Form a material made by bonding. After repeating the above-described process five times or more to form a material of about 5 to 30 kPa, a first flushing gas containing a second element is applied to the formed material to improve the properties of the material. Since carbon in the thin film can be effectively removed, leakage current can be significantly reduced, and oxygen deficiency can be prevented to form a thin film having excellent insulation performance. In addition, high-quality thin films and highly reliable memory devices can be economically produced in an in-situ process, thereby reducing the overall time and cost of the semiconductor manufacturing process.

Description

METHODS OF FORMING MATERIAL USING ATOMIC LAYER DEPOSITION PROCESS, METHOD OF FORMING THIN FILM, AND METHOD OF FORMING CAPACITOR USING THE SAME}

1 is an X-ray diffraction pattern graph showing the degree of crystallization in a thin film according to a rapid heat treatment temperature according to the prior art.

2 is a graph showing the density of carbon in a thin film before and after plasma O ₂ treatment according to the prior art.

3 is a flowchart illustrating a method of forming a material using an atomic layer deposition process according to an embodiment of the present invention.

4A to 4F are cross-sectional views illustrating a method of forming a material on a semiconductor substrate using an atomic layer deposition process according to an embodiment of the present invention.

FIG. 5 is a timing chart illustrating a method of forming a material on a semiconductor substrate using an atomic layer deposition process according to an embodiment of the present invention.

6 is a flowchart illustrating a method of forming a material using an atomic layer deposition process according to another embodiment of the present invention.

FIG. 7 is a timing chart illustrating a method of forming a material shown in FIG. 6.

8 is a flowchart illustrating a method of forming a material using an atomic layer deposition process according to another embodiment of the present invention.

FIG. 9 is a timing chart illustrating a method of forming a material shown in FIG. 8.

10 is a flowchart illustrating a method of forming a material using an atomic layer deposition process according to another embodiment of the present invention.

FIG. 11 is a timing chart for explaining a method of forming a material shown in FIG. 10.

12 is a flowchart illustrating a thin film forming method according to an embodiment of the present invention.

13A to 13F are cross-sectional views for describing the method of forming the thin film illustrated in FIG. 12.

14 is a flowchart illustrating a method of manufacturing a capacitor according to the present invention.

15A to 15E are cross-sectional views illustrating a method of manufacturing the capacitor shown in FIG. 14.

16 is a TOF-SIMS graph showing the density of carbon in a thin film.

17 is a graph showing leakage current control characteristics.

18 is a graph showing the leakage current control characteristics according to the temperature of the post-heat treatment process.

 19 is a graph showing the relationship between the leakage current and Toxeq according to the flushing time.

 20 is a graph illustrating leakage current control characteristics in a DRAM including a capacitor manufactured according to an embodiment of the present invention.

Brief description of the main parts of the drawing

1: 1st element 2: amino group etc.

3: first reactant 4: first layer

5: second layer 6: second reactant

8: substance 9: substance layer

10: substrate 20: nitride film

30, 30 ': thin film 32, 32': improved thin film

100: semiconductor substrate 101: active region

102: device isolation region 104: gate dielectric film

106: polysilicon film 110: gate electrode

116a and 116b: source / drain regions 118: first insulating film

120: contact hole 122: contact plug

123: etching prevention film 124: second insulating film

126: Opening part 127: Second conductive film

128: lower electrode 130: capacitor dielectric film

132: upper electrode

The present invention relates to a method of forming a thin film using an atomic layer deposition (ALD) process, and more particularly, a method of forming a material having a significantly improved electrical property by performing a flushing step during an atomic layer deposition (ALD) process. It relates to a thin film forming method and a capacitor manufacturing method used.

In general, the decrease in cell capacitance due to the reduction of the memory cell area makes it difficult to increase the integration density of a semiconductor memory device. This reduction in cell capacitance degrades the data readability of the memory cell, increases the soft error rate, and makes it difficult for the semiconductor memory device to operate at low voltages. Accordingly, various techniques have been developed for increasing cell capacitance without affecting the area occupied by the cell.

In order to increase capacitance in a limited cell region, a method of thinning a dielectric film of a capacitor or a method of increasing an effective area of a capacitor by forming a capacitor lower electrode having a structure such as a cylinder or a fin has been proposed. However, in dynamic random access memory (DRAM) of 1 gigabit or more, it is difficult to obtain a capacitance high enough to operate a memory device with these methods.

In order to solve this problem, in the manufacture of a dielectric film of a capacitor of a highly integrated semiconductor memory device having a design rule of 1 μm or less, a conventional nitride film, tantalum oxide (Ta ₂ O ₅ ) or alumina (Al ₂ O ₃₎ Dielectric layer of a material having a relatively high dielectric constant (κ), for example, a Y ₂ O ₃ film, a HfO ₂ film, a ZrO ₂ film, a Nb ₂ O ₅ film, a BaTiO ₃ film, or a SrTiO ₃ film How to use it has been actively studied.

In particular, instead of using alumina alone as the dielectric film of the capacitor, a capacitor is manufactured by using a composite film including hafnium oxide (HfO ₂ ) -alumina (Al ₂ O ₃ ), or further, a metal-insulating film-semiconductor that is easy to laminate ( The use of hafnium oxide alone in the manufacture of metal-insulator-semiconductor (MIS) capacitors makes it possible to use smaller Toxeq (thickness of equivalent oxide) to obtain the same capacitance.

In other words, the hafnium oxide film is superior to other insulating films and has excellent insulating properties and is suitable for fabricating highly integrated devices. In recent years, hafnium oxide films are attracting attention as materials such as gate insulating films and capacitor dielectric films in combination with the atomic layer deposition (ALD) process. The inventors have invented a method of forming hafnium oxide by an atomic layer deposition (ALD) process and using it as an insulating film of a capacitor, and has filed it as Korean Patent Application No. 2002-42217. .

However, in the above-described high dielectric constant dielectric film including a hafnium oxide film, since an impurity such as carbon, which is present in the dielectric film, serves as a trap site, there is a problem that the insulating property is deteriorated.

In order to overcome this problem, Korean Patent Laid-Open Publication No. 1994-5289 proposes a method of overcoming an oxygen deficiency phenomenon in a dielectric film and removing carbon by continuously performing a dielectric film formation and an O ₃ annealing process in a method of forming a semiconductor high dielectric film. Doing. Specifically, a first process of forming a metal film by introducing a metal source and oxygen gas and a second process of performing annealing using O ₃ are periodically repeated in an in situ environment.

However, when a high temperature heat is applied during a process for manufacturing a semiconductor device, for example, the thin film undergoes crystallization from an amorphous structure while undergoing rapid thermal heat treatment (RTP). A boundary boundary is formed, and the grain boundary acts as a leakage current path of the leakage current, thereby increasing the leakage current.

FIG. 1 shows an X-ray diffraction pattern graph which shows the degree of crystallization in a thin film according to temperature when the rapid heat treatment according to the prior art is performed.

Referring to FIG. 1, when the heat treatment temperature is increased, peaks are frequently observed on the graph, and this peak means that crystallization in the thin film has progressed. When the material in the thin film is crystallized, leakage currents are generated along the grain boundaries, thereby degrading the insulating property of the thin film. In addition, when a thin film is formed by a general chemical vapor deposition (CVD) process, it is difficult to precisely control the thickness of the thin film, thereby making it unsuitable for the recent highly integrated memory manufacturing process.

In consideration of these problems, it is necessary to proceed with the film quality improvement process at a low temperature in the treatment of the thin film. For example, a method is known for removing carbon and solving oxygen deficiency by treating the dielectric film with plasma O ₂ after the formation of the capacitor dielectric film.

2 is a graph showing the density of carbon in a thin film before and after plasma O ₂ treatment according to the prior art.

Referring to FIG. 2, it can be observed that the concentration of carbon in the thin film is reduced when the plasma O _{2 is} treated as a whole. However, in the graph, as the sputtering time elapses, that is, the inside of the thin film, the carbon concentration does not show a big difference from the case where the plasma treatment is not performed. In other words, the film quality improvement of the dielectric film is not easy by surface treatment of the dielectric film by plasma O ₂ . Of course, if the treatment time with plasma O ₂ is increased, the film quality improvement effect also reaches the inside of the film. For example, a problem arises in that Toxeq increases due to oxidation of a lower structure such as a lower electrode of the capacitor.

In order to solve this problem, a method of removing residual carbon by adding ozone or the like to an alumina insulating film in the middle of an atomic layer deposition process is known. For example, U. S. Patent No. 6,124, 158 repeats a unit process for atomic layer deposition consisting of adsorption and purge of a first compound including an aluminum precursor, adsorption of a second compound such as a purge, an oxidant, and purge one to three times. Techniques for improving membrane quality by introducing ozone for from 10 seconds, preferably from 3 to 10 seconds, are disclosed. However, according to the method disclosed in the patent, since the ozone is added only after performing the unit process for atomic layer deposition only once or three times, there is a possibility that the lower substrate is oxidized and reproducibility is not secured. In addition, since it is necessary to repeat a separate process a number of times using ozone different from the reaction gas, it is not economically preferable.

The hafnium insulating film needs to be subjected to a high temperature heat treatment in order to remove residual carbon. However, when the hafnium insulating film is subjected to high temperature heat treatment, crystallization of the hafnium insulating film proceeds to increase the leakage current. Therefore, the development of a technology that can achieve a residual carbon removal effect uniformly over the entire insulating film by a low temperature process is required.

It is a first object of the present invention to provide a method of forming a material having a significantly improved leakage current control property and an excellent insulation property by performing a process for improving the property of a material having a high dielectric constant at low temperature using an atomic layer deposition process.

It is a second object of the present invention to provide a method for forming a thin film which can be applied to a gate oxide film, a capacitor dielectric film, or the like having excellent leakage current control characteristics and insulation characteristics using the material formation method.

It is a third object of the present invention to provide a method of manufacturing a capacitor including a dielectric film using the above-described material forming method.

In order to achieve the first object of the present invention described above, according to a preferred embodiment of the material forming method according to the present invention, first, the first reactant containing the first element is chemisorbed on the substrate, the chemically adsorbed agent The first reactant and the second reactant including the second element are chemically reacted to form a material formed by chemical bonding of the first element and the second element on the substrate. This process is repeated about five times or more to form a material of about 5 to 30 kPa, and then a flushing gas containing a second element is applied to the formed material to improve the properties of the material. Here, the flushing gas includes an activated oxidant, and improving the material properties is preferably performed at a temperature of about 200 to 400 ° C.,

In order to achieve the above-mentioned second object of the present invention, according to a preferred embodiment of the thin film forming method according to the present invention, the substrate is first placed in a reactor. Subsequently, a first reactant including a first element constituting a thin film to be formed in the reactor is introduced to chemically adsorb a portion of the first reactant onto a substrate, and then a first purge gas is introduced into the reactor to obtain a non-chemically adsorbed material. First purge. Subsequently, a second reactant including a second element is introduced into the reactor to chemically react the chemically adsorbed first reactant with the second reactant to form a thin film on the substrate, and introduce a second purge gas into the reactor. To purge the microchemically adsorbed material. By repeating the above step five times or more, the thin film is grown to a thickness at which the flushing process described later can be most efficiently performed. Subsequently, a first flushing gas containing a second element is introduced into the reactor and applied to the thin film to improve characteristics of the thin film. The above steps can be repeated to grow the thin film to the intended thickness.

 In order to achieve the third object of the present invention described above, according to a preferred embodiment of the method for forming a capacitor according to the present invention, a lower structure such as a lower electrode is formed on a substrate. A first reactant comprising a first element is introduced into the reactor to chemically adsorb a portion of the first reactant onto the lower electrode and remove the residue by first purging with a first purge gas. Subsequently, a second reactant including a second element bonded to the first element is introduced into the reactor to chemically react the chemisorbed first reactant with the second reactant to chemically react the first and second elements on the lower electrode. Secondary purge of the microchemically adsorbed material is formed by forming an insulating material by bonding and introducing a second purge gas. This process is repeated to stack the material to a thickness at which the flushing process can proceed most efficiently. Subsequently, a first flushing gas containing a second element is introduced into the reactor and applied to an insulating material to form an insulating film having improved characteristics. Subsequently, the above-described steps are repeated to grow an insulating film to the thickness required on the lower electrode. The capacitor is manufactured by forming an upper electrode on the insulating film having improved characteristics.

According to the present invention, it is possible to effectively remove the carbon in the thin film, to significantly reduce the leakage current, and to prevent the oxygen deficiency to form a thin film having excellent insulating properties. In addition, since the thin film is modified through a low temperature flushing step, crystallization and deterioration of the thin film due to heat treatment may be prevented. Moreover, such a method can be widely used, for example, in a gate oxide film, a capacitor dielectric film, or the like, and thus has a wide range of application, and in combination with an existing atomic layer deposition process, it is possible to form an ultra-thin and high-quality insulating film. In particular, when the thin film according to the present invention is used as an insulating film of a semiconductor memory device, it becomes possible to use a relatively thin insulating film in order to obtain the same insulating effect, so that the manufacture of highly integrated memory devices requiring the latest design rules of 1 μm or less Can effectively cope with the process. As a result, according to the present invention, it is possible to economically produce a high quality thin film and a reliable memory device using the same in an in-situ process, thereby reducing the time and cost required for the overall semiconductor manufacturing process. do.

 Hereinafter, a method of forming a material, a method of forming a thin film, and a method of manufacturing a capacitor according to preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

3 is a flowchart illustrating a method of forming a material using an atomic layer deposition (ALD) process according to an embodiment of the present invention.

Referring to FIG. 3, first, a first reactant including a first element is chemically adsorbed onto a substrate (step S11), and then a second element that combines the first reactant chemisorbed on the substrate with the first element is added. By chemically reacting with the second reactant to form a material formed by chemical bonding of the first element and the second element on the substrate (step S13). Steps S11 and S13 are usually repeated about 5 or more times to form a material having a thickness of about 5 to 30 mm 3. In general, when the step S11 and S13 is performed once, the material is formed to a thickness of about 0.7 to 1Å, so that the material is repeated about 5 to 50 times or less and forms a material having a thickness of about 5 to 30Å. Then, the first flushing gas containing the second element is applied to the material formed on the substrate to improve the properties of the material (step S15).

Here, the step of depositing the material (S11, S13) is made through an atomic layer deposition process, the step of applying to the material of the first flushing gas (S15) is at a temperature of about 200 to about 400 ℃ Is performed. Deposition of the material (S11, S13) and the application of the first flushing gas (S15) may be repeated several times to form a material having improved properties on the substrate. That is, impurities such as carbon may be removed from a material formed on the substrate by introducing a flushing step, a so-called layered oxidation treatment (LOT) process, during the atomic layer deposition (ALD) process, and oxygen deficiency in the material. (oxygen deficiency) can be eliminated.

During the steps described above, steps S12 and S14 may be additionally performed to introduce a purge gas to remove unreacted compounds. That is, after first chemically adsorbing the first reactant (step S11), a first purge gas is introduced to first purge the unreacted material that is not chemisorbed (step S12). In addition, after the second reactant is reacted with the chemisorbed first reactant, a second purge gas is introduced to remove the chemisorbed unreacted material (step S14).

Hereinafter, an example of applying a material forming method according to an embodiment of the present invention to a manufacturing process of a semiconductor device will be described in detail with reference to the accompanying drawings.

4A through 4F are cross-sectional views illustrating a method of forming a material on a semiconductor substrate using an atomic layer deposition (ALD) process according to an embodiment of the present invention, and FIG. 5 illustrates one embodiment of the present invention. A timing chart for explaining a method of forming a material on a semiconductor substrate using an atomic layer deposition process according to an embodiment is shown. In the present embodiment, specific semiconductor devices, metal precursors, processes, and the like are illustrated to effectively explain the material forming method according to the present invention, but this description is merely exemplary, and the present invention is limited by these examples. It doesn't happen.

3 and 4A, a substrate 10 made of a semiconductor material such as silicon is placed in a reactor (not shown), followed by a first element (1; for example, metal), an amino group, a halide, an alkyl group. Or a first reactant (3) comprising an alkoxide group (hereinafter referred to as 'amino group', etc.) in part within the reactor in which the substrate (10) is located to partially introduce the first reactant (3). Is adsorbed onto the substrate 10 (step S11).

Here, the first reactant 3 is hafnium (Hf), tantalum (Ta), aluminum (Al), silicon (Si), lanthanum (La), yttrium (Y), zirconium (Zr), magnesium (Mg), Strontium (Sr), Lead (Pb), Titanium (Ti), Niobium (Nb), Cerium (Ce), Ruthenium (Ru), Barium (Ba), Calcium (Ca), Indium (In), Germanium (Ge), Metals containing any one of tin (Sn), vanadium (V), arsenic (As), praseodymium (Pr), antimony (Sb) or phosphorus (P), amino compounds, halide compounds , Alkyl compounds, and metal alkoxides.

The amino compound may be Hf (NCH ₃ CH ₃ ) ₄ , Hf (NCH ₃ C ₂ H ₅ ) ₄ , Hf (NC ₂ H ₅ C ₂ H ₅ ) ₄ , Hf (NCH ₃ C ₃ H ₇ ) ₄ , Hf (NC ₂ H ₅ C ₃ H ₇ ) 4, or Hf (NC ₃ H ₇ C ₃ H ₇ ) ₄ .

With the halide compound is _{AlCl 3, GaCl, GaCl 3,} GaBr, GaI, InCl, InCl 3, SiCl 4, Si 2 Cl 6, GeCl 4, SnCl 4, SbCl 4, TiCl 4, TiI 4, ZrCl 4, ZrI 4 _{, HfCl 4, NbCl 5, TaCl} 5, TaI 5, MoCl 5, there may be mentioned the _{WOxFy, WF 6, MnCl 2,} MnI 2, CuCl, ZnCl 2, CdCl ₂ or example.

The alkyl compound may be Al (CH ₃ ) ₃ , Al (CH ₃ ) ₂ Cl, Al (CH ₃ ) ₂ H, Al (C ₂ H ₅ ) ₃ , Al (CH ₂ CH ₂ (CH ₃ ) ₂ ) ₃ , Ga (CH ₃ ) ₃ , Ga (CH ₃ ) ₂ (C ₂ H ₅ ), Ga (C ₂ H ₅ ) ₃ , Ga (C ₂ H ₅ ) ₂ Cl, Ga (CH ₂ CH ₂ (CH ₃ ) ₂ ) ₃ , Ga (CH ₂ C (CH ₃ ) ₃ ) ₃ , In (CH ₃ ) ₃ , ((CH ₃ ) ₂ (C ₂ H ₅ ) N) In (CH ₃ ) ₃ , In (CH ₃ ) ₂ Cl, In (CH ₃ ) ₂ (C ₂ H ₅ ), In (C ₂ H ₅ ) ₃ , Sn (CH ₃ ) ₄ , Sn (C ₂ H ₅ ) ₄ , Zn (CH ₃ ) ₂ , Zn ( C ₂ H ₅ ) ₂ , Cd (CH ₃ ) ₂ , or Hg (CH ₃ ) ₂ may be exemplified.

In addition, the metal alkoxide may be a group 3 such as alkoxide, boron (B), aluminium (Al) to lanthanum (La), etc. of a group 2 metal element such as magnesium (Mg), calcium (Ca) to strontium (Sr), or the like. Alkoxides of Group 4 metal elements such as alkoxides of metal elements, titanium (Ti), zirconium (Zr), hafnium (Hf), silicon (Si), germanium (Ge), tin (Sn) to lead (Pb), or vanadium And alkoxides of Group 5 metal elements such as (V), niobium (Nb), tantalum (Ta), phosphorus (P), arsenic (As) to antimony (Sb), and the like. Preferably, the first reactant 3 comprises an alkoxide of the Group 4 metal element described above.

Meanwhile, examples of the magnesium (Mg) alkoxide include Mg [OC ₂ H ₄ OCH ₃ ] ₂ , and examples of the calcium (Ca) alkoxide include Ca [OC ₂ H ₄ OCH ₃ ] ₂ . An example of tronium (Sr) alkoxide includes Sr [OC ₂ H ₄ OCH ₃ ] ₂ .

In addition, examples of the boron (B) alkoxide include B [OCH ₃ ] ₃ , B [OC ₂ H ₅ ] ₃ , B [OC ₃ H ₇ ] _3, B [OC ₄ H ₉ ] ₃ , and the like. Examples of aluminum (Al) alkoxides include Al [OC ₄ H ₈ OCH ₃ ] ₃ , Al [OCH ₃ ] ₃ , Al [OC ₂ H ₅ ] ₃ , Al [OC ₃ H ₇ ] ₃ or Al [OC ₄ H ₉ ] ₃ and the like. Examples of the lanthanum (La) alkoxide include La [OC ₂ H ₄ OCH ₃ ] ₃ or La (OC ₃ H ₇ CH ₂ OC ₃ H ₇ ] ₃ .

In addition, examples of the titanium (Ti) alkoxide include Ti [OCH ₃ ] ₄ , Ti [OC ₂ H ₅ ] ₄ , Ti [OC ₃ H ₇ ] ₄ , Ti [OC ₄ H ₉ ] ₄ to Ti [OC ₂ H ₅ ] ₂ [OC ₂ H ₄ N (CH ₃ ) ₂ ] ₂ and the like, examples of the zirconium (Zr) alkoxide include Zr [OC ₃ H ₇ ] ₄ , Zr [OC ₄ H ₉ ] ₄ or Zr [OC ₄ H ₈ OCH ₃ ] ] 4 and the like.

In addition, examples of the hafnium alkoxide include Hf (OtBu) ₄ (tetra tert-butoxy hafnium), Hf (mmp) ₄ (Tetrakis- (mmp) hafnium), Hf (OtBu) ₂ (dmae) ₂ , Hf (OtBu ) ₂ (mmp) ₂ , Tetrakis (triethylsiloxy) Hafnium, Hf (OEt) ₄ , Hf (OiPr) ₄ , Hf (OnBu) ₄ (tetra n-butoxy Hafnium), Hf (OtAm) ₄ , Hf (OPr) ₃ , Hf (OBu) ₄ can be illustrated. Here, dmae represents dimethyaminoethoxide (-OC ₂ H ₄ N (CH ₃ ) ₂ , mmp represents 1-methoxy-2-methyl-2-propoxy (-OC ₄ H ₈ OCH ₃ ). .

More specifically, Hf (OtBu) ₄ is Hf [OC4H9] ₄ , Hf (mmp) ₄ is Hf [OC ₄ H ₈ OCH ₃ ] ₄ , Hf (OtBu) ₂ (dmae) ₂ is Hf [OC ₄ H ₉ ] ₂ [OC ₂ H ₄ N (CH ₃ ) ₂ ] ₂ , Hf (OtBu) ₂ (mmp) ₂ is Hf [OC ₄ H ₉ ] ₂ [OC ₄ H ₈ OCH ₃ ] ₂ , Tetrakis (triethylsiloxy) Hafnium is Hf [OSi (C ₂ H ₅ ) ₃ ] ₄ , Hf (OEt) ₄ is Hf [OC ₂ H ₅ ] ₄ , Hf (OiPr) ₄ is Hf [OC ₃ H ₇ ] ₄ , Hf (OnBu) ₄ is Hf [ OC ₄ H ₉ ] ₉ and Hf (OtAm) ₄ represent Hf [OC ₅ H ₁₁ ] 4, respectively.

Examples of the silicon (Si) alkoxide include Si [OCH ₃ ] ₄ , Si [OC ₂ H ₅ ] ₄ , Si [OC ₃ H ₇ ] ₄ , Si [OC ₄ H ₉ ] ₄ , HSi [OCH ₃ ] ₃ , HSi [OC ₂ H ₅ ] ₃ , Si [OCH ₃ ] ₃ F, Si [OC ₂ H ₅ ] ₃ F, Si [OC ₃ H ₇ ] ₃ F to Si [OC ₄ H ₉ ] 3 _F , and the like. Examples of the germanium (Ge) alkoxide include Ge [OCH ₃ ] ₄ , Ge [OC ₂ H ₅ ] ₄ , Ge [OC ₃ H ₇ ] _4, Ge [OC ₄ H ₉ ] ₄ , and the like.

Examples of the tin (Sn) alkoxide include Sn [OC ₄ H ₉ ] _4, Sn [OC ₃ H ₇ ] ₃ [C ₄ H ₉ ], and the like. Examples of the lead (Pb) alkoxide include Pb [OC ₄ H]. ₉ ] ₄ or Pb ₄ O [OC ₄ H ₉ ] ₆ and the like.

Examples of the vanadium (V) alkoxide include VO [OC ₂ H ₅ ] ₃ or VO [OC ₃ H ₇ ] _3. Examples of the niobium (Nb) alkoxide include Nb [OCH ₃ ] ₅ and Nb [OC _2. H ₅ ] ₅ , Nb [OC ₃ H ₇ ] ₅ , Nb [OC ₄ H ₉ ] ₅ , and the like, and examples of the tantalum (Ta) alkoxide include Ta [OCH ₃ ] ₅ and Ta [OC ₂ H ₅ ] ₅ , Ta [OC ₃ H ₇ ] ₅ , Ta [OC ₄ H ₉ ] ₅ , Ta (OC ₂ H ₅ ) ₅ , Ta (OC ₂ H ₅ ) ₅ [OC ₂ H ₄ N (CH ₃ ) ₂ ] or Ta [OC ₂ H ₅ ] ₄ [CH ₃ COCHCOCH ₃ ], and the like.

Examples of the phosphorus (P) alkoxide include P [OCH ₃ ] ₃ , P [OC ₂ H ₅ ] ₃ , P [OC ₃ H ₇ ] ₃ , P [OC ₄ H ₉ ] ₃ , PO [OCH ₃ ] ₃ , PO [OC ₂ H ₅ ] ₃ , PO [OC ₃ H ₇ ] ₃ or PO [OC ₄ H ₉ ] ₃ , and the like. Examples of the arsenic (As) alkoxide include As [OCH ₃ ] ₃ and As [OC _2. H ₅ ] ₃ , As [OC ₃ H ₇ ] ₃ to As [OC ₄ H ₉ ] ₃ , and the like, and examples of the antimony (Sb) alkoxide include Sb [OC ₂ H ₅ ] ₃ and Sb [OC ₃ H ₇ ] ₃ or Sb [OC ₄ H ₉ ] ₃ .

In the present embodiment, the material or thin film formed on the substrate 10 using the first reactant 3 having the above-described composition may be an insulating material or an insulating thin film. Such an insulating material or insulating thin film may be, for example, HfO ₂ , Ta ₂ O ₅ , Al ₂ O ₃ , SiO ₂ , La ₂ O ₃ , Y ₂ O ₃ , ZrO ₂ , MgO, SrO, PbO, TiO ₂ , Nb _{2 O 5, CeO 2, SrTiO} 3, PbTiO 3, SrRuO 3, (Ba, Sr) TiO 3, Pb (Zr, Ti) O 3, (Pb, La) (Zr, Ti) O 3, (Sr, Ca RuO ₃ , In ₂ O ₃ , RuO ₂ , B ₂ O ₃ , GeO ₂ , SnO ₂ , PbO ₂ , Pb ₃ O ₄ , V ₂ O ₃ , As ₂ O ₅ , As ₂ O ₃ , Pr ₂ O ₃ , Sb ₂ O ₃ , Sb ₂ O ₅ , CaO, P ₂ O _5, Si ₃ N ₄ , AlON, SiON, AlN or a compound thereof.

3, 4A, and 4B, the first reactant 3 including the first element, the amino group, and the like 2 is chemisorbed onto the substrate 10 (step S11), and then the substrate ( 10) A first purge gas is introduced into the phase and a first purging step is performed to remove unreacted compounds remaining on the substrate 10 and the first reactant 3 (step S12).

Specifically, while introducing the first reactant 3 onto the substrate 10, a first portion of the first reactant 20 is chemisorbed onto the substrate 10 to allow the surface of the substrate 10 to be adsorbed. The first layer 4 is formed on it. At this time, since the second layer 5, which is the second part of the first reactant 3, is physically adsorbed on the first part, the second layer 5 is formed of the substrate Loosely bonded to the first layer 4 chemisorbed onto (10). Subsequently, the first purging or vacuum is performed using an inert gas such as argon (Ar), helium (He), neon (Ne), or nitrogen (N ₂ ) as the first purge gas. Purge. During this first purging step, the second layer 5 of unreacted first reactant 3 is removed from the reactor, whereby the first reactant 3 of the first reactant 3 that is not damaged on the substrate 1 is removed. The first layer 4, which is a chemisorbed layer, remains.

3 and 4c, a second reactant 6 including a second element capable of bonding with the first element 1 of the first reactant 3 inside the reactor in which the substrate 10 is located ) Is chemically reacted with the first reactant 3 formed on the substrate 10. As a result, a material 8 formed by chemical bonding between the first element 1 of the first reactant 3 and the second element of the second reactant 6 is formed on the substrate 10 (step S13). This will be described in more detail as follows.

When the second reactant 6 is introduced into the reactor, the first reactant 3 and the second reactant 6 chemically adsorbed on the substrate 10 are chemically reacted to form an atomic layer unit on the surface of the substrate 10. Furnace material 8 is formed. That is, on the substrate 10, oxygen of the first element 1 of the first reactant 3 and the oxygen of the second reactant 6 react to form an atomic layer unit 8, for example, a metal oxide film. . In this case, the second reactant 6 is 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ , It may include at least one or more of N ₂ or a compound that is activated in a manner using a plasma (remote plasma), a remote plasma (remote plasma) or ultraviolet (UV).

In the case of forming an insulating material containing oxygen on the substrate 10, a compound including oxygen also is used as the second reactant 6, and an insulating material containing nitrogen is formed on the substrate 10. In this case, it is preferable that the second reactant 6 also use a compound containing nitrogen.

 3 and 4D, the second reactant 6 which is not chemically reacted by secondary purging or vacuum purging the reactor in which the substrate 10 is located using an inert gas such as argon or nitrogen as the second purge gas (6). ) Is removed from the reactor (step S14).

Referring to FIG. 4E, adsorbing the first reactant 3 on the substrate 10 (S11), first purging the first reactant 3 (S12), and the second reactant 6. Is repeatedly adsorbed to the first reactant 2 (S13) and the second purging step (S14) of the second reactant 6 two or more times, thereby effectively flushing the substrate 1. The material layer 9 can be appropriately formed to a thickness that can be implemented.

In addition, when the above-described steps are repeated, the composition of the first reactant 3 and the second reactant 6 may be different to form the material layer 9 made of a composite on the substrate 10.

In the present embodiment, it is preferable that the material layer 9 formed on the substrate 10 has a thickness of about 5 to 30 mm 3. With respect to the subsequent flushing step, when a material layer 9 having a thickness of less than about 5 mm 3 is formed, the number of iterations of the flushing step with respect to the thickness of the final material layer 9 to be obtained is increased so that the semiconductor fabrication is performed. The overall economics of the process fall. On the other hand, if the thickness of the material layer 9 exceeds about 30 kPa, the flushing time should be increased, and it becomes difficult to secure a uniform flushing effect over the entire material layer 9.

3 and 4F, the first flushing gas is applied to the material layer 9 formed on the substrate 10 to improve characteristics of the material layer 9 (S15). The first flushing gas may include any one or more of 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH _3, or N ₂ . Preferably, the first flushing gas is 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ or N activated using plasma, remote plasma or ultraviolet (UV) light. _It contains any one or more of _two . In this case, the first flushing gas is selected from the same kind of materials as the second reactant 6 described above, but it is not necessary to use a material having the same composition in one embodiment. That is, the second both as a reactant and the first flush gas, but can use the O ₂ plasma, the second reactant is using O ₂ plasma and the first flushing gas, it is also possible to use H ₂ O.

Improving the characteristics of the material layer 9 by using the first flushing gas is performed at a temperature of about 200 to 400 ℃. In this case, since the reactivity between the first flushing gas and the material layer 9 increases at a high reaction temperature, the flushing step of the material layer 9 should be performed at a temperature of at least about 200 ° C. or higher, but the temperature is about 400 If it exceeds C, the crystallization of the material 8 of the material layer 9 proceeds, resulting in a problem of an increase in leakage current. In addition, this flushing step may vary depending on the thickness of the material layer 9 to be flushed, but is generally performed for about 1 to 10 minutes. If the flushing step is performed for less than about 1 minute, the film quality improvement effect of the material layer 9 is not sufficient, and if the flushing step is performed for a long time for more than about 10 minutes, the material layer 9 is not economically desirable. This is because it may lead to deterioration of the membrane quality.

In this embodiment, the carbon in the material 8 is carbon dioxide (CO ₂ ) while suppressing crystallization of the material 8 by supplying an oxidant to the material layer 9 by performing a flushing step at a relatively low temperature as described above. While eliminating in form, oxygen deficiency in the material 8 can be eliminated. As a result, leakage current of the material layer 9 can be suppressed through this flushing step.

FIG. 5 is a timing chart illustrating a method of forming a material shown in FIG. 3.

3 and 5, step I-1 is a conventional atomic layer deposition step, wherein the first reactant, the first purge gas, the second reactant, and the second purge gas are repeatedly supplied to the substrate. To form a material having a thickness of. Forming such a material corresponds to repeating the steps S11 to S14 in the flowchart shown in FIG. In this case, the composite material may be formed on the substrate by changing the composition of the first reactant and the second reactant at every repetition cycle of steps S11 to S14.

In step II-1 of FIG. 5, the first flushing gas is introduced onto the material formed on the substrate to improve the properties of the material. This step corresponds to step S15 of the flowchart shown in FIG. By repeatedly performing steps I-1 and II-2 as a whole, a material having a required thickness can be grown on a substrate, and a material having excellent leakage current control characteristics can be formed. In this case, when the steps I-1 and II-2 are repeatedly performed, the time required for one time execution of the steps I-1 and II-2 may be kept constant. However, when the steps I-1 and II-2 are repeatedly performed, the one execution time of the step I-1 is increased every time the number of repetitions is increased, and the flushing time of the step II-2 can be kept constant. have. In addition, when the steps I-1 and II-2 are repeatedly performed, the one-time execution time of the step I-1 is kept constant even if the number of repetitions is increased, and the flushing time of the step II-2 is gradually increased. It may be. According to this, the deposition time or the flushing time of the material or thin film can be reduced to form a material or thin film of a desired thickness in a short time.

6 is a flowchart illustrating a method of forming a material using an atomic layer deposition process according to another embodiment of the present invention.

As shown in FIG. 6, in this embodiment, the adsorption step (S21) of the first reactant, the first purging step (S22), the adsorption step (S23) of the second reactant, the second purging step (S24), Since the step S25 of applying the first flushing gas is substantially the same as in the above-described embodiment, detailed descriptions of these steps will be omitted.

In the present embodiment, after the first flushing gas application step S25, a third purging step S26 using a third purge gas may be introduced to enhance the residue removal effect. At this time, the third purge gas used in the third purging step S26 may include, for example, an inert gas such as argon or nitrogen.

FIG. 7 is a timing chart illustrating a method of forming a material shown in FIG. 6.

6 and 7, the step I-1 is a conventional atomic layer deposition step, wherein the first reactant, the first purge gas, the second reactant and the second purge gas are repeatedly supplied onto the substrate. A material having a predetermined thickness is formed on the substrate. These steps correspond to repeating the steps S21 to S24 shown in FIG. 6, respectively. In this case, the composite material may be formed on the substrate by varying the composition of the first reactant and the second reactant at every repetition period of the entire steps S21, S22, S23, and S24.

As shown in FIG. 7, in step II-2, the first purging gas is introduced into the material formed on the substrate to improve the properties of the material, and then the third purge gas onto the material to improve the residue removal effect. Is introduced to remove unreacted compound. These steps correspond to the steps S25 and S26 shown in FIG. 6, respectively. By repeatedly performing steps I-1 and II-2 as a whole, a material having excellent leakage current control characteristics can be formed on a substrate to a predetermined thickness.

8 is a flowchart illustrating a method of forming a material using an atomic layer deposition process according to another embodiment of the present invention.

Referring to FIG. 8, in the present embodiment, the adsorption step S31 of the first reactant, the first purging step S32, the adsorption step S33 of the second reactant, the second purging step S34, and The application step S35 and the like of one flushing gas are substantially the same as in the above-described embodiment.

According to the present embodiment, after the application step S35 of the first flushing gas, a second flushing gas is introduced onto the material to further improve the flushing effect. In the present embodiment, since the composition of the first flushing gas and the second flushing gas may be different, a combination of a flushing gas particularly suitable for the composite material may be used when forming the composite material on the substrate. That is, when the oxide film and the nitride film are formed on the substrate, a compound containing oxygen may be used as the first flushing gas, and a compound containing nitrogen may be used as the second flushing gas.

FIG. 9 is a timing chart illustrating a method of forming a material shown in FIG. 8.

8 and 9, step I-1 is a step of performing an atomic layer deposition method, wherein the first reactant, the first purge gas, the second reactant, and the second purge gas are repeatedly supplied to the substrate. To form the material in a predetermined thickness. These steps shown in FIG. 9 correspond to repeating steps S31 to S34 shown in FIG. 8, respectively. In this case, the material including the composite may be formed on the substrate by changing the composition of the first reactant and the second reactant at every repetition period of the steps S31, S32, S33, and S34.

In FIG. 9, in step II-3, the first flushing gas is introduced to first improve the properties of the material, and then the second flushing gas is introduced to improve the properties of the material secondly. The step II-3 is particularly preferable when the composite material is formed on the substrate in step I-1. For example, when a composite film including an oxide film and a nitride film is formed on the substrate, the first flushing gas may be O ₃ , H ₂ 0, N ₂ 0 or activated by plasma, remote plasma, or ultraviolet light containing oxygen. CO ₂ is used, and as the second flushing gas, it is preferable to use N ₂ O, NH ₃ or N ₂ activated by a plasma containing nitrogen, a remote plasma or ultraviolet rays. As shown in FIG. 9, by repeatedly performing steps I-1 and II-3 as a whole, a material or a composite material having excellent leakage current control characteristics may be formed on the substrate.

10 is a flowchart illustrating a method of forming a material using an atomic layer deposition process according to another embodiment of the present invention.

Referring to FIG. 10, in the present embodiment, the adsorption step S41 of the first reactant, the first purging step S42, the adsorption step S43 of the second reactant, the second purging step S44, and the first The application step S45 of the one flushing gas is substantially the same as the above-described embodiments.

In the present embodiment, the residue by further performing the third purging step (S46), the second application step (S47) and the fourth purging step (S48) after the application step (S45) of the first flushing gas. Maximize the removal effect and the improvement of membrane quality. According to the present embodiment, since the composition of the first flushing gas and the second flushing gas may be different, a combination of first and second flushing gases suitable for the composite material may be used when forming the composite material on the substrate. Can be.

FIG. 11 is a timing chart for explaining a method of forming a material shown in FIG. 10.

10 and 11, step I-1 is a conventional atomic layer deposition step in which a first reactant, a first purge gas, a second reactant, and a second purge gas are repeatedly supplied onto a substrate. A material having a predetermined thickness is formed on the phase. These steps in FIG. 11 correspond to repeating steps S41 to S44 shown in FIG. 10, respectively. In this case, the composite material may be formed on the substrate by differentiating the first reactant and the second reactant at every repetition period of the entire steps S41, S42, S43, and S44.

In FIG. 11, in step II-4, the first flushing gas is introduced (S45) to improve characteristics of the material formed on the substrate, and the third purge gas is introduced to perform tertiary purging (S46). Subsequently, after introducing the second flushing gas (S47) to improve the properties of the material, finally, the fourth purge gas is introduced to perform the fourth purging (S48) to maximize the residue removal effect. In the present embodiment, the step II-4 is particularly preferable when the composite material is formed on the substrate in the step I-1. For example, when a composite film including an oxide film and a nitride film is formed on the substrate, the first flushing gas may be O ₃ , H ₂ 0, N ₂ 0 or activated by plasma containing oxygen, remote plasma, or ultraviolet light. CO ₂ may be used, and N ₂ O, NH _3, or N ₂ activated with a plasma containing nitrogen, a remote plasma, or ultraviolet rays may be used as the second flushing gas. In addition, various modifications are possible. That is, by changing the order of purging gas, the purging gas containing nitrogen may be added first, and the purging gas containing oxygen may be added. The third purging may be omitted, and the first flushing gas containing oxygen and the second flushing gas containing nitrogen may be introduced at the same time. In addition, first a first flushing gas containing oxygen is first introduced, followed by a mixed gas of a first flushing gas containing oxygen and a second flushing gas containing nitrogen, and then a second flushing containing nitrogen. It is also possible to inject gas. In addition, if necessary, one step of the third purging (S46) or the fourth purging (S48) can be omitted. By repeatedly performing steps I-1 and II-4, a material or a composite material having excellent leakage current control characteristics and excellent removal of residues can be formed on the substrate.

 Hereinafter, a method of forming a thin film on a substrate using the above-described material forming method will be described in detail with reference to the accompanying drawings.

12 is a flowchart illustrating a thin film formation method according to an embodiment of the present invention.

Referring to FIG. 12, first, a substrate is placed in a reactor (S110). Subsequently, a first reactant is introduced onto the substrate to partially chemisorb the first reactant onto the substrate (step S120). Subsequently, the first purge gas is purged first (S130) to remove residues that are not chemisorbed. Subsequently, a second reactant is introduced into the reactor to chemically react the chemisorbed first reactant with the second reactant to form a thin film on the substrate (step S140). Subsequently, the second purge gas is purged with the second purge gas (S160) to remove the non-chemosorbed material.

Repeating the above steps as necessary to grow a thin film on the substrate to a thickness suitable for flushing, and then applying a first flushing gas containing a second element to the reactor to the thin film to improve the characteristics of the thin film (step S160). In this case, the first flushing gas includes at least one of 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH _3, or N ₂ . Preferably, the first flushing gas is at least one of 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ or N ₂ activated using plasma, remote plasma or ultraviolet light. It includes one or more. In addition, a material having the same composition as the second reactant may be used as the first flushing gas.

Applying the first flushing gas to the thin film formed on the substrate to improve the characteristics of the thin film is performed at a temperature of about 200 to about 400 ℃. At this time, since the reactivity increases at a high reaction temperature, the flushing step should be performed at a temperature of at least about 200 ° C. However, when the flushing step is performed at a temperature exceeding about 400 ° C., the crystallization of the material constituting the thin film proceeds, resulting in a problem of increased leakage current. In addition, the flushing step of the thin film depends on the thickness of the thin film to be flushed, but preferably for about 1 to 10 minutes. When the flushing step is performed in less than about 1 minute, the film quality improvement effect of the thin film is not sufficient, whereas if the flushing step is performed for a long time exceeding about 10 minutes, it is not economically desirable, This can lead to deterioration.

As described above, after the thin film is formed on the substrate, the third purging step, the application of the second flushing gas, and the fourth purging step may be further performed according to the material formation method using the atomic layer deposition process.

In detail, after applying the first flushing gas to the thin film formed on the substrate, the second flushing gas including the second element may be applied to the thin film to further improve the material properties. . In addition, after applying the second flushing gas to the thin film, the fourth purge gas may be further introduced by introducing a fourth purge gas. Furthermore, after applying the first flushing gas to the thin film, a third purging gas may be introduced to third purge the non-chemically adsorbed material, thereby improving the residue removal effect.

In the present embodiment, the carbon to an oxidizing agent through the flushing phase of the cold from the material constituting the other hand films that by feeding in the material constituting the thin film, inhibiting the crystallization of the material constituting the thin film CO ₂ type, as described above The oxygen deficiency phenomenon in the material constituting the thin film can be eliminated. Thereby, leakage current generation of the thin film formed on the board | substrate can be suppressed.

13A to 13F illustrate cross-sectional views for describing the method of forming the thin film of FIG. 12.

12 and 13A, the substrate 10 is placed in a reactor (not shown) (step S110). In this case, the substrate 10 may be, for example, a conventional silicon wafer, and the silicon wafer may include lower structures on which various active devices are formed. Also, the reactor is preferably an atomic layer deposition (ALD) reactor, and the substrate 10 is introduced into the reactor by a substrate transfer device such as a robot arm.

Referring to FIG. 13B, after the substrate 10 is positioned in the reactor, a nitride film 20 such as a thermal nitride film or a plasma nitride film is selectively formed on the substrate 10. When the nitride film 20 is formed on the substrate 10, it is possible to prevent the interfacial oxide film from growing during the subsequent process.

12 and 13C, in order to form a thin film on the substrate 10, a first reactant including a first element constituting the thin film is introduced into the reactor to partially deposit the first reactant. 10) and chemically adsorbed onto the phase (step S120), and then purged first with a first purge gas to remove the material that has not been chemisorbed (step S130). Subsequently, a second reactant including a second element bonded to the first element is introduced into the reactor to chemically react the first chemically adsorbed reactant with the second reactant (S140). Subsequently, the second thin film 30 including a chemical combination of the first reactant and the second reactant on the substrate 10 by introducing a second purge gas into the reactor and purging the second non-chemosorbed material. (Step S150).

The above-described steps are repeated two or more times to form the thin film 30 on the substrate 10 to a thickness of about 5 ~ 30Å. When the thickness of the thin film 30 is less than about 5 mm, the number of repetitions of the flushing step is excessively increased with respect to the thickness of the thin film 30 to be finally obtained, thereby reducing the economic efficiency of the overall thin film 30 forming process. On the other hand, when the thickness of the thin film 30 exceeds about 30 μs, the flushing time should be increased, and it becomes difficult to secure a uniform flushing effect to the inside of the thin film 30.

12 and 13D, by introducing a first flushing gas containing the second element into the reactor and applying it to the thin film 30 grown on the substrate 10, the thin film 30 is formed. The characteristics are improved to form the improved thin film 32 having the improved characteristics on the substrate 10 (step S160).

13E and 13F illustrate cross-sectional views illustrating the steps of increasing the thickness of the improved thin film 32 having improved properties by repeating the steps of FIGS. 13C and 13D, respectively.

As shown in FIGS. 13E and 13F, the steps of forming and improving the characteristics of the thin films 30 and 30 ′ are repeatedly performed two or more times to adjust the thickness of the improved thin films 32 and 32 ′. These steps are carried out at a temperature of about 200 to about 400 ° C. As the reaction temperature generally increases at higher reaction temperatures, the flushing step should be performed at a temperature of at least about 200 ° C or higher. However, when the temperature of the flushing step exceeds about 400 ° C, crystallization of the material constituting the improved thin films 32 and 32 'proceeds, leading to a problem of an increase in leakage current.

In the present embodiment, the first flushing gas is, for example, 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO _{2 when the} thin film 30, 30 ′ is an oxide film. Or combinations thereof, and when the improved thin films 32 and 32 'are nitride films, for example, N ₂ O, NH ₃ , N _3, or a combination thereof. In addition, the first flushing gas is preferably 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ , N ₂ or activated using plasma, remote plasma or ultraviolet light. Combinations thereof.

According to the present embodiment, by performing the flushing step (LOT) during the atomic layer deposition process, an improved thin film 32 'having excellent insulating properties can be formed on the substrate 10, and the improved thin film 32' can be formed. ) Has sufficient characteristics for use as a gate insulating film, a capacitor dielectric film, or the like.

Hereinafter, a method of manufacturing a capacitor of a semiconductor device using the aforementioned thin film forming method will be described in detail with reference to the accompanying drawings.

14 is a flowchart illustrating a method of manufacturing a capacitor according to the present invention.

Referring to FIG. 14, a substrate having a lower electrode formed thereon is positioned in a reactor (step S210). Subsequently, a first reactant including a first element constituting a dielectric material is introduced into the reactor to partially adsorb the first reactant on the lower electrode (step S220), and then a first purge gas into the reactor. To first purge the material that has not been chemisorbed (step S230).

Subsequently, a second reactant including a second element that combines with the first element is introduced into the reactor to chemically react the chemisorbed first reactant with the second reactant to form the first reactant on the lower electrode. After forming a dielectric material by chemical bonding of the element and the second element (step S240), a second purge gas is introduced into the reactor to secondary purge the unchemically adsorbed material (step S250).

Next, a first flushing gas containing a second element in the reactor is applied to the dielectric material to form a dielectric film having improved properties on the substrate (step S260). In this case, the first flushing gas includes at least one selected from 0 ₃ , O ₂ , H ₂ O, H ₂ O ₂ , N ₂ 0, CO ₂ , NH _3, or N ₂ . Preferably, the first flushing gas is any one of 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ or N ₂ activated using plasma, remote plasma or ultraviolet light. It includes one or more. In addition, the first flushing gas may include a material having the same composition as the aforementioned second reactant.

Applying the first flushing gas to the dielectric material to form a dielectric film having improved properties is performed at a temperature of about 200 to about 400 ℃. Generally, a higher reaction temperature leads to increased reactivity, so the flushing step is performed at a temperature of at least about 200 ° C or higher. However, when the temperature of the flushing step exceeds about 400 ° C., crystallization of the dielectric material proceeds to increase the leakage current of the dielectric film. In addition, the flushing step is changed depending on the thickness of the dielectric material to be flushed, but preferably about 1 minute to about 10 minutes. If the flushing step is performed in less than about 1 minute, the film quality improvement effect of the dielectric film is not sufficient, but if it proceeds for a relatively long time for more than about 10 minutes, it is not economically desirable and may lead to deterioration of the film quality. .

Thereafter, an upper electrode is formed on the dielectric film having improved characteristics according to a conventional capacitor manufacturing process (step S270) to complete the capacitor on the substrate.

Hereinafter, a method of manufacturing a capacitor according to an embodiment of the present invention will be described in more detail.

15A to 15E are cross-sectional views illustrating a method of manufacturing the capacitor shown in FIG. 14. However, the manufacturing method of the following capacitor is an illustration, The present invention is not limited by the following Example.

Referring to FIG. 15A, a gate dielectric layer 104, a gate electrode 110, and source / drain regions 116a and 116b may be formed on a semiconductor substrate 100 having an active region 101 defined by an isolation region 102. To form a transistor comprising a. In general, a semiconductor device of 1 gigabit or more requires a very thin gate dielectric film having a Toxeq of about 10 mW, and therefore, it is preferable to form the thin gate dielectric film 104 using an atomic layer deposition (ALD) process. That is, as shown in FIGS. 4A to 4E, for example, a semiconductor substrate is subjected to an atomic layer deposition (ALD) process using a metal alkoxide precursor and an activated oxidant such as O 3, plasma O 2, remote plasma O 2 or plasma N 2 O. A gate dielectric film 104 made of a metal oxide film is formed on the (100). Preferably, the HfO2 gate dielectric layer 104 is formed on the substrate 100 by an atomic layer deposition (ALD) process using Hf (OtBu) 4 and O3.

The gate electrode 110 may be formed of a polyside structure in which a polysilicon layer 106 doped with impurities and a metal silicide layer 108 are sequentially stacked. Capping insulating layers 112 and spacers 114 made of silicon oxide or silicon nitride are formed on the top and sidewalls of the gate electrode 110, respectively.

Referring to FIG. 15B, after the first insulating layer 118 made of oxide is formed on the entire surface of the semiconductor substrate 100 on which the transistors are formed, the first insulating layer 118 is etched by a photolithography process to form the source region ( A contact hole 120 is formed to partially expose 116a.

Subsequently, a first conductive layer, for example, a polysilicon layer doped with phosphorus (P), is deposited on the contact hole 120 and the first insulating layer 118, and then the surface of the first insulating layer 118 is formed. The first conductive layer is removed by an etch back process or a chemical mechanical polishing (CMP) process to form the contact plug 122 in the contact hole 120 until it is exposed.

Referring to FIG. 15C, an etch stop layer 123 is formed on the contact plug 122 and the first insulating layer 118. The etch stop layer 123 is formed of a material having a high etching selectivity with respect to the first insulating layer 118, for example, silicon nitride (SixNy) or silicon oxynitride (SiON).

After forming the second insulating layer 124 made of oxide on the etch stop layer 123, the opening 126 exposing the contact plug 122 is formed by etching the second insulating layer 124. In detail, the second insulating layer 124 is partially etched until the etch stop layer 123 is exposed, and then excessively etched for a predetermined time to partially expose the contact plug 122 and the first insulating layer 118. The opening 126 is formed. In this case, the opening portion 126 is formed with a predetermined sidewall slope so that the bottom portion is narrower than the upper mouth. This is because the etching rate at the bottom of the opening 126 is reduced by the loading effect when the etching process is performed.

Subsequently, a second conductive layer 127 is formed on the side and bottom surfaces of the opening 126 and the second insulating layer 124. The second conductive layer 127 may be formed of a semiconductor material such as polysilicon, a rare metal such as ruthenium (Ru), platinum (Pt) or iridium (Ir), titanium nitride (TiN), tantalum nitride (TaN), or tungsten nitride (WN). It is formed using a conductive metal nitride such as).

14 and 15D, after a sacrificial film (not shown) is formed on the second conductive film 127 and the opening 126, the second conductive film is formed only on the side and bottom of the opening 126. The top of the sacrificial film is removed by an etch back or chemical mechanical polishing process so that 127 remains. Accordingly, the second conductive layer 127 that has been deposited on the surface of the second insulating layer 124 is removed to separate the second conductive layer 127 deposited along the profile of the opening 126 in each cell unit. do.

Next, the sacrificial layer is removed by a wet etching process to form the lower electrode 128 of the capacitor in each cell region, and then the substrate on which the lower structure including the lower electrode 128 is formed is subjected to an atomic layer deposition (ALD) reactor. It is introduced in (S210).

Subsequently, as illustrated in FIGS. 4A to 4E, hafnium alkoxide precursors such as Hf (OtBu) ₄ , O ₃ , plasma O ₂ , remote plasma O ₂ to plasma N ₂ O, and the like are formed on the lower electrode 128. By depositing HfO ₂ by an atomic layer deposition (ALD) process using an activated oxidant, a dielectric film 130 of a capacitor is formed (S220 to S250). As described above, for example, by applying an atomic layer deposition (ALD) process using a metal alkoxide precursor and an activated oxidant, the top thickness and bottom on the bottom electrode 128 having a high aspect ratio of about 13: 1 or greater. It is possible to form the dielectric film 130 having excellent step coating property with a thickness ratio of about 1: 0.8 or more. In this case, the dielectric film 130 may be formed as a single film of HfO ₂ as described above, or may be formed as a composite film in which two or more metal oxide films are alternately stacked. For example, a dielectric film 130 having a stacked structure of Al ₂ O ₃ / HfO ₂ / Al ₂ O ₃ / HfO ₂ is formed on the lower electrode 128 while changing a metal precursor in an atomic layer deposition (ALD) process. can do.

Here, when the lower electrode 128 includes polysilicon, oxygen derived from an oxidant reacts with the silicon of the lower electrode 128 to oxidize the lower electrode 128 during the formation of the dielectric layer 130. . Therefore, before forming the dielectric layer 130, the lower electrode is nitrided by a rapid thermal nitriding (RTN) process or a plasma nitridation process under an atmosphere containing nitrogen gas. The oxidation of 128 can be prevented.

Referring to FIG. 15D, as described above, after forming the dielectric film 130 by an atomic layer deposition (ALD) process using a metal alkoxide precursor and an O ₃ oxidant, a film of the dielectric film 130 is introduced by introducing a first flushing gas. To improve (S260). The film quality improvement process of the dielectric film 130 is performed substantially the same as the above-described thin film formation method.

Referring to FIG. 15E, a capacitor C including a lower electrode 128, a dielectric layer 130, and an upper electrode 132 is formed by forming an upper electrode 132 of the capacitor C on the dielectric layer 130. To form (S270). In this case, the upper electrode 132 may be a semiconductor material such as polysilicon, a rare metal such as ruthenium (Ru), platinum (Pt) or iridium (Ir), or titanium nitride (TiN), tantalum nitride (TaN) to tungsten nitride ( It is formed using a conductive metal nitride such as WN). Preferably, the upper electrode 132 has a structure in which a titanium nitride (TiN) film and a polysilicon film are sequentially stacked. At this time, the titanium nitride (TiN) film is preferably formed at a temperature of about 550 ℃ or less in order to prevent degradation of the lower structure of the capacitor (C).

Meanwhile, a step of forming a conductive film (not shown) on the upper electrode 132 may be additionally performed. For example, a titanium nitride (TiN) thin film may be formed using the upper electrode 132, and then an additional conductive material may be deposited for a subsequent process of manufacturing a real semiconductor memory device. In this case, the conductive material may be n-type or p-type doped silicon, n-type or p-type silicon germanium (SixGey), or tungsten (W), tungsten nitride (WN) to aluminum nitride ( Metal or metal nitride such as AlN).

Hereinafter, the present invention will be described in more detail with reference to experimental and comparative examples.

Experimental Example

Formation of a thin film

A nitride film was formed on a cylindrical, phosphorus-doped polysilicon substrate by Rapid Thermal Nitridation (RTN).

Subsequently, Tetrakis Ethyl Methyl Amino Hafnium, a hafnium source, is introduced and chemically and physically adsorbed onto the substrate, and then physically adsorbed using nitrogen (N ₂ ) gas. ) The source was removed. Inflowing ozone (O ₃ ) gas and reacting with hafnium (Hf) to form a hafnium oxide (HfO ₂ ) film on the substrate, and then using the residual secondary reactant or ozone (O ₃ ) nitrogen (N ₂ ) gas To remove. The process was performed at about 300 ° C. in an atomic layer deposition (ALD) reactor and was repeated until a hafnium oxide (HfO ₂ ) thin film was formed on the substrate with a thickness of about 10 μs.

Thin film reforming-flushing process

Only ozone (O ₃ ) gas was introduced for about 5 minutes (Sample 1; test results in the examples unless otherwise indicated below means test results using Specimen 1) and for about 1 minute (Sample 2) The step of removing impurities such as carbon in the hafnium oxide (HfO ₂ ) thin film formed on the phase and preventing oxygen deficiency was performed. The hafnium oxide (HfO ₂ ) thin film was repeatedly deposited three times and the film quality improvement step was repeated three times to form a hafnium oxide (HfO ₂ ) thin film on the substrate.

Formation of superstructure

TiN ₄ and NH ₃ are used as a reactant and the reaction temperature is about 450 ° C. at low temperature to form a TiN film on the formed HfO ₂ thin film by atomic layer deposition (ALD), and SiH ₄ and GeH on the TiN film. SiGe capping film was formed in a single wafer type CVD apparatus using ₄ precursors and a reaction temperature of about 420 ° C. At this time, PH ₃ was doped when the SiGe capping layer was formed to form an activated dopant in the SiGe capping layer.

Comparative example

In addition, a comparative specimen was obtained by forming a thin film on the substrate in the same manner as described above except that the flushing process was not performed.

Comparison of Carbon Density in Thin Films

16 is a TOF-SIMS graph showing the density of carbon in a thin film.

As shown in FIG. 16, the carbon content in the specimen bivalent thin film of the Experimental Example in which the flushing was performed for 1 minute was relatively lower than that of the comparative example in which the flushing was not performed. It can be observed that almost all residual carbon is removed at the interface between the substrate and the substrate.

Comparison of Leakage Current Control Characteristics of Thin Films

17 is a graph showing leakage current control characteristics.

Specifically, FIG. 17 is a graph illustrating leakage current control characteristics after forming a thin film on a substrate according to the above Examples and Comparative Examples. As a result, the Toxeq value was about 20 dB. As shown in FIG. 17, it can be seen that the leakage current is remarkably improved in the dielectric film according to the present invention, while maintaining the equivalent Toxeq as compared with the dielectric film according to the comparative example. In the case of the experimental example at about 1.0V, the leakage current control effect was about 100 times higher than that of the comparative example. That is, in the case of the dielectric film according to the present invention, a capacitor having a Toxeq value of about 20 mA can be manufactured while maintaining a leakage current of femto A level per cell at about 1.0V.

Comparison of Degradation Degree of Thin Films by Heat Treatment

18 is a graph showing leakage current control characteristics of a heat treatment process subsequent to forming a dielectric film. That is, FIG. 18 is a graph showing changes in leakage current control characteristics of hafnium oxide films when the upper structure is formed on the hafnium oxide films (dielectric films) and various heat treatment processes performed thereafter are performed in the above Examples and Comparative Examples. to be.

Referring to FIG. 18, in the case of the dielectric film according to the embodiment, excellent leakage current control characteristics are maintained up to a temperature of about 500 ° C., but in the case of the dielectric film according to the comparative example, deterioration is rapidly performed at a temperature of about 450 ° C. It can be seen that the leakage current is greatly increased.

Relationship between Leakage Current and Toxeq

19 is a graph showing the relationship between leakage current and Toxeq according to the flushing time of the dielectric film according to the experimental example.

In general, as the flushing time increases, leakage current of the dielectric film increases while Toxeq decreases, so it is important to determine an optimal flushing time. Therefore, as shown in FIG. 19, it can be seen that about 5 minutes is the optimal flushing time in the case of the experimental example.

DRAM performance test

Fig. 20 is a graph showing leakage current control characteristics in a DRAM including a capacitor according to the embodiment.

Referring to FIG. 20, when the metal-insulating film-semiconductor (MIS) capacitor according to the above embodiment is integrated in an 80nm DRAM, excellent leakage current control characteristics are exhibited, in particular, a capacitance of about 31.5fF at 0.9V. It can be seen that the leakage current is very small.

According to the present invention, the carbon in the thin film can be effectively removed through the in-situ process, thereby significantly reducing the leakage current, and preventing the oxygen deficiency to form a thin film having excellent insulating properties on the substrate.

In addition, since the thin film characteristics are improved through a low temperature flushing step, it is possible to prevent crystallization and deterioration caused by the thin film due to heat treatment. In addition, such a thin film can be widely used, for example, as a gate oxide film or a capacitor dielectric film, and thus has a wide application range, and can be combined with a conventional atomic layer deposition process to form an ultra-thin and high-quality insulating film.

In particular, when the thin film according to the present invention is used as an insulating film of a semiconductor memory device, it is possible to use a relatively thin insulating film in order to obtain the same insulation effect, so that a high density memory device requiring a recent design rule of 1 μm or less is required. It can cope effectively with the manufacturing process. As a result, according to the present invention, it is possible to economically produce a high quality thin film and a reliable memory device using the same, thereby reducing the time and cost required for the overall semiconductor manufacturing process.

 Although the above has been described with reference to preferred embodiments of the present invention, those skilled in the art will variously modify and change the present invention without departing from the spirit and scope of the invention as set forth in the claims below. I can understand that you can.

Claims (64)

a) chemisorbing a first reactant comprising a first element onto the substrate; b) chemically reacting the chemically adsorbed first reactant with a second reactant comprising a second element that bonds with the first element to form a chemical bond between the first element and the second element on the substrate. Forming a material;  c) repeating steps a) and b) five or more times to form a material having a thickness of 5 to 30 mm on the substrate; And d) applying a flushing gas comprising the second element to the material to improve the properties of the material. The method of claim 1, wherein the first reactant is Hf, Ta, Al, Si, La, Y, Zr, Mg, Sr, Pb, Ti, Nb, Ce, Ru, Ba, Ca, In, Ge, Sn, V And a precursor compound comprising at least one selected from the group consisting of As, Pr, Sb, and P. The method of claim 1, wherein the first reactant is Hf (OtBu), Hf (mmp) ₄ , Hf (OtBu) ₂ (dmae) ₂ , Hf (OtBu) ₂ (mmp) ₂ , Tetrakis (triethylsiloxy) Hafnium, Hf ( OEt) ₄ , Hf (OiPr) ₄ , Hf (OnBu) ₄ , Hf (OtAm) ₄ , Hf (OPr) ₃ , and Hf (OBu) ₄ , at least one selected from the group consisting of Way. The method of claim 1, wherein the first reactant is Hf (NCH ₃ CH ₃ ) ₄ , Hf (NCH ₃ C ₂ H ₅ ) ₄ , Hf (NC ₂ H ₅ C ₂ H ₅ ) ₄ , Hf (NCH ₃ C ₃ H ₇ ) ₄ , Hf (NC ₂ H ₅ C ₃ H ₇ ) 4, and Hf (NC ₃ H ₇ C ₃ H ₇ ) ₄ . The method of claim 1 wherein the first reactant is _{AlCl 3, GaCl, GaCl 3,} GaBr, GaI, InCl, InCl 3, SiCl 4, Si 2 Cl 6, GeCl 4, SnCl 4, SbCl 4, TiCl 4, TiI 4 _{include, ZrCl 4, ZrI 4, HfCl} 4, NbCl 5, TaCl 5, TaI 5, MoCl 5, WOxFy, WF 6, MnCl 2, MnI 2, CuCl, ZnCl 2, and at least one selected from the group consisting of CdCl ₂ Method for forming a material, characterized in that. The method of claim 1, wherein the first reactant is Al (CH ₃ ) ₃ , Al (CH ₃ ) ₂ Cl, Al (CH ₃ ) ₂ H, Al (C ₂ H ₅ ) ₃ , Al (CH ₂ CH ₂ ( CH ₃ ) ₂ ) ₃ , Ga (CH ₃ ) ₃ , Ga (CH ₃ ) ₂ (C ₂ H ₅ ), Ga (C ₂ H ₅ ) ₃ , Ga (C ₂ H ₅ ) ₂ Cl, Ga (CH ₂ CH ₂ (CH ₃ ) ₂ ) ₃ , Ga (CH ₂ C (CH ₃ ) ₃ ) ₃ , In (CH ₃ ) ₃ , ((CH ₃ ) ₂ (C ₂ H ₅ ) N) In (CH ₃ ) ₃ , In (CH ₃ ) ₂ Cl, In (CH ₃ ) ₂ (C ₂ H ₅ ), In (C ₂ H ₅ ) ₃ , Sn (CH ₃ ) ₄ , Sn (C ₂ H ₅ ) ₄ , Zn (CH ₃ ) A method for forming a material comprising at least one selected from the group consisting of ₂ , Zn (C ₂ H ₅ ) ₂ , Cd (CH ₃ ) ₂ , and Hg (CH ₃ ) ₂ . The method of claim 1, wherein the second reactant comprises at least one selected from the group consisting of 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ and N ₂ . A substance formation method to make. The group of claim 1, wherein the second reactant is 0 ₃ , O ₂ , H ₂ O, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ and N ₂ activated with plasma, remote plasma or ultraviolet light. A method for forming a material, characterized in that it comprises at least one selected from. The method of claim 1 wherein the material is an insulating material. The method of claim 9, wherein the insulating material is HfO ₂ , Ta ₂ O ₅ , Al ₂ O ₃ , SiO ₂ , La ₂ O ₃ , Y ₂ O ₃ , ZrO ₂ , MgO, SrO, PbO, TiO ₂ , Nb _{2 O 5, CeO 2, SrTiO 3} , PbTiO 3, SrRuO 3, (Ba, Sr) TiO 3, Pb (Zr, Ti) O 3, (Pb, La) (Zr, Ti) O 3, (Sr, Ca) RuO ₃ , In ₂ O ₃ , RuO ₂ , B ₂ O ₃ , GeO ₂ , SnO ₂ , PbO ₂ , Pb ₃ O ₄ , V ₂ O ₃ , As ₂ O ₅ , As ₂ O ₃ , Pr ₂ O ₃ , Sb ₂ O ₃ , Sb ₂ O ₅ , CaO, P ₂ O _5, Si ₃ N ₄ , AlON, SiON and at least one selected from the group consisting of AlN. 2. The method of claim 1 wherein the material is an insulating thin film. The method of claim 11, wherein the insulating thin film is HfO ₂ , Ta ₂ O ₅ , Al ₂ O ₃ , SiO ₂ , La ₂ O ₃ , Y ₂ O ₃ , ZrO ₂ , MgO, SrO, PbO, TiO ₂ , Nb _{2 O 5, CeO 2, SrTiO 3} , PbTiO 3, SrRuO 3, (Ba, Sr) TiO 3, Pb (Zr, Ti) O 3, (Pb, La) (Zr, Ti) O 3, (Sr, Ca) RuO ₃ , In ₂ O ₃ , RuO ₂ , B ₂ O ₃ , GeO ₂ , SnO ₂ , PbO ₂ , Pb ₃ O ₄ , V ₂ O ₃ , As ₂ O ₅ , As ₂ O ₃ , Pr ₂ O ₃ , Sb ₂ O ₃ , Sb ₂ O ₅ , CaO, P ₂ O _5, Si ₃ N ₄ , AlON, SiON and at least one selected from the group consisting of AlN. The method of claim 1, wherein the flushing gas comprises at least one selected from the group consisting of 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ and N ₂ . Material formation method. The method of claim 1, wherein the flushing gas is from the group consisting of 0 ₃ , O ₂ , H ₂ O, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ and N ₂ activated by plasma, remote plasma or ultraviolet light. A method of forming a material comprising at least one selected. The method of claim 1, wherein the flushing gas is applied to the material at a temperature of 200 to 400 ° C. 3.  The method of claim 1, wherein the flushing gas is applied to the material for 1 to 10 minutes. The method of claim 1, further comprising, after chemisorbing the first reactant, purging the unreacted material by introducing a purge gas. 18. The method of claim 17, wherein the purge gas comprises argon (Ar), helium (He), neon (Ne), or nitrogen (N ₂ ). The method of claim 1, further comprising reacting the second reactant with the chemisorbed first reactant, followed by introducing a purge gas to purge and remove the unchemisorbed material. 2. The method of claim 1, further comprising, after applying the flushing gas to the material, purging the microchemically adsorbed material by introducing a purge gas. a) chemisorbing a first reactant having a first element comprising a transition element onto the substrate; b) chemically reacting the chemically adsorbed first reactant with a second reactant comprising a second element that bonds with the first element to form a chemical bond between the first element and the second element on the substrate. Forming a material; c) repeating steps a) and b) five or more times; And d) applying a flushing gas comprising the second element to the material to improve the properties of the material. 22. The method of claim 21 wherein the transition element is a Group 4 transition element. 22. The method of claim 21 wherein the first reactant comprises a precursor compound comprising the transition element. The method of claim 21, wherein the second reactant is 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ , N ₂ , plasma, remote plasma or ultraviolet activated 0 _3. , O ₂ , H ₂ O, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ and at least one selected from the group consisting of N ₂ . 22. The method of claim 21, wherein c) is performed by repeating steps a) and b) five or more times to form a material having a thickness of 5 to 30 mm on the substrate . The method of claim 21, wherein the flushing gas is 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ , N ₂ , plasma, remote plasma or ultraviolet activated 0 ₃ , _{O 2, H 2 0, H} 2 O 2, N 2 0, CO 2, materials forming method characterized in that it includes at least one selected from the group consisting of NH ₃ and N _2. 22. The method of claim 21 wherein the flushing gas is applied to the material at a temperature of 200 to 400 ° C.  22. The method of claim 21 wherein the flushing gas is applied to the material for 1 to 10 minutes. a) chemisorbing a first reactant comprising a first element onto the substrate; b) chemically reacting the chemically adsorbed first reactant with a second reactant comprising a second element that bonds with the first element to form a chemical bond between the first element and the second element on the substrate. Forming a material; c) applying a first flushing gas comprising the second element to the material to improve properties of the material; And d) applying a second flushing gas comprising the second element to the material to improve the properties of the material. 30. The method of claim 29 wherein the first flushing gas and the second flushing gas are different. 31. The method of claim 30, further comprising applying a mixed gas of the first flushing gas and the second flushing gas to the material after applying the first flushing gas to the material, wherein the second flushing gas comprises: Method for forming a material, characterized in that applied to the mixed gas applied material. The method of claim 30, wherein the first and second flushing gases are 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ , N ₂ , plasma, remote plasma or A material forming method comprising at least one selected from the group consisting of 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ and N ₂ activated by ultraviolet light. a) chemisorbing a first reactant comprising a first element onto the substrate; b) first purging the microchemically adsorbed material by introducing a first purge gas; c) chemically reacting the first reactant with the first element and the second reactant including a second element that bonds with the first element to form a chemical reaction between the first element and the second element on the substrate. Forming a material; d) introducing a second purge gas to secondary purge the microchemically adsorbed material; e) repeating steps a) to d) five or more times to form a material having a thickness of 5 to 30 mm on the substrate; And f) applying a flushing gas comprising the second element to the material to improve the properties of the material; g) introducing a third purge gas to third purge the microchemically adsorbed material. 34. The method of claim 33 wherein the second reactant and the flushing gas are the same. The method of claim 34, wherein the second reactant is 0 ₃ activated by 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ , N ₂ , plasma, remote plasma, or ultraviolet light. , O ₂ , H ₂ O, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ and at least one selected from the group consisting of N ₂ . 34. The method of claim 33 wherein the second reactant and the flushing gas are different. The method of claim 34, wherein the second reactant and the flushing gas are each 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ , N ₂ , plasma, remote plasma or ultraviolet light. Method of forming a material, characterized in that it comprises at least one selected from the group consisting of activated 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ and N ₂ . a) chemisorbing a first reactant comprising a first element onto the substrate; b) first purging the microchemically adsorbed material by introducing a first purge gas;  c) chemically reacting the first reactant with the first element and the second reactant including a second element that bonds with the first element to form a chemical reaction between the first element and the second element on the substrate. Forming a material; d) introducing a second purge gas to secondary purge the microchemically adsorbed material; e) repeating steps a) to d) to form a material having a thickness of 5 to 30 microns on the substrate; f) applying a first flushing gas comprising the second element to the material to improve properties of the material; g) further improving the properties by applying a second flushing gas comprising the second element to the material having improved properties; And h) introducing a third purge gas to third purge the microchemically adsorbed material. 39. The method of claim 38 wherein the first flushing gas and the second flushing gas are different from each other. 39. The method of claim 38, wherein the first flushing gas and the second flushing gas are 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ , N ₂ , plasma, remote plasma or Method for forming a material, characterized in that it comprises at least one selected from the group consisting of 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ and N ₂ activated by ultraviolet light. 39. The method of claim 38 wherein the second reactant is different from the first flushing gas and the second flushing gas. The method of claim 41, wherein the second reactant is 0 ₃ activated by 0 ₃ , O ₂ , H ₂ 0, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ , N ₂ , plasma, remote plasma, or ultraviolet light. , O ₂ , H ₂ O, H ₂ O ₂ , N ₂ 0, CO ₂ , NH ₃ and at least one selected from the group consisting of N ₂ . a) positioning the substrate in the reactor; b) introducing a first reactant comprising a first element into the reactor to chemisorb a portion of the first reactant onto the substrate; c) first purging the microchemically adsorbed material by introducing a first purge gas into the reactor; d) introducing a second reactant including a second element that combines with the first element into the reactor to chemically react the chemisorbed first reactant with the second reactant to form a thin film on the substrate ; e) introducing a second purge gas into the reactor to secondary purge the microchemically adsorbed material; f) repeating steps b) to e) five or more times to form a thin film of 5 to 30 microns on the substrate; And g) applying a first flushing gas comprising a second element in the reactor to the thin film to improve the properties of the thin film. 45. The method of claim 43, wherein the steps b) to g) are repeated two or more times to adjust the thickness of the thin film. 45. The method of claim 44, wherein as the number of steps b) to g) is repeated, the thickness of the thin film formed by one step of steps b) to f) increases, The thin film forming method of claim 1, wherein the first application time of the flushing gas is constant. 45. The method of claim 44, wherein as the number of steps b) to g) is repeated, the thickness of the thin film formed by one step of steps b) to f) is constant, The thin film forming method of claim 1, wherein the application time of the first flushing gas is increased. 44. The method of claim 43 wherein said thin film is a gate insulating film. 44. The method of claim 43 wherein the thin film is a capacitor dielectric film. 45. The method of claim 43, further comprising forming a thermonitride film or plasma nitride film on the substrate after placing the substrate in the reactor, wherein a portion of the first reactant is chemisorbed on the thermonitride film or plasma nitride film. Thin film formation method characterized in that. 45. The method of claim 43, further comprising: after applying the first flushing gas to the thin film, introducing a third purge gas to third purge the unchemically adsorbed material. 45. The method of claim 43, further comprising applying the first flushing gas to the thin film, and then applying a second flushing gas containing the second element to the thin film to improve characteristics of the thin film. Thin film formation method. 52. The method of claim 51, further comprising applying a third purge gas to the third thin film and then purging the third chemically adsorbed material by third purging gas. 52. The method of claim 51, further comprising: after applying the second flushing gas to the thin film, introducing a fourth purge gas to fourth purge the unchemically adsorbed material. a) positioning the substrate in which the lower electrode is formed in the reactor; b) introducing a first reactant comprising a first element into the reactor to chemisorb a portion of the first reactant onto the lower electrode; c) first purging the microchemically adsorbed material by introducing a first purge gas into the reactor; d) introducing a second reactant including a second element that combines with the first element into the reactor to chemically react the chemisorbed first reactant with the second reactant to form the first element on the lower electrode; Forming an insulating material by chemical bonding of the second element; e) introducing a second purge gas into the reactor to secondary purge the microchemically adsorbed material; f) introducing a first flushing gas containing a second element into the reactor and applying it to the insulating material to form an insulating film having improved properties on the lower electrode; And g) forming a top electrode on the insulating film having improved characteristics. 55. The method of claim 54, wherein the lower electrode and the upper electrode each comprise at least one conductive material selected from the group consisting of metals, metal oxides, metal nitrides, metal oxynitrides, and conductive silicon. 55. The method of claim 54, further comprising forming a thermonitride film or plasma nitride film on the lower electrode after placing the substrate in the reactor, wherein a portion of the first reactant is chemically deposited on the thermonitride film or plasma nitride film. Method for producing a capacitor, characterized in that the adsorption. 55. The method of claim 54, wherein the steps b) to e) are repeated five times or more to form an insulating film of 5 to 30 microns. 58. The method of claim 57, wherein the thickness of the insulating film is adjusted by repeating steps b) to f) two or more times. 55. The method of claim 54, further comprising forming a conductive film on the upper electrode. 60. The method of claim 59, wherein the conductive film comprises at least one selected from the group consisting of doped silicon, doped silicon germanium, tungsten, tungsten nitride, and aluminum nitride. 55. The method of claim 54, further comprising: after applying the first flushing gas to the insulating material, introducing a third purge gas to third purge the unchemically adsorbed material. . 55. The method of claim 54, further comprising applying the first flushing gas to the insulating material and then applying a second flushing gas comprising the second element to the insulating material to improve the property of the insulating material. The manufacturing method of a capacitor characterized by the above-mentioned. 63. The method of claim 62, further comprising: after applying the first flushing gas to the insulating material, introducing a third purge gas to third purge the unchemically adsorbed material. . 64. The method of claim 63, further comprising: after applying the second flushing gas to the insulating material, introducing a fourth purge gas to fourth purge the unchemically adsorbed material. .

Images